Recent Advances in Microenvironment Regulation for Electrocatalysis

REVIEW National Science Review
11: nwae315, 2024

https://doi.org/10.1093/nsr/nwae315
Advance access publication 19 September 2024
CHEMISTRY
Special Topic: Local Environments in Electrochemistry

Recent advances in microenvironment regulation
1 Engineering
Research Center of
for electrocatalysis
Downloaded from https://academic.oup.com/nsr/article/11/12/nwae315/7762206 by guest on 16 December 2024

Advanced Rare Earth
Materials, Zhiyuan Xu1 ,† , Xin Tan 1 ,† , Chang Chen1 ,† , Xingdong Wang2 , Rui Sui1 ,
Department of
Chemistry, Tsinghua
Zhongbin Zhuang3 , Chao Zhang4 , ∗ and Chen Chen1 , ∗
University, Beijing
100084, China;
2 Research Institute of
ABSTRACT
Petroleum Processing,
SINOPEC, Beijing
High-efficiency electrocatalysis could serve as the bridge that connects renewable energy technologies,
100083, China; 3 State hydrogen economy and carbon capture/utilization, promising a sustainable future for humankind. It is
Key Lab of therefore of paramount significance to explore feasible strategies to modulate the relevant electrocatalytic
Organic-Inorganic reactions and optimize device performances so as to promote their large-scale practical applications.
Composites, Beijing Microenvironment regulation at the catalytic interface has been demonstrated to be capable of effectively
University of Chemical enhancing the reaction rates and improving the selectivities for specific products. In this review we
Technology, Beijing summarize the latest advances in microenvironment regulation in typical electrocatalytic processes
100029, China and (including water electrolysis, hydrogen–oxygen fuel cells, and carbon dioxide reduction) and the related in
4 MOE International
situ/operando characterization techniques and theoretical simulation methods. At the end of this article, we
Joint Laboratory of
present an outlook on development trends and possible future directions.
Materials
Microstructure, Keywords: microenvironment regulation, electrical double layer, hydrogen electrocatalysis, oxygen
Institute for New electrocatalysis, CO2 reduction reaction
Energy Materials and
Low-Carbon
Technologies, School INTRODUCTION still exist quite a few obstacles on the way towards
of Materials Science their large-scale application. For instance, water elec-
The pressing issue of continuously elevating CO2
and Engineering, trolyzers and hydrogen–oxygen fuel cells are facing
Tianjin University of
concentrations in the Earth’s atmosphere ur-
the issues of sluggish kinetics of the oxygen reduc-
Technology, Tianjin gently calls for a fundamental paradigm shift in
tion reaction (ORR) and oxygen evolution reaction
300384, China energy-related technologies and the recycling of this
(OER), unsatisfactory catalyst stability, and high
greenhouse gas, and electrocatalysis powered by sus-
costs due to inclusion of noble metal components
tainable energies is expected to play a substantial role
∗ Corresponding [2,4,5]; for CO2 RR, it is still rather challenging to
in this grand picture [1]. Hydrogen economy and
authors. E-mails: achieve high selectivity for specific target high-value
electrochemical CO2 reduction reaction (CO2 RR)
[email protected]. products [6]. Therefore, it is of great significance,
have been extensively acknowledged as two promis-
edu.cn; both scientific and practical, to explore feasible
ing solutions. Green hydrogen produced via water
[email protected]. strategies to boost the related electrocatalytic
edu.cn
electrolysis, in combination with hydrogen–oxygen
reactions.
† Equally contributed
fuel cells, could potentially lead to a sustainable en-
Electrocatalytic reactions take place at the cata-
ergy infrastructure with net-zero carbon emissions
to this work. lyst/electrolyte interface, where the electrical double
[2]. On the other hand, CO2 RR could recycle CO2
layer (EDL) structure plays a crucial role in influ-
and convert it into value-added chemical feedstocks
encing reaction kinetics. Optimizing the catalytic
Received 29 April and fuels, representing an attractive alternative for
structures and regulating the microenvironment at
2024; Revised 9 July closing the carbon cycle [3]. At the current stage,
2024; Accepted 1 the interface are two effective options for promoting
water electrolyzers, hydrogen–oxygen fuel cells, and
August 2024 electrocatalytic processes [7]. The former aims to
CO2 electrolyzers have demonstrated considerable
optimize the adsorption energies and activation
prospects for commercialization. However, there
© The Author(s) 2024. Published by Oxford University Press on behalf of China Science Publishing & Media Ltd. This is an Open Access article distributed under the terms of the Creative
Commons Attribution License (https://creativecommons.org/licenses/by/4.0/), which permits unrestricted reuse, distribution, and reproduction in any medium, provided the original
work is properly cited.
Natl Sci Rev, 2024, Vol. 11, nwae315
barriers for the involved chemical species (including

reactants, intermediates, and products) at the cat-
alytically active sites in pursuit of high-performance
catalysts, which has been one of the hottest topics
in electrocatalysis during the past few decades [8].
Several review articles have already summarized
research progress in the field of electrocatalysis,
providing important guidance for the modulation of
the microenvironment of electrocatalyst structures
[9–11]. The latter, on the other hand, resorts to
tactics such as controlling the electrolyte compo-

sitions (including pH, [12,13] anions [14–16] and
cations [17,18]), altering the interfacial hydrophilic-
ity/hydrophobicity [19–21], and constructing the
organic-compound/electrode interface [22,23], and
has also demonstrated its capabilities of elevating
reaction rates, tuning reaction selectivities, and
Figure 1. Schematic illustration of microenvironment regu-
enhancing reaction stability. In addition, investigat-
lation for electrocatalysis.
ing the effect of microenvironment on the overall
catalytic process could help to unveil the underlying from the electrode/electrolyte interface could help
catalytic mechanisms, and thus shed light on the to establish a more comprehensive and in-depth
development of next-generation electrocatalytic understanding on the fundamentals of electrocatal-
materials and devices [24]. For example, it has been ysis, to explore feasible strategies for regulating the
reported that adding cyclohexanol could effectively microenvironment, and to develop advanced elec-
block the direct adsorption of Nafion onto the Pt trochemical devices with superior performances.
surface [25], and that employing chemically modi- Here in this paper, we present a brief review on
fied carbon supports with tailored porosity enabled the recent advances in microenvironment regulation
the uniform dispersion of ionomer [26]. These for typical energy-related electrochemical processes
strategies have successfully optimized the interface (such as HOR, HER, ORR, OER, CO2 RR) asso-
microenvironment of ionomers/catalysts, thereby ciated with water electrolyzers, hydrogen–fuel cells,
improving the operational performance and robust- and CO2 electrolyzers (Fig. 1). In the following
ness of fuel cell devices. In addition, modulating sections, we first give an introduction on the estab-
the cation concentrations [17], local pH [27] and lishment and development of EDL theory. Then we
local CO2 /H2 O ratio [28] at the catalytic interface overview the latest advances in the research on mi-
could enable production of multi-carbon products croenvironment regulation, with particular empha-
via CO2 RR. These pioneering works showcase the sis on the effects of pH, anions, cations and organic
importance of microenvironment regulation for pro- compounds, and on the underlying principles for
moting practical applications. On the other hand, different regulation strategies. Next we summarize
there are still some issues that need to be noted: the most recent progress in the design and fabri-
most of the research works on microenvironment cation of membrane electrodes and corresponding
were based on the three-electrode system rather than electrocatalytic systems based on microenviron-
practical devices. Similar to the challenges faced in ment regulation. An extra section is given for the in
catalyst development, a number of extraordinary situ/operando characterization techniques (such as in
results have been obtained using the rotating disk situ visualization, surface-enhanced infrared/Raman
electrode (RDE) setup, and yet they could hardly spectroscopies) and theoretical simulation methods
be reproduced in the membrane electrode assembly (such as ab initio molecular dynamics and contin-
(MEA) configuration [29]. This is probably because uum modeling). At the end of this review, we present
when the catalytic reactions are transferred from the a brief summary on the challenges currently facing
planar electrodes in the conventional three-electrode this research area, and an outlook on possible future
setup to the triple-phase interface in MEA, the dis- directions. We believe this comprehensive review of
tinct differences in their operational conditions and recent advancements in microenvironment regula-
microenvironments could lead to significant discrep- tion across a broad spectrum of electrochemical pro-
ancies [30]. Therefore, it is necessary to conduct cesses, coupled with practical insights into device-
cross validation between the three-electrode system level optimization and in situ/operando characteriza-
and MEA for the research on microenvironment tion, can help to deepen understanding and facilitate
in the future. To sum up, the approach of starting the advance in microenvironment engineering.
Page 2 of 21
Metal Organic
intermediate species. On top is the outer Helmholtz
H O C Anion
cation compounds Bulk plane (OHP) formed through the solvation of
cations. On account of the high solvation enthalpies
of cations, it is generally believed that cations are not
A-
M+
Diffuse
layer
in direct contact with the electrode. Nonetheless,
A- the electrode interface would still be affected by the
H2O
quasi-specific adsorption of cations coupling with
Cation effect CO2
H2
other surface-adsorbed species (such as *OH) [18].
OHP
The electric potential in the vicinity of the electrode
+
Anion effect M O2 interface region (including IHP and OHP) is asso-
pH effect Organic IHP ciated with the surface charge of the electrode, and
- compounds
A

