Metal Complex Role in HER and OER

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Harnessing the electronic structure of active metals

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to lower the overpotential of the electrocatalytic

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Cite this: DOI: 10.1039/d3sc05891c
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oxygen evolution reaction†
have been paid for by the Royal Society
of Chemistry Lorenzo Baldinelli, a Gabriel Menendez Rodriguez, *a Iolanda D'Ambrosio,a
Amalia Malina Grigoras, a Riccardo Vivani, b Loredana Latterini, a
Alceo Macchioni, a Filippo De Angelis acde and Giovanni Bistoni *a
Despite substantial advancements in the field of the electrocatalytic oxygen evolution reaction (OER), the
efficiency of earth-abundant electrocatalysts remains far from ideal. The difficulty stems from the
complex nature of the catalytic system, which limits our fundamental understanding of the process and
thus the possibility of a rational improvement of performance. Herein, we shed light on the role played
by the tunable 3d configuration of the metal centers in determining the OER catalytic activity by
combining electrochemical and spectroscopic measurements with an experimentally validated
computational protocol. One-dimensional coordination polymers based on Fe, Co and Ni held together
by an oxonato linker were selected as a case study because of their well-defined electronic and
geometric structure in the active site, which can be straightforwardly correlated with their catalytic
activity. Novel heterobimetallic coordination polymers were also considered, in order to shed light on
the cooperativity effects of different metals. Our results demonstrate the fundamental importance of
electronic structure effects such as metal spin and oxidation state evolutions along the reaction profile
Received 3rd November 2023
Accepted 11th December 2023
to modulate ligand binding energies and increase catalyst efficiency. We demonstrated that these effects
could in principle be exploited to reduce the overpotential of the electrocatalytic OER below its
DOI: 10.1039/d3sc05891c
theoretical limit, and we provide basic principles for the development of coordination polymers with
rsc.li/chemical-science a tailored electronic structure and activity.
hydrogen production efficiency, leading to high overpotentials.3