OHad
follows a quasi-linear distribution. Farther out from
OHP is the diffuse layer, where the distribution of
cations/anions in this layer is still controlled par-
Figure 2. Schematic illustration of the EDL structure and the typical effects of microen- tially by the electric potential, which varies almost
vironment in electrocatalysis. The off-white, blue, red and silver-white spheres repre- exponentially with respect to the distance from the
sent the H, O, C and the metal (electrode material) atoms, respectively. The golden, pink electrode.
and green spheres represent the cations, the anions and organic species, respectively. The classic EDL model described above is
the foundation for understanding the interfacial
microenvironment, but it still has significant limita-
ELECTRODE–ELECTROLYTE INTERFACES:
tions. For example, the structure of interfacial water
ELECTRICAL DOUBLE LAYER (EDL) molecules, the degree of ion hydration and the posi-
STRUCTURE tion of cations at the interface are still rather vague.
The microenvironment of electrode–electrolyte in- Recently, Bonn et al. discussed the formation of EDL
terface (EEI) could have a significant impact on the on different types of charged interfaces and its im-
thermodynamics, kinetics, reaction pathways and pact on the interfacial water structure, emphasizing
thus product selectivity. On the other hand, the elec- the limitations of the classic mean-field description
trocatalytic reactions themselves could also alter the of EDL in depicting the real systems involving
interfacial microenvironment, such as the change of charged surfaces, water, and ions at the molecular
electric field, dynamic adsorption/desorption of re- level [33]. Taking into consideration more micro-
actants, intermediates and products at the electrode scopic details (such as interfacial water properties
surface; in particular, when the reaction involves the and specific ion interactions) as well as developing
generation/consumption of H+ /OH− , the local pH density functional theory (DFT)-based molecular
at the electrode surface could deviate substantially dynamics simulations has positive implications for
from the bulk electrolyte. Understanding the struc- understanding interfacial water structures. In situ
ture of EEI at the atomic/molecular scale is a ma- spectroscopies are crucial for probing the micro-
jor challenge owing to the dynamic and complex in- scopic details of interfacial water structures. Tian
teractions between electrocatalytic reactions and the et al. observed the interfacial water structure on
interfacial environment [31]. Electrical double layer electrified Au single-crystal electrode surfaces via
(EDL) theory lays the foundation of theoretical re- in situ Raman spectroscopy [34]. They discovered
search on the EEI, and during nearly two centuries that the O–H stretching vibrational mode of interfa-
of development, the EDL model has undergone sig- cial water underwent two transitions, accompanied
nificant modifications, currently leading to the well- by two changes in the number of hydrogen bonds
known Gouy–Chapman–Stern (GCS) model. After when sweeping to negative potentials. In combi-
further incorporating the solvated ions and adsorp- nation with ab initio molecular dynamics (AIMD)
tion [32], the schematic illustration of the classic simulations, it was demonstrated that these transi-
EDL model is shown in Fig. 2, which has been widely tions are due to the evolution of interfacial water
applied in the field of electrocatalysis. molecules from the ‘parallel’ configuration to ‘one-
The EDL extends from the electrode towards H-down’ and then to ‘two-H-down’ configurations
the electrolyte, with the layer nearest to the elec- with the variation in interfacial electric potential.
trode surface composed of solvent molecule dipoles Furthermore, the determination of actual param-
arranged in an ordered manner, forming the inner eters for the EDL, such as the potential drop (PD)
Helmholtz plane (IHP). Certain specific adsorbed and the potential of zero charge (PZC), is crucial
anions may lose a portion of their solvation shells for validating models and making necessary adjust-
and directly adhere to the electrode surface, which ments. Crumlin et al. directly probed the electric
might compete with the adsorption of the reactant/ potential distribution in the EDL at the interface
Page 3 of 21
between electrified gold polycrystalline electrode energy (HBE) of Pt based on DFT calculations [40],
and liquid electrolyte under polarization conditions and thus the pH effect on Epeak seems to suggest that
via ambient-pressure X-ray photoelectron spec- HBE is the sole descriptor of the HER/HOR activ-
troscopy [35]. This not only discerned the shape of ities on Pt. As is shown in Fig. 3a, a universal de-
the EDL profile, but also helped to further under- pendence between pH and the measured HBE has
stand the influence of electrolyte concentration and also been found on Pt-group metals other than Pt
applied potential on the EDL structure. Koper et al. (including Ir, Pd and Rh) [12]. This provides an ex-
determined the PZC as 0.3 V vs. normal hydrogen planation for the suppressed HER/HOR activities in
electrode (NHE) on Pt(111) by measuring the alkaline solutions, that the OH species would lead to
Gouy–Chapman capacitance minimum at the inter- the overbinding of Had owing to the higher HBE.
face between Pt(111) and aqueous perchlorate elec- However, it does not seem sufficiently rigorous

trolyte [36]. Owing to the stronger ‘effective screen- to directly associate the measured Hupd peak with
ing’ than predicted by purely electrostatic mean-field HBE. The similar pH dependence of Hupd peaks on
Poisson–Boltzmann theory, the actual diffuse dou- different metals suggests that this is not related to the
ble layer structure of Pt(111) deviates more from the innate properties of electrodes, but rather dominated
theoretical values. Recently, Suntivich et al. reported by the interfacial microenvironment. Therefore, the
a novel optical method for determining the PZC, apparent HBE (HBEapp ), which takes the Gibbs
which directly probes the electric field at the elec- free energy of interfacial water adsorption (WBE)
trochemical interface through field-induced second- into consideration, was proposed as a more proper
harmonic generation (SHG) effects [37]. Using this descriptor for hydrogen electrocatalysis. Koper
method, the team determined the PZC value of the et al. suggested that the non-Nernstian pH shift of
polycrystalline Pt/water interface to be 231 ± 76 mV Hupd peak is due to the fact that the co-adsorbed
vs. standard hydrogen electrode (SHE). This phase- alkali metal cations along the step weaken the OH
sensitive SHG method, which does not require adsorption at the step sites on Pt(553) [41]. Xu
probe molecules, also provides a promising ap- and Yan et al. combined cyclic voltammetry and
proach to determining the PZC of other metal elec- surface-enhanced infrared absorption spectroscopy
trodes under different electrochemical conditions. (SEIRAS), and proposed that the pH-dependent
With the advance of in situ testing techniques shift of the Hupd peak on Pt may be attributed to the
and theoretical simulation methods, new impetus altered structure of interfacial water by the electrode
has been added to the development of EDL models. potential, rather than by cations [42]. Shao et al.
Understanding of the EDL structure at the atomic tracked the changes in HBE and WBE on Pt thin
scale is of important significance for better utilizing film under different pH conditions, and claimed
the microenvironment to regulate electrocatalytic that the experimentally determined HBE is actually
performances. the combined result of electric field, Had coverage,
Pt–water and Had –water interactions [43]. In elec-
trolytes with higher pH values, the lowered WBE
MICROENVIRONMENTAL REGULATION leads to an increased distance between the Pt surface
FOR HYDROGEN ELECTROCATALYSIS and the interfacial water layer, thus hindering charge
Electrochemical hydrogen evolution and oxidation transfer and resulting in slower reaction kinetics
reactions (HER/HOR) are not only the foundation (Fig. 3b). The results on the kinetic isotope effect
of a sustainable hydrogen economy, but also the typ- (KIE) of HER/HOR on single-crystalline Pt(111)
ical processes for electrocatalytic reactions, serving and Pt(110) also support the significant influence
as models for studying electrode kinetics and the of pH on water structure at the interface [44]. No
fundamental principles of electrocatalysis. The non- significant KIE for hydrogen reactions was observed
Nernstian pH dependency of the HER/HOR kinet- in acidic media, but a KIE as high as 3.4 was ob-
ics leads to notably lower reaction rates in alkaline served for HOR on Pt(111) in alkaline solution,
environments than under acidic conditions, and the indicating that interfacial water plays a crucial role in
origins are still unclear [38]. Yan et al. assessed the promoting proton adsorption and overall hydrogen
HER/HOR activities of Pt catalysts and the oxida- reaction kinetics in alkaline media (Fig. 3c). The
tion peak for the underpotentially deposited hydro- interfacial electric field is also considered an intrinsic
gen (Hupd ) in different buffer solutions over a wide origin of the pH effect on hydrogen electrocatalysis.
pH range (0–13). It was found that as the pH in- Surendranath et al. quantified the interfacial electric
creases, the HER/HOR activities gradually decrease field strength on Pt as a function of pH by using a
whereas the Hupd peak potential (Epeak ) shifts anod- non-Faradaic reaction probe and tracking the pH
ically [39]. Nørskov et al. established a direct cor- sensitivity of H2 /H+ catalysis [45]. The results
relation between Epeak and the hydrogen binding show that with each unit increment in pH, the
Page 4 of 21
b 3540 c 4.0
a Pt/C
pH=1.1 Pt (111) in acid
Ir/C pH=3.1 3.5 Pt (111) in base
10 Pd/C -1 -1 pH=7.0 3.0
Pt (110) in acid
-322 cm V
Wavenumber (cm )
Rh/C pH=10.9
-1
i0 (mA/cm2 Metal)
3520 2.5
pH=12.9
KIE (kH/kD)
1 -1
-252 cm V
-1
2.0
-1 -1 -1 -1
-52 cm V -108 cm V 1.5
3500
0.1 1.0
-20 cm-1 V-1 0.5 HER/DER HOR in H2O/D2O
0.01 3480 0.0
0.0 0.1 0.2 0.3 0.4 -0.06 -0.03 0.00 0.03 0.06 -0.4 -0.3 -0.2 -0.1 0.0 0.1 0.2 0.3 0.4
Epeak, iR-free vs RHE (V) Potential (V vs RHE) Potential vs RHE (V)
RE CE
1.00 0.1 M LiOH –
d e f H
Normalized conductance (a.u.)

– + ‡
0.1 M NaOH –
∆G +
–
0.1 M KOH –
H
Electrolyte +

–
0.95 H + Solvated
ETS –
ions
–
Electrode
+
– H H
V – – +
–
OH +
H
D 0.90 – H2O
– H
– +
+ –
–
S – H +
0.85 HER Hupd EDL OHdes +
–
PtNWs (WE) – H
Alkaline interface
0 0.3 0.6 0.9
Si/SiO2/PMMA Potential (V versus RHE)
Helmholtz H-bond Diffuse layer
4 layer gap
g h i
2
O
Current density (mA/cm2)
0
H H H c
-2 b
O N
-4
a
4
-6 5
3
Pt(111) H 2
-8 Pt(111)+caffeine
1
-10
-0.4 -0.2 0 0.2 0.4 0.6 0.8 1.0 Pt
H O N C Pt
E vs. RHE (V)
Figure 3. Microenvironmental regulation for hydrogen electrocatalysis. (a) The exchange current density of HOR/HER on Pt/C,
Ir/C, Pd/C and Rh/C as a function of Epeak . Reproduced with permission from Ref. [12]. Copyright 2016 American Association
for the Advancement of Science. (b) The O–H stretching wavenumber of interfacial water as a function of potential. Repro-
duced with permission from Ref. [43]. Copyright 2020 American Chemical Society. (c) KIE of HER/HOR on Pt(111) and Pt(110)
in HClO4 /DClO4 and KOH/KOD. Reproduced with permission from Ref. [44]. Copyright 2020 American Chemical Society.
(d) Schematic of operando ETS measurements and (e) the normalized ETS conductance of the PtNW device in 0.1 M MOH
(M = Li, Na and K) electrolyte solutions as a function of potential. Reproduced with permission from Ref. [47]. Copyright
2022 Nature Publishing Group. (f) Schematic diagram of the proton transfer from diffuse layer to Helmholtz layer across
the H-bond gap in the alkaline EDL. Reproduced with permission from Ref. [48]. Copyright 2022 Nature Publishing Group.
(g) HER/HOR polarization curves of Pt(111) and Pt(111) + caffeine in 0.1 M KOH. Reproduced with permission from Ref. [49].
Copyright 2020 American Chemical Society. (h) Atomic configuration of an equilibrated H2 O–Me-N1 C2 –Pt(100) interface. The
grey, brown, blue, red and white spheres represent Pt, C, N, O and H atoms, respectively. (i) Schematic illustration of an
interfacial water dimer on Pt(100) interface with Me-N1 C2 . (h, i) Reproduced with permission from Ref. [22]. Copyright 2023
Nature Publishing Group.
electrostatic potential at the Pt surface increases et al. investigated the cation effect on hydrogen elec-
significantly, indicating a distinct difference in electrocatalysis in Pt, Ni and PtNi systems, and found
tric field strengths between acidic and alkaline condi- that Li+ does not affect the HER on Pt, but signifi-
tions. The pronounced difference in interfacial elec- cantly improves the HER on Ni and PtNi [46]. This
tric field strength at RHE would influence the rate of implies that Li+ could not only facilitate the OHad
solvent molecule reorganization, thereby contribut- removal by forming a OHad –(H2 O)x –Li+ structure,
ing to the pH dependence of HER/HOR kinetics. but also hinders HOR by weakening the adsorp-
Different alkali metal cations (AM+ ) have been tion strength of OHad . It was also observed that in-
found to significantly affect the HER in alkaline so- creasing the Li+ concentration only promotes HER,
lutions, but the cation effect is rather insignificant whereas changing the identity of AM+ affects both
in acidic media. This may be due to the presence of HER/HOR on Pt. These experimental results col-
a large amount of OH species in alkaline solutions, lectively indicate that the cation effect could alter
leading to a more complex interfacial microenviron- the rate of hydrogen electrocatalytic reactions by in-
ment, with the cations believed to influence the influencing the OHad on Pt. Duan et al. investigated
terfacial solvent layer through these OHad species. Jia the cation effects of HER on Pt via electrochemical
Page 5 of 21
impedance spectroscopy and electrical transport ing alkyl chain lengths, consistent with the trend of
spectroscopy (Fig. 3d, e) [47]. In situ experimental corresponding HOR/HER exchange current densi-
evidence on surface adsorbates and charge-transfer ties. This indicates that theophylline derivatives can
resistance (Rct ) at the electrode/electrolyte interface enhance the HOR/HER activity by promoting inter-
indicates that the high polarity of OHad allows it to face water reorganization through increased weakly
act as electrically favored proton acceptors and ge- hydrogen-bonded water. In addition to caffeine-like
ometrically favored proton donors, thereby acceler- reagents, Jia et al. found that N-methylimidazoles
ating the kinetics of the Volmer step. Cations with at the Pt–water interface can also accelerate the hy-
smaller atomic numbers (such as Li+ ) could min- drogen reaction [22]. The more negatively charged
imize the interference with OHad on Pt, resulting pyridinic nitrogen (N3 ) in N-methylimidazole
in a higher OHad coverage and thus a better HER forms a strong N3 ···H2 O bond with interfacial H2 O,

activity than Na+ and K+ . These works imply that keeping the second layer of water molecules close
the cation effect is often closely related to the OHad . to the Pt surface to facilitate OH− diffusion at the
Although the bifunctional mechanism of hydrogen interface, thereby accelerating the Volmer step on Pt
electrocatalysis in alkaline is still a topic of much de- (Fig. 3h, i). This organic interface strategy has been
bate, it is almost unanimously agreed that OHad has shown to be quite feasible for practical devices, with
a significant impact on the kinetics of HER/HOR. a 40% performance enhancement achieved in an
Chen et al. conducted in situ surface-enhanced in- anion exchange membrane electrolyzer by adding
frared absorption spectroscopy and AIMD simula- 1,2-dimethylimidazole to the Pt cathode.
tions, and argued that the main origin for the sup- As manifested in the non-Nernstian pH effect, the
pressed activity of HER/HOR on Pt in alkaline elec- interface microenvironment could have profound in-
trolytes is the presence of water gaps in the EDL and fluences on the HER/HOR kinetics. Current re-
the weakened connectivity of hydrogen bond net- search suggests that the underlying mechanisms may
works (Fig. 3f) [48]. Furthermore, OHad could sig- involve alteration in the EDL structure (such as the
nificantly improve the connectivity of the hydrogen interfacial water layer) and the electric field. Con-
bond network, which explains the fact that the hy- sidering the scientific and practical importance of
drogen reaction activity of PtRu is higher than that hydrogen electrocatalytic reactions, delving into the
of Pt in alkaline media. regulation mechanisms of interface effects can not
In addition to electrolytes, some recent stud- only aid in optimizing the design of hydrogen-related
ies have shown that organic additives adsorbed energy devices, but also help in understanding the in-
on electrode surfaces can fine-tune the interfacial trinsic connections between interfacial structure and
microenvironment and improve the kinetics of alka- catalytic performance.
line hydrogen reactions. Snyder et al. used caffeine
adsorbed on Pt surface as a ‘double-layer dopant’
and enhanced the rates of HER/HOR on Pt by
more than 5-fold (Fig. 3g) [49]. Fourier Trans- MICROENVIRONMENTAL REGULATION
form Infrared Spectrometer (FTIR) spectroscopy FOR OXYGEN ELECTROCATALYSIS
provides evidence that the caffeine molecules are Hydrogen and oxygen electrocatalysis form
adsorbed on the Pt surface and can be stabilized and the foundation of water electrolyzers and
regenerated through electrochemical deposition hydrogen−oxygen fuel cells. Compared with
during load/potential cycling. The hydrophobic and hydrogen-related reactions, OER/ORR have much
oxophobic nature of caffeine can inhibit electrode slower kinetics, and the high overpotential for the
corrosion and thus enhance catalytic stability. In ad- oxygen reaction side is the primary origin of device
dition, its slight polarity weakens the OHad , leading polarization. Therefore, optimizing the efficiency
the team to speculate that it may affect the hydrogen of oxygen electrocatalytic reactions is crucial for
bonding network and the mobility of surrounding further improving device performance.
water molecules, thus leading to an elevated rate Currently, it has been found that properly de-
of hydrogen reactions. Inspired by the intriguing signed electrolyte compositions can accelerate
results regarding caffeine, Xu et al. used theophylline OER, known as the electrolyte effect. Zhang et al.
derivatives with partial structural similarities to showcased that the addition of selenites (SeO3 2− )
caffeine and investigated the effect of different or sulfate (SO4 2− ) in the electrolyte could signifi-
molecular fragments of caffeine on the HOR/HER cantly improve the OER performance of transition
activity on Pt in alkaline media [50]. In situ Ra- metal hydroxides such as Ni(OH)2 , Cu(OH)2 and
man spectroscopy provided the intensity of weakly Co(OH)2 (Fig. 4a) [14]. In situ Raman spectroscopy
hydrogen-bonded water on Pt decorated with and theoretical calculations indicate that these
7-alkyl substituted theophylline derivatives of vary- surface-adsorbed chalcogenates can significantly
Page 6 of 21
a 300 Pure KOH b 0.4 M KBi + 1.5 M KF c 12

NiIFe-[TA]-Catalyst f 0.02 M HCIO4
Current density (mA/cm2)

40 1.5 M KF 10 LiOH 0.05 M HCIO4
0.01 M SeO32- 0.4 M KBi NaOH 0.1 M HCIO4
0.05 M SeO32- 0.5 M NaClO4 8 KOH 0.1 0.2 M HCIO4
j (mA cm-2)
200
j (mA cm-2)
j (kA g-1)
CsOH
0.1 M SeO32- 6
0.5 M SeO32- 20
100 4 0
2
0 *H DL *OH *O
0 -0.1
0
1.2 1.4 1.6 1.8 1.0 1.1 1.2 1.3 1.4 1.5 1.1 1.2 1.3 1.4 1.5 1.6 1.7 1.8 0 0.2 0.4 0.6 0.8 1.0 1.2
Potential (V vs. SHE) E-iR (V vs. RHE) E (V) (versus RHE)
E / V vs. RHE
g 5 HClO4
d e
jk at 0.9 V (mA cm–2)

MSA
Elongated
Li+ Co--O
Aqueous solution 4
76 pm d2
Li--O
3
Proton gate 2
(protic ionic liquid)

Elongated
1
Elongated Co-O bonds
Na+ Co--O
d3
102 pm
Na--O 0
ORR catalysts 0.02 0.05 0.10 0.20
(Pt, Au) Electrolyte concentration (mol l–1)
–1
K+ h [NC] (mg ml )
Elongated
Co--O 0
Current density (mA cm–2)

138 pm d4 25.0
Tuning the proton affinity Protic cations 15 37.5
K--O 54.5
81.8
H
122.7 3.9×
N
H N N H
N
H
N
10
N N N N
N N N N N
H H
Elongated
Cs+ Co--O + + + + + + +
5
d5 [C4C1im] [TMPim] [MTBD] [DBU] [DEMA] [TEMEDA] [C4Him]
167 pm 23.3 21.3 15.0 13.5 10.3 8.9 7.1 –1
Cs--O 5 mV s
0
Li
+
Na
+ +
K Cs
+
CoO6 1.2 1.1 1.0 0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2
High pKa Low pKa
Potential (V versus RHE)
Figure 4. Microenvironmental regulation for oxygen electrocatalysis. (a) OER polarization curves of Ni(OH)2 in 1 M KOH with different concentrations of
SeO3 2− . Reproduced with permission from Ref. [14]. Copyright 2020 John Wiley & Sons, Inc. (b) OER polarization curves of Co(OH)2 in neutral electrolytes
with different concentrations of borate and fluoride anions. Reproduced with permission from Ref. [16]. Copyright 2022 Elsevier Inc. (c) OER polarization
curves of the NiFe-based catalysts recorded in alkaline electrolytes with different alkali metal cations. Reproduced with permission from Ref. [52].
Copyright 2022 John Wiley & Sons, Inc. (d) The schematic illustration of alkali cation intercalation and elongated Co–O bonds in CoOOH during the
OER. Reproduced with permission from Ref. [53]. Copyright 2023 John Wiley & Sons, Inc. (e) The schematic illustration of tuning local proton activity
for the ORR via protic cations of ionic liquids with different pKa . Reproduced with permission from Ref. [23]. Copyright 2021 Nature Publishing Group.
(f) Cyclic voltammograms of Pt(111) in HClO4 solutions of different concentrations. (g) Summary of specific activities at 0.9 V (vs. RHE) of Pt(111) in HClO4
and methanesulfonic acid (MSA) of different concentrations. (f, g) Reproduced with permission from Ref. [55]. Copyright 2022 Nature Publishing Group.
(h) ORR polarization curves of Pt/C in phosphate-buffered water (0.5 M KPi ) solutions with different concentrations of zeolitic nanocrystals. Reproduced
with permission from Ref. [57]. Copyright 2023 Nature Publishing Group.
lower the Gibbs free energy of the intermediate fectively disrupt the polymer hydrogen-bonding
of OER (*OOH), thus promoting OER activity. network in water, sustaining a larger current.
Similarly, surface-adsorbed carboxylate ligands Similar to anions, alkali metal cations have also
(CLs) on bi/trimetallic layered double hydroxides been found to significantly affect the OER perfor-
(LDHs)/MOFs materials also exhibit a universal mance of electrode materials, although the intrinsic
boosting effect for OER [15]. In situ spectroscopic role of the cations is still rather vague thus far.
evidence shows that the negatively charged CLs Koper et al. found that regardless of the presence
adsorbed on NiFeMn MOFs can act as mediators of Fe impurities in alkaline electrolytes, the OER
for proton transfer, accelerating and facilitating the activities of NiOOH always show an intrinsic cation
adsorption, activation, and dissociation of OH− to dependency [51]. In situ surface-enhanced Raman
promote the OER. Besides these individual anions, scattering (SERS) results suggest that the cation
the combinations of different anions have been effect is related to the interaction with the superoxo
found to exhibit interesting synergistic effects. Gong OER intermediate (NiOO− ). Cations with larger
et al. discovered that the combination of borate and atomic numbers (such as Cs+ ) are supposed to
fluoride anions can have an intriguing synergistic be capable of better stabilizing the NiOO− −M+
effect for OER under neutral conditions, with the species, thereby promoting O2 evolution. Advanced
water oxidation current almost an order of magni- in situ characterization technologies provide new
tude higher than that for individual anions (Fig. 4b) opportunities to probe the cations effect. Fischer
[16]. This synergy was considered to be due to et al. further demonstrated the correlation between
the hierarchical arrangement of these two anions the cations effect on the NiFe(OOH)-based elec-
at the interface, where borate anions in the inner trocatalysts and the potential of maximum entropy
Helmholtz layer promote proton-coupled electron (PME) using the laser-induced current transient
transfer (PCET) steps, lowering the onset potential, (LICT) technique (Fig. 4c) [52]. The results sug-
while fluoride anions located further outside ef- gest that Cs+ cations may accelerate the kinetics of
Page 7 of 21
the OER by altering the structure of the interfacial and have little impact on ORR. Yet recently, Koper
water layer. Combining the results from operando et al. unearthed an unexpected effect of non-
powder X-ray diffraction (PXRD), high-resolution specifically adsorbed anions (ClO4 − ) on the ORR
transmission electron microscopy (HRTEM) and kinetics on Pt(111) (Fig. 4f, g) [55]. The role of
X-ray absorption spectroscopy (XAS), Luo et al. the non-specifically adsorbed anions was explained
demonstrated that cations enter the layers of the by introducing the *O ↔ *OH transition as a new
Co-OOH catalyst through intercalation, leading kinetic descriptor for ORR on Pt(111). This de-
to an increase in interlayer spacing (Fig. 4d) [53]. scriptor also successfully elucidated the impact of
Cations with larger atomic numbers could facilitate perfluorosulfonic acid (PFSA) ionomer and cations
the elongation of Co–O bonds, promoting the in alkaline media on the ORR activity on Pt(111). In
formation of high-valence OER-active *O–Co(IV) addition, the mechanism for the significantly lower

species. Co-OOH–Cs exhibits the lowest energy activity of M-N-C materials in acid (than in alkaline
barrier for the rate-determining step (RDS), which media) has also attracted attention. Chen et al. used
explains the enhanced OER activity. FeCo-N6-C DAC as a model system and combined
Similarly, the cations effects for ORR are also AIMD simulation with in situ ATR-SEIRAS to study
quite significant. Marković et al. proposed that hy- the pH effect on its ORR activity [56]. The results
drated alkali metal cations M+ (H2 O)x form OHad – indicate that the difference in activity stems from
M+ (H2 O)x clusters at the interface via non-covalent the distinct EDL structures in acidic and alkaline
interactions with OHad [18]. Cations with larger environments, where the orientation of interfacial
atomic numbers have lower hydration energies, lead- water on electrode surfaces varies, impacting the for-
ing to the higher ORR activities on Pt(111). More- mation of hydrogen bonds between the oxygenated
over, organic cations have been found capable of ef- intermediates and the interfacial water molecules,
fectively promoting the ORR on Pt. Nakamura et al. eventually leading to differences in ORR kinetics.
studied the effect of tetraalkylammonium (TAA) In addition to the above ion effects, introducing
cations with different alkyl chain lengths on the ORR microporous nanocrystals with hydrophobic in-
on Pt(111) [54]. The high hydrophobicity of TAA ternal surfaces and hydrophilic external surfaces
cations with longer alkyl chains significantly alters into the electrolyte generates ‘microporous water’,
the hydration structure of TAA. Among them, THA which exhibits an O2 -carrying capacity two orders
with the longest alkyl chain (n = 6) boosted the per- of magnitude higher than pure water [57]. This
formance of Pt(111) by 8-fold. The high hydropho- enhancement in O2 supply at the electrode interface
bicity of THA and its hydration shell weakens the mitigates mass transport limitations (Fig. 4h), and
binding of surrounding OHad and H2 Oad through thus facilitates the direct measurement of intrinsic
weaker interactions, lowering the coverage of OHad ORR activity on Pt. This optimized mass transport
and disrupting the stable hydrogen-bonding net- strategy may offer a straightforward and effective
work, thus facilitating the entry of oxygen molecules intermediate testing method to bridge the gap
onto the Pt(111) surface. Shao-Horn et al. recently between RDE and MEA measurement.
reported the acceleration of the ORR kinetics of Au
and Pt using protic cations of ionic liquids (Fig. 4e),
where the ORR on Au mainly proceeds via the 2e− MICROENVIRONMENTAL REGULATION
pathway, whereas on Pt it follows the 4e− pathway FOR CO2 REDUCTION REACTION
[23]. The ORR specific kinetic currents exhibit a Electrochemical CO2 RR powered by renewable
volcano-shaped relationship vs. the pKa of protic energies is a promising route to transforming CO2
cations in the ionic liquids, with the maximum en- into value-added products and achieving sustain-
hancement obtained when the pKa values of the pro- able carbon recycling. The microenvironment of
tic cations and the reaction intermediate in the RDS electrocatalysis has a significant impact on CO2 RR
are similar. The optimal pKa for Pt is around 15, close activity and selectivity. In comparison to HER and
to the pKa value of H2 O, whereas the optimal pKa for ORR, most CO2 RR cases occur in a more negative
Au is around 11, close to the pKa value of H2 O2 . In potential range, where the cations tend to migrate to
situ attenuated total reflection surface-enhanced in- the cathode under the driving force of the electric
frared absorption spectroscopy (ATR-SEIRAS) and field. These cations, serving as crucial components
kinetic simulation results indicate a strong hydrogen at the reaction interface, play a significant role in the
bond interaction between the protic cations and the CO2 RR process. It has been noted in the majority
ORR intermediate, leading to faster proton tunnel- of studies that the influence of alkali metal cations
ing kinetics and accelerated oxygen catalysis. on CO2 RR activity follows the order of Cs+ > K+
Earlier research suggested that the non- > Na+ > Li+ [58,59]. Although this order is con-
specifically adsorbed anions act as spectator species sistent across various research works, the intrinsic
Page 8 of 21

Figure 5. Microenvironmental regulation for CO2 reduction reaction. (a) Illustration of the origin of cation effects in field-
driven electrocatalysis. Reproduced with permission from Ref. [61]. Copyright 2019 the Royal Society of Chemistry. (b) The
schematic illustration of the distribution of pH and CO2 concentration in the boundary layer, and FE for CO increases and
for H2 decreases with increasing cation size due to a decrease in polarization. Reproduced with permission from Ref. [58].
Copyright 2016 American Chemical Society. (c) The recorded anodic scans performed to oxidize any CO produced in argon
and CO2 atmosphere. (d) Average CO2 adsorption Gibbs free energy at U = 0 V vs. standard hydrogen electrode (SHE) in the
absence (grey) or presence (light to dark brown) of an alkali cation, with CO2 and the environment (Au–H2 O or Au–H2 O–M+ )
as the energy references. (e) α CO2 and CO2 Bader charge, qCO2 , are shown in red and black, respectively. (c–e) Reproduced
with permission from Ref. [64]. Copyright 2021 Nature Publishing Group. (f) Plotting the selectivity toward formic acid against
the contact angle yields a marked relationship, with modifiers 2 and 4 as outliers at 65° and 97°, respectively. Reproduced
with permission from Ref. [71]. Copyright 2019 American Chemical Society.
mechanism of the cation effect remains controver- through non-covalent interactions under CO2 RR
sial. Hori et al. proposed that cations could alter the conditions, thus generating a high interfacial electric
OHP potential through specific adsorption, which field. Weakly hydrated cations, with their smaller
in turn influences the concentration of H+ on the hydrated ionic radii, exhibit the least repulsion near
electrode surface, leading to different product selec- the electrode. The resulting high concentration of
tivities [60]. On the other hand, Chan et al. refuted cations leads to a higher surface charge density and a
the possibility of cations undergoing specific ad- stronger interfacial electric field. Such modifications
sorption (Fig. 5a) [61]; instead they suggested that on the potential across the electron transfer plane
cations would accumulate on the electrode surface could affect the apparent activation energy of the
Page 9 of 21
entire reaction, thereby influencing the adsorption on CO2 RR [65]. They found that H2 PO4 − , having
and activation processes of CO2 . a strong buffering capacity, could easily neutralize
Distinct from the local electric field effect, Bell OH− near the copper electrode surface, maintaining
et al. proposed another theory, suggesting that a lower local pH, which correlates with high selectiv-
cations could modulate the process by buffering ity for H2 and CH4 , while suppressing the formation
the local pH (Fig. 5b) [58]. Due to electrolyte of C2 H4 . In contrast, ClO4 − , which lacks the buffer-
polarization during the CO2 RR process, the local ing ability, led to a higher local pH at the copper elec-
pH at the electrode surface tends to increase, and trode surface and enhanced the selectivity for C2 H4 .
a large amount of OH− would react with CO2 to Cuenya et al. explored the influence of different
form (bi)carbonate, thus lowering the accessibility halide anions on the restructuring process of metallic
of CO2 . At the negatively charged cathode surface, Cu surfaces [66]. Their findings indicated that dif-

the hydration shell of cations with larger atomic ferent halide ions induce varying degrees of surface
numbers experiences a stronger electrostatic field, roughness. Compared with the original copper cat-
thereby lowering its pKa of hydrolysis. This low- alyst, the halide-ion–induced restructured catalysts
ered pKa enables the hydrated cations to act as a exhibited improved selectivities for C2+ products.
buffering agent, suppressing the rise of local pH near The pH effect has been indirectly demonstrated
the cathode. This leads to an increase in the local through the effects of alkali metal cations and an-
concentration of dissolved CO2 , thereby facilitat- ions, significantly influencing reaction rate and prod-
ing the CO2 RR process. Zhang et al. detected the uct selectivity [58]. In CO2 RR, the local pH near
changes in local pH during the CO2 RR process on the electrode surface is typically higher than the pH
Au [62]. They found that cations with larger atomic of the bulk electrolyte, owing to the consumption of
numbers have a stronger buffering effect, with the protons and the subsequent production of OH− dur-
interfacial pH values following the order of Li+ > ing surface reactions. Thus, the impact of local pH
Na+ > K+ > Cs+ , which is in good agreement with on CO2 RR is more pronounced than that of bulk
Bell’s results. Nørskov et al. suggested that the high pH. For instance, Koper et al. discovered that as the
local electric field produced by solvated cations can CO2 RR proceeds, the local pH increases, which pro-
stabilize adsorbed intermediates with large dipole motes the HER on gold electrodes [67]. Controlling
moments, thereby influencing the CO2 RR process the local pH through mass transport conditions can
[63]. According to the GCS model, the strength of regulate the rate of competing HER, thereby facili-
the electric field within the EDL under a given PZC tating the CO2 RR process on gold electrodes. In ad-
is influenced by the size of the hydrated cations in dition, CO2 as a reactant itself also acts as a buffering
the electrolyte. Cations with larger atomic num- agent by reacting with OH− at the electrode surface
bers would experience stronger driving forces and to form (bi)carbonates, thus significantly suppress-
accumulate near the electrode surface, generating ing the rise in local pH during the CO2 RR process.
a stronger interfacial electric field, which enhances Therefore, the pH effect of CO2 RR can be better ob-
the adsorption stability of some important CO2 RR served in CORR with similar reaction pathways and
intermediates. Therefore, a higher CO2 RR activity RDS. For instance, the selectivity for acetate prod-
on copper was observed in the presence of cations ucts in CORR can be significantly improved under
with larger atomic numbers, which is attributed conditions of high alkalinity. This may be due to
to their higher concentration in the OHP [59]. the higher local pH facilitating the reaction of OH−
Koper et al. further refined this model and discov- with certain intermediates to produce acetate [24].
ered that CO2 RR does not occur in the absence of To sum up, understanding the impact of local pH is
metal cations on gold, copper and silver electrodes of increasing importance for distinguishing between
(Fig. 5c) [64]. Only models considering the elec- product selectivities.
trostatic interaction between metal cations and key Strongly alkaline microenvironments are gener-
intermediates can explain this observation. Through ally believed to inhibit the HER and promote the for-
AIMD, the team further confirmed the stabilizing mation rate of C2+ products on Cu electrodes, but
effect of partially desolvated metal cations on CO2 this inevitably leads to a crossover between pH and
adsorption, activation, and the formation of CO2 − cation effects. Sargent et al. suggested that OH− on
intermediates (Fig. 5d, e). or near the copper surface can effectively lower the
The anion effects differ from those for cations, activation energy barriers for CO2 RR and CO–CO
with most studies focusing on adjusting the local pH coupling [68]. Experimental results showed that the
(through distinct buffering capacities) and inducing onset of ethylene evolution at −0.165 V vs. RHE in
catalyst restructuring. For instance, Hori et al. inves- 10 M KOH occurs almost simultaneously with the
tigated the impact of anions with different buffer- production of CO. This study proposed a plausible
ing capacities (pKa : H2 PO4 − < HCO3 − < ClO4 − ) strategy to enhance the formation of C2+ products
Page 10 of 21
by increasing the pH of the electrolyte. However, this CO2 to H2 O. Cation-exchange ionomers (CEIs), on
hypothesis contradicts the current understanding of the other hand, raise the local pH by capturing the
the mechanisms involved in the formation of C2+ OH− produced during the CO2 RR and blocking
products. Recent research indicated that the RDS for the transport of buffering carbonate species into the
C2+ product formation involves the dimerization of catalyst microenvironment (via Donnan exclusion).
two adsorbed CO molecules through the Langmuir– In combination with pulsed electrolysis, the local
Hinshelwood process, which does not involve pro- ratio of CO2 /H2 O and pH were further increased on
ton transfer [69,70]. Thus, the formation rate of C2+ the ionomer-layer–modified Cu electrode, thereby
products theoretically should not depend so strongly improving the selectivity for C2+ products. Toma
on the pH of the electrolyte. Lu et al. discovered that et al. employed a range of polymeric and molec-
at the same SHE potential, the concentration of Na+ ular modifiers with different hydrophilicity and

has a greater promoting effect on the formation rate hydrophobicity to adjust the selectivity of CO2 RR
of C2+ products in CORR than does the concen- on Cu surfaces [71]. Their research revealed that
tration of OH− [69]. This finding suggests that in protic species could enhance the selectivity for
strongly alkaline electrolytes, the primary factor en- H2 , hydrophilic additives could facilitate the for-
hancing the C2+ product formation rate could be the mation of formic acid, and cationic hydrophobes
high concentration of cations, rather than OH− . would improve the selectivity for CO (Fig. 5f).
In addition to altering the composition of elec- The molecular dynamics simulations indicated that
trolytes to regulate cations, anions and pH, recent hydrophilic and hydrophobic modifiers would influ-
studies have shown that the modulation of reactant ence the formation of surface hydrides. Specifically,
composition, catalyst surface functionalization (in- surface hydrides are more stable in the presence of
cluding modifications with organic molecules and hydrophobic species compared with hydrophilic
polymers), and alterations in electrolysis methods ones. Consequently, the team suggested that the
can also regulate the interfacial microenviron- promotion of formic acid formation on hydrophilic
ment, thereby improving the activity and selectivity surfaces is due to the weakening of the M–H bond.
of the CO2 RR [10,28,71]. Lu et al. demonstrated that In contrast, hydrophobic species would lead to
the introduction of a moderate amount of O2 into stronger M–H bonds, thus inhibiting the formation
the CO2 RR system increased the production rate of formic acid and allowing the formation of CO to
of oxygenates and hydrocarbons by 216 times [72]. prevail. Pulsed electrolysis, by applying periodically
Mechanistic studies revealed that the introduction alternating potentials, offers new possibilities for
of O2 created a hydroxyl-rich microenvironment regulating the reaction microenvironment and the
on the surface of the Cu catalyst, thereby lowering electrocatalytic process. For example, Cuenya et al.
the energy barriers for the formation of oxygenates studied the effects of different anodic oxidation
and hydrocarbons. Bao et al. employed a co-feeding potentials (Ea ) during pulsing on CO2 RR. They
method of CO and CO2 , whereby increasing the found that at Ea = 0.9 V vs. RHE, a significant
pressure of CO in the feeder resulted in a shift of the number of grain boundaries and defect sites formed
primary electrolysis product from ethylene to acetate on the surface of copper particles, leading to a
[73]. Further studies revealed that this switching in substantial increase in the Faradaic efficiency for
selectivity is closely related to the increased coverage C2+ products [75]. At Ea = 1.2 V vs. RHE, the
of CO intermediates and the rise in local pH. Specif- regeneration of Cu2 O consumed an excess of OH− ,
ically, ethylene is preferentially formed at low *CO causing a decrease in the local pH at the catalyst
coverage, whereas a high *CO coverage and elevated surface, which favored the reaction pathway towards
local pH would favor the formation of acetate. In CH4 formation.
terms of catalyst surface functionalization, Wang CO2 RR could give a variety of products, which
et al. innovatively developed a universal amino acid significantly adds to the complexity of its reaction
modification strategy, whereby copper electrodes pathways. The microenvironment not only affects
functionalized with amino acids exhibited enhanced the CO2 RR kinetics, but also alters the selectivity of
capability for hydrocarbon production regardless the final products. This provides a broader stage for
of electrode morphology [74]. Mechanistic studies microenvironment regulation strategies, but also in-
indicated that the –NH3 + group of the adsorbed creases the difficulty of understanding their intrinsic
zwitterionic glycine could effectively facilitate the mechanisms.
stable adsorption of the key intermediate CHO*.
Bell et al. used bilayer cation- and anion-conducting
ionomer coatings to control the catalytic microen- MICROENVIRONMENT REGULATION FOR
vironment on the surface of copper electrodes [28]. PRACTICAL ELECTROCHEMICAL DEVICES
Anion-exchange ionomers (AEIs), on account of In practical electrochemical devices (often featur-
their high CO2 solubility, increase the local ratio of ing high current densities), gases are often used
Page 11 of 21
directly (rather than in the dissolved form) as the the catalyst/ionomer interface. In proton exchange
reactants to ensure an efficient mass transport, membrane fuel cells (PEMFCs), the adsorption
which, on the other hand, also leads to a more of sulfonate groups in the ionomer on the surface
complex reaction microenvironment. Consequently, of Pt-based catalysts would hamper their catalytic
investigations into microenvironments relevant to activities. To address this issue, Wei et al. employed
practical electrochemical devices are of great neces- cyclohexanol with the chair or boat conformations
sity. It is encouraging that some progress has been to coordinate with the ionomer, thus effectively
made in this field recently. blocking the way in which the ionomer is adsorbed
onto the Pt surface (Fig. 6b) [25]. This approach led
to the liberation of Pt active sites and significantly en-
Water electrolyzers and hanced mass transport. On the other hand, the uni-

hydrogen–oxygen fuel cells form distribution of ionomer can effectively improve
Producing green hydrogen via water electrolysis is oxygen mass transport at the Pt/ionomer interface,
generally considered an ideal solution for achieving allowing for a lower Pt loading without incurring
a future of renewable energy and carbon neutrality. high voltage losses. Strasser et al. achieved this by in-
Anion exchange membrane water electrolyzers troducing balanced sp2 pyridinic/pyrrolic/graphitic
(AEMWEs), benefiting from the use of inexpensive N functional groups interacting with the ionomer
metal catalysts, offer notable advantages in cost. chains, ensuring homogeneous coverage of the
Typically, electrolyzing alkaline solutions may im- ionomer on carbon supports [26]. Furthermore,
prove the performance and stability of AEMWEs in considering the poor dispersion characteristics
contrast with directly electrolyzing pure water, yet of conventional ionomers, Sung et al. employed
the exact mechanism underlying this performance supercritical isopropyl alcohol (IPA) in conjunction
enhancement remains uncertain. Weber et al. em- with water as cooperative polar co-solvents to boost
ployed experimental and mathematical modeling the polarity of the solvent and intensify solvation
approaches to expound the impact of hydroxide con- by creating hydrogen bonds. This, in turn, led to
centration on the performance of water electrolyzers the formation of an ionomer dispersion featuring
[76]. They demonstrated the functional relationship colloidal particles significantly smaller on average
between polarization curves and high-frequency re- than those present in commercially accessible dis-
sistance with hydroxide concentration. The findings persions [79]. For PEMFCs, water is solely formed
indicated that increased hydroxide concentration at the cathode; in contrast, for AEMFCs, water
is vital not only for the membrane and catalyst is generated at the anode, while the water at the
layer’s ohmic resistance, but also for the reaction cathode is consumed. This poses more challenges
kinetics. Direct electrolysis of seawater is another for water management in the operation of AEMFCs.
cost-effective strategy, but it faces major challenges Mustain et al. incorporated hydrophobic compo-
such as chloride corrosion and electrode passivation. nents (PTFEs) into the gas diffusion layer and
Ling et al. introduced a Lewis acid layer (Cr2 O3 ) on catalyst layer, resulting in gas diffusion electrodes
the surface of the catalyst (CoOx ) to electrolyze wa- (GDEs), and the water management was optimized
ter molecules and capture the in situ generated OH− by regulating the hydrophilicity/hydrophobicity of
[77]. This in situ enrichment of OH− effectively the catalyst/ionomer interface [80]. This design
inhibits chloride corrosion on the catalyst sur- led to a stable operation, demonstrating continuous
face and mitigates the issue of precipitate formation, functioning for more than 10 0 0 h at 600 mA cm−2 .
achieving long-term stability of seawater electrolyzer
exceeding 100 h at 500 mA cm−2 . Compared with
the same pH environments at both the cathode CO2 RR electrolyzers
and anode in conventional electrolyzers, bipolar GDEs enhance the mass transport of CO2 to the ac-
membrane (BPM) devices enable the independent tive electrocatalysts, leading to greater current densi-
selection of ideal pH conditions for each half- ties and carbon conversion efficiencies, thus consti-
reaction, along with compatible catalysts. Boettcher tuting a key technology that is expected to achieve
et al. designed a BPM water electrolyzer that can large-scale application of CO2 RR. The GDE-based
provide an acidic environment for the HER side to CO2 RR electrolyzer could fail typically owing to car-
accelerate its kinetics (Fig. 6a), while providing an bonate deposition. Specifically, this is due to the high
alkaline environment on the OER side to allow for local concentration of carbonates formed from the
the utilization of low-cost base metal catalysts [78]. reaction of CO2 with generated OH− , combined
The performance and durability of fuel cells are with the crossover of cations such as K+ and Na+
influenced not only by the inherent properties of from the anolyte [81,82]. The carbonate deposi-
the catalysts but also by the microenvironment at tion in GDEs would block the transport pathways of
Page 12 of 21
a b Ionomer backbone Ionomer backbone

–CF2-CF2– –CF2-CF2–
+ Proton
H3O transfer
electrolysis Proton transfer (H2O)λ
MEA water SO3 H SO3 H (H2O)λ H SO3 Increasing proton
Poisoned Coordination transport channel
O O O
Pt sites SO3 H (H2O)λ H SO3 (H2O)λ H SO3 Cyclohexanol H (H2O)λ H (H2O)λ H
2H2O blocking Releasing the
poisoned Pt sites
Pt Pt Pt
2H2
VS
Increased O2 Improving oxygen
transport
RO2 local oxygen +
Nafion transport H3O

ionomer resistance
H3O +
ping
O2
Hop
V Pt Pt Cyclohexanol-Nafion
e– e– ionomer
acid
0,acid+η HER
0,base base
0
-ηwd +EH+ /H2 Carbon Carbon
- -ηOER+E wd
V tot = -E O2/OH Conventional contact Proposed non-contact
Pt/ionomer interface Pt/ionomer space
c d

CO2-saturated KOH solution 100
FECO (%)
KHCO3 solution
90
80
Hydrophilic Hydrophilic 80
carbon fabrics Ni foam J FE
60 Ag-TEL in the FTDT cell
Ecell = 3.5 V, EA = 100 cm2
Jtot (A)
40
Ecell = 2.9 V, EA = 100 cm2
20 Ecell = 3.5 V, EA = 1 cm2
2
1
Hydrophobic
0
Cathode Anode Hydrophobic 0 12 24 36 48 60 72 84 120 160 200
venting layer CEM venting layer
Time (h)
e CF2 CF2 f
CF2 CF Nafion O O H NH3 Cl
x y
pKa < 1 PAA PAH CAL Bulk electrolyte
O
CF2 pKa 4–6 pKa ~8 K+
n n OH- H+ H+
CF SO3 H
CF3 O
CF2
CF2 -SO3 – H+ K+
K+ K+ K+
K+ K+
Nafion K+ K+ -SO3 – K+ H+
PAA PAH Cu
H+ H+
-
GO OH K+ -SO3 – K+
K+ K+
AEM
K+ -
H+
OH -SO3 – H+
K+ K+ H+
K+
Glass substrate
Figure 6. Microenvironmental regulation for practical electrochemical devices. (a) BPM water-dissociation measurements.
WD is studied in an electrolyzer fed by only pure water. Reproduced with permission from Ref. [78]. Copyright 2020 American
Association for the Advancement of Science. (b) Illustration of the conventional direct-contact Pt/ionomer interface and the
proposed non-contact Pt/ionomer space for the cathode catalyst layer. Reproduced with permission from Ref. [25]. Copyright
2023 Nature Publishing Group. (c) Schematic illustration of FTDT cell. (d) Electrode stability tests for 1 cm2 and 100 cm2 FTDT
cells at different cell voltages. (c, d) Reproduced with permission from Ref. [85]. Copyright 2022 Nature Publishing Group.
(e) Molecular structures of the polyelectrolytes and schematic drawing of the membrane structure. Reproduced with permis-
sion from Ref. [86]. Copyright 2021 Nature Publishing Group. (f) Schematic illustration of ionic environment and transport
near the catalyst surface functionalized by the PFSA ionomer. Reproduced with permission from Ref. [17]. Copyright 2021
American Association for the Advancement of Science.
CO2 , thus leading to device failure. Therefore, pre- to assemble an MEA electrolyzer capable of oper-
cise control of the microenvironment in GDEs, espe- ating in pure water without adding any alkali metal
cially the regulation of carbonate chemistry, is crucial cations, thereby avoiding the issue of carbonate
for CO2 RR devices. deposition from the start [84]. When operated
Janáky et al. developed an operando activation and at a cell voltage of 3.54 V, ethylene is produced
regeneration process in which a solution containing with an industrial-scale partial current density of
alkaline metal cations is periodically injected into 420 mA cm−2 without any electrolyte consumption.
the cathode of a zero-gap electrolyzer to alleviate Chen et al. addressed the carbonate deposition issue
carbonate deposition [83]. This enables water-fed by modifying the method of CO2 feeding [85]. They
electrolyzers to operate with a CO2 RR efficiency developed an electrolyzer that utilizes the forced
comparable to that using alkaline electrolytes (CO convection of an aqueous CO2 -saturated catholyte
partial current density of 420 ± 50 mA cm−2 , throughout a porous electrode (Fig. 6c). The de-
sustained for over 200 h). Additionally, the team crease in local pressure led to increased exsolution of
demonstrated the scalability of this method across gaseous CO2 from dissolved CO2 and bicarbonate,
multiple electrolyzer stacks, each with an effective which in turn significantly decreased the thickness
area of 100 cm2 . Recently, Zhuang et al. employed of the diffusion layer (by a factor of ten). They as-
a bifunctional ionomer as the polymer electrolyte sembled a scaled-up 4 × 100 cm2 electrolyzer stack
Page 13 of 21
that produced CO at a remarkable rate of 90.6 L h−1 In summary, the research on the microenviron-
and maintained good stability (Fig. 6d). ment effects at the EEI provides guidance for the de-
BPMs composed of a cation exchange layer sign of practical electrochemical devices. However, it
(CEL) and an anion exchange layer (AEL) have also remains to be verified whether these anions, cations,
been explored for managing ion transport within the and organic compounds would affect the long-term
CO2 RR electrolyzer [82]. A reverse-bias BPM can stability of ionomers or membranes. Therefore, we
effectively control the ion transport across the bulk encourage the validation of strategies based on pla-
of the membrane. Here, cations from the anode are nar electrode systems in practical devices, with par-
repelled by the AEL, while anions from the cathode ticular emphasis on long-term stability tests to drive
are repelled by the CEL. This configuration effec- the practicality of these devices.
tively regulates the microenvironment at the GDL

surface, suppressing the deposition of carbonates
and the crossover of products. However, the acidic IN SITU/OPERANDO CHARACTERIZATION
environment at CEL usually results in a low-pH TECHNIQUES AND THEORETICAL
microenvironment at the CEL/cathode interface, SIMULATIONS
resulting in low CO2 RR efficiency. In light of this, Conventional characterization techniques are often
Mallouk et al. utilized ratiometric indicators and inadequate for observing the dynamic changes in
layer-by-layer polyelectrolyte assembly to deposit mass/charge transport occurring at the EEI during
weakly acidic polyelectrolyte layers on the strongly electrocatalysis. To address this issue, a range of in
acidic CEL (Fig. 6e) [86]. This arrangement allows situ/operando characterization techniques (includ-
for the measurement and manipulation of local ing in situ visualization and spectroscopic meth-
pH at the GDL surface with a spatial resolution of ods) have been developed. Meanwhile, significant
tens of nanometers. The results indicate that the progress has been made in theoretical computa-
presence of the weak acid layer suppresses HER tional techniques based on EDL (AIMD) and elec-
without adversely affecting CO2 RR. trochemical devices (continuum modeling) recently.
Compared with electrolyzers working under
alkaline or neutral conditions, those working under
acidic conditions typically exhibit higher carbon In situ visualization methods
conversion efficiencies by inhibiting the formation In situ visualization can help monitor the bubble be-
of carbonates. However, the kinetically favored HER havior at the interface, which is crucial for guiding
tends to dominate under acidic electrolytes. Sargent the design of more efficient devices, especially for
et al. addressed this challenge by modifying the cat- water/CO2 RR electrolyzers. Sun et al. developed a
alyst surface with a cation-augmenting layer, main- simple method called bubble pump consumption
taining a high concentration of K+ around the GDL chronoamperometry (BPCC) involving the use of a
surface (Fig. 6f) [17]. This approach enabled an effi- gas supply unit and a data acquisition system (com-
cient CO2 RR process on Cu catalysts at pH <1 with prising high-speed camera, light source, and electro-
a single-pass CO2 utilization of 77%. The research chemical workstation) [88]. By injecting individual
by Hu et al. further demonstrated that in acidic oxygen bubbles into GDEs and monitoring the dif-
electrolytes, the hydrated alkali cations physisorbed fusion behavior along real-time current evolution,
on the cathode could alter the distribution of the the exact correlation between the actual current over
electric field within the EDL [87]. This alteration time and the dynamics of oxygen diffusion consump-
inhibits the migration of hydronium ions towards tion was established. This enabled the determina-
the cathode, thereby impeding hydrogen evolution tion of key parameters such as the gas diffusion co-
and facilitating the reduction of CO2 . Moreover, efficient and density of effective catalytic sites of
Sinton et al. reported the development of a het- GDEs. Zhang et al. observed the process of H2 evolu-
erogeneous catalyst adlayer composed of covalent tion in proton exchange membrane electrolyzer cells
organic framework (COF) nanoparticles and cation (PEMECs) through a specialized high-speed micro-
exchange ionomers [27]. The imine and carbonyl- scopic visualization setup [89]. They demonstrated
functionalized COFs formed uniformly distributed that gas evolution and bubble nucleation predomi-
cation-carrying and hydrophilic–hydrophobic nantly take place on catalyst layers at the edges of
nanochannels. This structure led to a high local pores in the thin/tunable liquid/gas diffusion lay-
alkalinity and cation-enriched catalytic microenvi- ers (TT-LGDLs). In addition to bubble behavior, in
ronment near the GDL surface, which suppresses situ visualization can also help observe the wetting
HER and enhances the conversion of CO2 to characteristics at the interface. Tileti et al. employed
multi-carbon products on copper in strongly acidic in situ liquid-phase TEM with an electrochemi-
conditions. cal approach to uncover the variation of wetting
Page 14 of 21
a Image To test station Image

3D X-ray image processing
e-in Airin Airout
processing
3D neutron image
Aluminum flow field Stainless steel bolt X-ray Neutron

detector Fuel cell detector Liquid water droplet
MEA
Land Neutrons X-rays

Channel
CT rotation
z
y 1 mm
x Catalyst coated membrane e-out H H2, out
2, in Stainless steel bolt
To test station
b c E (V vs SHE)

O2 Laser H2O Φ – ΦPZC -1.1 -0.45 0.1
(EPZC) Φ – ΦPZC
High Low
potential potential ρwat
4
2
Cathode
Raman 0
Anode
signal
ρelectrode ρ+ion ρ–ion ρelectrode

0 5 10 10 5 0
Distance (Å)
IHL OHL DifL DifL OHL IHL
d Top
Bridge
e To product quantification f
Hollow3 Reference Bulk
Hollow4 electrode Mass transport Working
electrolyte boundary layer electrode
Membrane
Creactant e-
1.00
0.75
dmin
fg (d)
0.50 Counter
electrode 50-200 μm
0.25 O-ring
Anodic Modeled domain
Reactant
0.00 reactants flow
-0.5 0.0 0.5 1.0 Working
d (Å) Cathodic reactants electrode
Figure 7. In situ/operando characterization techniques and theoretical simulations. (a) Fuel cell imaging schematic and sam-
ple neutron and X-ray images. Reproduced with permission from Ref. [91]. Copyright 2020 American Association for the
Advancement of Science. (b) Model of shell-isolated nanoparticles (Au@SiO2 NPs, SHINs) at a Pt(111) surface and the mech-
anism of the ORR process revealed by the EC-SHINERS method. Reproduced with permission from Ref. [96]. Copyright 2019
Nature Publishing Group. (c) Representative structures of hydrated ions near the electrodes. Reproduced with permission
from Ref. [102]. Copyright 2022 Nature Publishing Group. (d) Surface sites for the 3 × 4-(111) (top left) and 3 × 1-(211) (top
right) slab models used for the site-partitioning of the AIMD trajectories. Symmetrically equivalent sites are shown in the
same color. (Bottom) Schematic of Gaussian weights on surface sites with the Gaussian weighting function (fg ) against the
distance d. The weighting function overlap is depicted for two sites separated by the minimum distance dmin . Reproduced
with permission from Ref. [103]. Copyright 2020 AIP Publishing LLC. (e) Standard electrochemical compression cell and corre-
sponding physical model schematic representation of a typical experimental setup, and (f) the corresponding modeled domain
for the BL model. Reproduced with permission from Ref. [107]. Copyright 2023 Elsevier Inc.
characteristics of cobalt-based oxide catalysts during techniques for processing images (iterative recon-
potential cycling [90]. This method establishes the struction and metal artifact reduction) for character-
real-time correlations between the wetting behavior ization of fuel cell components (Fig. 7a) [91]. This
of materials and OER, providing visual evidence for method allows for the simultaneous, high-contrast,
the study of solid–liquid interfacial interactions in yet independent spatial and temporal analysis of
electrochemistry. both the morphology and moisture content of MEA
The establishment of real-time characterization components. In addition, Mustain et al. employed
of component morphology and fluid dynamics is neutron imaging with operando micro–X-ray com-
crucial for optimizing the performance and stabil- puted tomography (CT) to observe the distribu-
ity of fuel cells. Notably, Bazylak et al. combined tion of liquid water over time and space within the
advanced dual-modality tomography (simultaneous functioning device [80]. This could lay the basis for
neutron and X-ray tomography) with sophisticated optimizing water management.
Page 15 of 21
In situ spectroscopies Raman spectroscopy (SHINERS) technique [95].

As a good complement to in situ visualization In SHINERS, the application of an ultra-thin and
methods, in situ spectroscopies (including in situ consistent silica shell on gold nanoparticles proves
X-ray scattering, surface-enhanced infrared/Raman effective in amplifying the Raman signals from
spectroscopies) provide molecular-level experimen- molecules near the nanoparticle surface without
tal evidence for the chemical composition and disruption. This enables Raman signal acquisition
adsorption–desorption information at the EEI. from various substrates. Li et al. investigated the
In situ X-ray scattering can probe deep into con- ORR process at Pt(hkl) single-crystal surfaces us-
densed matter (such as solid phase and liquid phase) ing the SHINERS technique (Fig. 7b) [96]. They
without hindering mass transport and electrochem- acquired direct spectral proof of *OH, *HO2 and
ical reactions, making it relatively easy to operate. O2 − , elucidating the ORR mechanism at both the

The MEA components of CO2 RR electrolyzers have molecular and atomic levels under acidic and alka-
long been struggling with poor stability attributed line conditions. SHINERS’ distinct benefit lies in
to cathode flooding and salt precipitation. However, its specific adaptability to investigate the adsorption
the understanding of the mechanisms behind these arrangement and catalytic mechanisms of probe
local environmental changes remains rather limited. molecules on surfaces of single crystals. The team
Seger et al. employed operando X-ray analysis com- further employed SHINERS to study the structure
bined with online gas chromatography and mass and dissociation procedure of interfacial water on
spectrometry to monitor electrolyte precipitation Pd single-crystal surfaces, offering insights into the
and salt deposition in the GDE of CO2 RR electrolyz- mechanism of structural arrangement of interfacial
ers [92]. Concurrently, direct evidence of bicarbon- water and the influence of local cation disruption on
ate salt precipitation at the cathode was identified, the water structure [97].
which exacerbates the issue of electrolyte flooding ATR-SEIRAS is another commonly used in situ
and shifts the reaction selectivity towards HER. Fur- spectroscopic technique supplementary to SERS.
thermore, the team employed operando wide-angle Smith et al. investigated the pH gradients at the poly-
X-ray scattering (WAXS) to reveal how salt forma- crystalline Cu and phosphate buffer interface during
tion in the MEA cathode varies with changes in alka- CO2 RR using in situ SEIRAS [98]. The results in-
line cations [93]. The findings indicate that salts with dicate that at the potential of −1 V vs. RHE, where
lower solubilities (e.g. Li/Na-based) would crystal- hydrocarbons are formed, there is a significant dif-
ize faster, which limits the CO2 from accessing the ference of 5 pH units between the local pH near
catalyst and enhances the competing HER. The key the electrode surface and the bulk solution pH. This
to avoiding salt precipitation is to use highly solu- suggests that activity analysis under mass transport
ble alkali metal salts (e.g. CsHCO3 ) in the anolytes limitations must consider the impact of the large
along with an optimal salt concentration ranging concentration gradients. Xu et al. employed ATR-
from 0.01 to 0.1 M. SEIRAS to investigate the impact of different alkali
Infrared/Raman spectroscopies serve as po- metal cations on the Au electrode surface CO2 con-
tent tools for molecular fingerprinting based on centration [99]. At −0.8 V vs. RHE, the interfacial
vibration modes. In previous sections discussing hy- CO2 concentrations were found to be lowest in the
drogen/oxygen reactions and CO2 RR, many works presence of Cs+ , providing a plausible explanation
have demonstrated the importance of these two for the cation effect. Recently, Yang et al. combined
spectroscopies in analyzing microenvironmental in situ infrared nanospectroscopy (nano-FTIR) with
effects [14,15,23,42,43,48,50]. Here, we will further in situ SERS and successfully revealed the formation
elaborate on their respective characteristics, drawing pathway of NP/ordered-ligand interlayer induced
from recent representative studies. Generally, IR by bias-induced dissociation of tetradecylphospho-
spectroscopy detects dipole-moment-induced light nic acid (TDPA) ligands on Ag NPs [100]. They
absorption, whereas Raman spectroscopy assesses also found that the accumulation of non-covalent in-
polarizability-induced inelastic scattering. Raman teractions in the interfacial microenvironment dur-
active centrosymmetric molecules are typically ing ligand dissociation promotes the development
IR-inactive in IR owing to the mutual exclusion rule, of surface-constrained electric fields, eventually en-
and vice versa. Consequently, in the majority of in- hancing the selectivity and activity for CO2 RR. The
stances, Raman and IR spectroscopies provide sup- combined spectroscopic approach provides an excel-
plementary information to each other [94]. In order lent example for investigating the dynamic response
to address the enduring constraints of SERS related of microenvironments with nanoscale resolution, of-
to structure and material applicability, Tian et al. fering guidance for studying the interfacial microen-
introduced the shell-isolated nanoparticle-enhanced vironments of nanomaterials.
Page 16 of 21
Ab initio simulation and continuum continuum modeling can play a crucial role in ana-
modeling lyzing the microenvironment effects of electrochem-
ical devices (include water electrolyzers, hydrogen–
The progress of in situ characterization techniques
oxygen fuel cells, and CO2 electrolyzers), as it can
has helped deepen the understanding of microen-
link the device performance with electrode char-
vironmental effects. However, these techniques
acteristics and operational conditions, and obtain
still require further refinement to enhance the ap-
theoretical product distributions and other device
plicability in different EEIs and the reliability of
parameters [105]. This is crucial for the rational
data analysis. The theoretical simulation method
utilization of microenvironment effects to drive the
can supplement, to some extent, the deficiency of
design and preparation of high-performance devices.
experimental methods.
For instance, Weber et al. simulated the performance
AIMD can efficiently establish the atomic-scale

of Cu-based MEA for CO2 RR through continuum
structure of the EDL, adjust the basic characteristics
modeling [106]. In this model, the team systemati-
of the electrochemical interface, and deliberately in-
cally investigated the effects of gas and liquid water
troduce specific ions and solvents [101]. Kim et al. re-
transport, temperature, the properties of ionomer
produced the experimentally observed characteristic
and membrane, heat transfer, and different feed con-
peaks of electrochemical impedance spectroscopy
ditions (liquid-fed and vapor-fed) on product distri-
(EIS) in dilute aqueous electrolyte through AIMD,
bution. The results indicate that higher temperatures
and revealed that the origins for the two peaks ob-
(350 K) and sufficient water supply are advanta-
served at anodic and cathodic potentials are the elec-
geous for the formation of C2+ products. In addition,
trosorption of ions and structural phase transition,
Bell et al. integrated continuum modeling and the
respectively (Fig. 7c) [102]. This work demonstrates
covariance matrix adaptation evolutionary strategy
the advantages of the AIMD approach in building
(CMA-ES) to fit Tafel parameters for electrochem-
complex EDL structures, enabling direct validation
ical CO2 RR over Ag and Sn catalysts (Fig. 7e, f)
of simulation results through comparison with ex-
[107]. This method eliminates subjective errors in
perimental findings. In addition, AIMD can also pre-
fitting Tafel equations, establishing a more rigor-
dict solvent effects at solid/liquid interfaces with
ous benchmark test. These results underscore the
good accuracy. Chan et al. explored the solvation at
importance of accounting for mass transport and
charge-neutral metal/water interfaces using exten-
buffer kinetics in the analysis of the product of CO2
sive AIMD simulations with commonly used con-
electrolyzers.
tinuum solvent models (Fig. 7d) [103]. They con-
In summary, advanced in situ/operando tech-
sidered multiple metals (including Cu, Au, Pt) and
niques provide evidence of adsorption/desorption
various adsorbates relevant to electrochemical reac-
of reactants, products and, in particular, the inter-
tions (including CO2 reduction and oxygen redox),
mediates, as well as real-time monitoring on the
and reasonably quantified the solvation energies.
microenvironment status of device components.
These results provide a reference for establishing ef-
Further integration with the new theoretical cal-
fective/parameterizable solvation models. Addition-
culation techniques can reasonably simulate the
ally, AIMD can effectively distinguish the configura-
process of catalytic reactions and the operating
tion of the electrolyte at the interface and in the bulk
status of devices. The development of these tech-
liquid phase. Grob et al. analyzed the atomic con-
nologies and methods could well assist the study of
figurations of water solvation layers on Pt(111) elec-
microenvironment effects.
trodes using AIMD [104]. The results revealed the
difference of water molecule configurations between
the surrounding solvation layer (through the oxygen
atom bounding on Pt) and the bulk electrolyte (via CONCLUSION AND PERSPECTIVE
H-up and H-down configurations), and less dense The past few decades have witnessed the booming
water solvation layers on hydrogen-covered Pt. development of sustainable electrocatalysis, cover-
Benefiting from its advantages in simulating the ing both fundamental research in laboratories and
EDL structure, AIMD is well suited as a powerful commercializable applications in industry. The reg-
tool for analyzing microenvironment effects based ulation of the microenvironment (by means of pH,
on EEI. However, it is not as applicable for practical cation/anion effects and constructing organic com-
electrochemical devices working at high current pound interface, for instance, caffeine) has proven
densities because the corresponding microenviron- successful in boosting the reaction kinetics and sta-
ment of porous electrodes often involves intricate bility and improving the selectivity for specific target
multiphase fluid, mass transport, temperature, pres- products in the hydrogen/oxygen reaction and car-
sure, and other physical variables. Physics-based bon dioxide reduction reaction. The rapid advance
Page 17 of 21
of in situ/operando characterization techniques and generality of this correlation for different

theoretical simulation methods offers powerful tools electrode surfaces needs to be further vali-
to probe the catalytic pathways in further depth, dated. Currently, a vast number of low-cost,
which adds to understanding of EDL structure and high-performance catalysts based on non-
microenvironment effect. Thanks to these advanced precious metals have been developed, and
methodologies, scientists have begun to try unveil- the research on microenvironment regula-
ing the underlying mechanisms of microenviron- tion for these electrode materials is of high
ment regulation, and found that the interfacial elec- necessity.
tric field, interfacial structures (such as water layer (iii) Emphasis on the research on microen-
and hydrogen bond network) and the local concen- vironment regulation of advanced
tration/coverage of relevant species (such as pro- electrochemical devices operating at

tons, hydroxide ion, reactants and intermediates) industrially-relevant current densities.
may play notable roles. On the basis of a more in- For those advanced electrochemical devices
depth understanding on the electrode/electrolyte such as MEA, the experimental tests are more
interface, the strategies for microenvironment reg- complicated than those for planar electrodes,
ulation could readily translate into the design and and the corresponding results are more
fabrication of high-performance electrochemical de- subject to stochastic errors. Therefore, it is
vices for practical applications, including water/CO2 necessary to standardize the measurements
electrolyzers and fuel cells, promising a grand pic- for these advanced devices and to conduct
ture of large-scale implementation for green en- multiple parallel tests so as to minimize er-
ergy and sustainable development. Nevertheless, rors. In addition, we noted that a few readily
some related topics are still under debate, and a implementable ‘intermediate test techniques’
few subareas may need to be explored in further (between the conventional three-electrode
depth. At the end of this review, we share our configuration and the MEA) have emerged
views on several aspects that call for more thorough recently, such as promoting the mass trans-
scrutiny. port for RDE [57], and using the floating
electrode setup [108]. From a technoeco-
(i) Emphasis on a more accurate model for nomic perspective, achieving high activity,
the electrical double layer model. A clear selectivity, and stability at low overpotentials
and complete model for the EDL structure and at industrial-level current densities in
is the key to deciphering the microenviron- advanced electrochemical devices presents
ment effect. It is of great necessity to con- greater challenges and significance. Another
duct standardized measurements on the EDL topic that needs particular attention is the
properties (for instance, the electric fields effect of microenvironment on the long-term
for different EEIs, PZC) and to establish a stability of devices. A typical example is the
more comprehensive database. The complex- CO2 electrolyzer designed on the basis of
ity in electrode preparation in metallic single- cation effects, where the high-concentration
crystal electrode and the high requirements cations could elevate catalytic efficiency and
on the precision of electrocatalytic measure- improve product selectivity, yet this could
ments call for advanced, high-efficiency char- also exacerbate the problem of carbonate
acterization methodologies. In addition, the precipitation, thereby shortening the life
emerging in situ/operando characterization cycle of the device. Therefore, in practice,
and theoretical simulation techniques are of a subtle balance needs to be maintained
great significance in providing more specific between the two conflicting aspects, so
information on the EDL (such as the solva- as to ensure the long-term operation of
tion of electrode surface, the location and in- the devices featuring optimized reaction
teraction of solvated anions/cations and im- microenvironments.
pact of the electric field).
(ii) Emphasis on the research on microen-
vironment regulation for low-cost cat- FUNDING
alysts based on non-platinum–group This work was supported by the National Key R&D Program of
metals. Historically, research on the mi- China (2021YFF0500500), the National Natural Science Foun-
croenvironment regulation of noble metal dation of China (21925202 and U22B2071), Yunnan Provincial
electrodes such as Pt electrodes helped to Science and Technology Project at Southwest United Graduate
establish the correlation between EEI and School (202302AO370017), and the International Joint Mission
hydrogen/oxygen reaction kinetics, yet the On Climate Change and Carbon Neutrality.
Page 18 of 21
Conflict of interest statement. None declared. 19. Niu Z-Z, Gao F-Y, Zhang X-L et al. Hierarchical copper with
inherent hydrophobicity mitigates electrode flooding for high-
rate CO2 electroreduction to multicarbon products. J Am Chem
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© The Author(s) 2024. Published by Oxford University Press on behalf of China Science Publishing & Media Ltd. This is an Open Access article distributed under the terms of the Creative
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REVIEW National Science Review

11: nwae315, 2024

Special Topic: Local Environments in Electrochemistry

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barriers for the involved chemical species (including

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Normalized conductance (a.u.)

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a 300 Pure KOH b 0.4 M KBi + 1.5 M KF c 12

Current density (mA/cm2)

jk at 0.9 V (mA cm–2)

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Current density (mA cm–2)

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a b Ionomer backbone Ionomer backbone

Nafion transport H3O

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Ecell = 3.5 V, EA = 100 cm2

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a Image To test station Image

Aluminum flow field Stainless steel bolt X-ray Neutron

Land Neutrons X-rays

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ρelectrode ρ+ion ρ–ion ρelectrode

IHL OHL DifL DifL OHL IHL

In situ spectroscopies Raman spectroscopy (SHINERS) technique [95].

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of in situ/operando characterization techniques and generality of this correlation for different

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