1. Introduction This stimulated intense research efforts towards the develop-
Water electrolysis powered by renewable energies has attracted ment of low-cost, efficient and stable OER-electrocatalysts.4–8
increasing interest in recent years as a sustainable source of Under acidic conditions, precious metal-based oxides such
molecular hydrogen, which is one of the most promising as IrO2 and RuO2 can be considered as the state-of-the-art OER
alternatives to fossil fuels as an energy carrier.1,2 This process is electrocatalysts because of their remarkable activity and
composed of two half-reactions, namely the oxygen evolution stability;9–12 however, their large-scale application is hindered
reaction (OER) at the anode and the hydrogen evolution reac- by the high cost and low abundance of the metals. Conse-
tion (HER) at the cathode. The sluggish four electron transfer quently, an intense research activity aimed at minimizing the
processes involved in the OER mechanism limit the overall amount of noble-metal utilization is ongoing.13–19
Non-precious metal-oxides and hydroxides under oxidative
potentials are only stable under alkaline conditions,20 and hence
a
Dipartmento di Chimica, Biologia e Biotecnologie, Università Degli Studi Di Perugia, great efforts have been made to develop earth-abundant
Via Elce di sotto, 8, 06123 Perugia, Italy. E-mail: gabriel.menendezrodriguez@unipg.
transition-metal-based OER-electrocatalysts with sustained
it; [email protected]
b
Dipartimento di Scienze Farmaceutiche, Università Degli Studi Di Perugia, Via del
stability in alkaline solution.21–25 Nevertheless, despite substan-
Liceo, 06123 Perugia, Italy tial advancements in the eld, the efficiency and stability of such
c
Computational Laboratory for Hybrid/Organic Photovoltaics (CLHYO), Istituto CNR OER catalysts remain far from ideal. In particular, there seems to
di Scienze e Tecnologie Chimiche “Giulio Natta” (CNR-SCITEC), 06123 Perugia, Italy be a lower bound for the overpotential that can be obtained,
d
Department of Mechanical Engineering, College of Engineering, Prince Mohammad which is approximately 0.2–0.4 V. This effect has been attributed
Bin Fahd University, Al Khobar 31952, Saudi Arabia
e
to linear scaling relationships between OOH and OH binding
SKKU Institute of Energy Science and Technology (SIEST), Sungkyunkwan University,
energies limiting the OER activity.26,27
Suwon 440-746, Korea
† Electronic supplementary information (ESI) available. See DOI:
A major difficulty in the development of new strategies for
https://doi.org/10.1039/d3sc05891c breaking such linear scaling relationships is the lack of
© 2023 The Author(s). Published by the Royal Society of Chemistry Chem. Sci.
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Scheme 1 Coordinating and bridging mode of the oxonato ligand in the studied CPs (top). Stereochemistry at the metal center (bottom).
fundamental knowledge on the electronic and geometric nature functional theory (DFT) calculations that such spin-crossover
of the active site for many heterogeneous catalysts.28–32 The effects might signicantly lower the OER overpotential of a co-
difficulty stems from the complex nature of the OER catalytic hexacyanoferrate electrocatalyst.47 Understanding to what
materials and of their interaction with the environment. On the extent this effect could be exploited in practical applications,
one hand, such complexity limits the chemical insights that can e.g., to break the above-mentioned linear scaling relationships,
be obtained from purely experimental investigations.33 This is would be an important step towards rational design.
especially evident for metal oxides, for which the geometric and In this work, our aim is to provide a fundamental insight into
electronic nature of the active site is still a matter of debate,34,35 the electronic effects that inuence a catalyst activity towards the
making rational design of new catalysts particularly chal- OER using a combined experimental and computational
lenging. On the other hand, the strong dependence of the strategy. Among the numerous families of OER catalysts studied
reaction free energies on the exchange-correlation functional and optimized over the years, we selected coordination polymers
choice together with the limited accuracy of standard compu- (CPs)48–52 as a prototype case study. These systems are crystalline
tational methodologies in the calculation of redox potentials, solids with well-dened periodic structures extending in 1, 2, or
acidity constants and reaction energies in water limits the 3 dimensions, in which metal “nodes” (clusters or ions) are
condence on purely computational predictions.33,36–39 Hence, linked by organic and/or inorganic ligands through coordination
synergistic computational and experimental studies are crucial bonds. Hence, these materials can be seen as heterogeneous
to elucidate the mechanistic underpinnings responsible for the assemblies of transition metal complexes, featuring active sites
catalyst activity and stability, and for deriving the rule of with well-dened structural and electronic properties, which can
thumbs for new materials with lower overpotentials. be readily correlated with their electrocatalytic activity.53,54
Although the integration of experimental and theoretical In the present case, we consider a series of one-dimensional
studies has already proven instrumental in this context,40 CPs containing the versatile oxonato linker (oxo), a bianionic
fundamental questions on the origin of the catalytic activity of multidentate ligand, exhibiting many coordinating and
many materials still remain unanswered.41 In particular, an in- bridging possibilities, which in the materials synthetized in this
depth understanding of the relationship between a material study shows only the bidentate chelating and bridging modality
catalytic activity and its electronic structure is oen lacking. For illustrated in Scheme 1 (top).
example, it is well known that the metal spin state has a deep Homometallic CPs based on oxonato linkers have been
inuence on the OER efficiency.42–44 However, the spin state of already reported in the literature for manganese, nickel, cobalt,
metals can change in the course of an electrochemical reac- zinc and iron.55,56 Depending on the nature of the metal ion, two
tion45 or in response to external stimuli such as an external different structures can be obtained. For M = Ni,55 the asym-
potential.46 Therefore, it is somewhat surprising that spin metric unit contains two metal ions, one with the nitrogen atoms
crossover effects in the heterogeneous electrocatalytic OER have of oxonato in the trans relative position, whereas in the other one
not been investigated in detail. As a notable exception, Hegner they are in the cis relative position and the metal center has a D
and coworkers recently suggested on the basis of density chirality (Scheme 1, bottom le). For M = Co and Mn,55 the
Chem. Sci. © 2023 The Author(s). Published by the Royal Society of Chemistry
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asymmetric unit contains one metal ion exhibiting a slightly (i)

distorted, L octahedral stereochemistry with the nitrogen atom
in the cis relative position (Scheme 1, bottom right). M(n) + OH− / M(n+1)–OH + e−
Heterobimetallic oxonato CPs have never been reported to
the best of our knowledge. In addition, oxonato CPs, in general, M(n) + OH− / M(n)c cOH + e−
have never been applied as OER catalysts.
Herein we describe the synthesis and detailed characteriza-
(ii)
tion of homometallic and heterobimetallic CPs constituted by
the [M(oxo)2(H2O)2] (Mn2+, Fe2+, Co2+, Ni2+) coordination unit, M(n+1)–OH + OH− / M(n+2)]O + H2O + e−
and their utilization as electrocatalysts. They were designed to

provide insight into cooperative effects between different metal M(n+1)–OH + OH− / M(n+1)c–cO + H2O + e−
nodes that might lower the overpotential.48,57 All systems were
synthesized and their electronic and catalytic properties were M(n)c cOH + OH− / M(n+1)c–cO + H2O + e−
characterized combining in-depth computational analyses with
experimental spectroscopic and cyclic voltammetry measure-
ments. The large number of systems investigated and the inte- (iii)
gration of theory and experiments allowed us to obtain clear-cut
insights into the electronic and geometric effects that inuence M(n+2)]O + OH− / M(n+1)–O–OH + e−
the oxygen evolution electrocatalytic activity of a material.
M(n+1)c–cO + OH− / M(n)c cO–OH + e−
2. Methods
(iv)
2.1 Mechanistic aspects
The commonly accepted mechanism for the electrocatalytic M(n+1)–O–OH + OH− / M(n) + O2 + H2O + e−
OER under alkaline conditions involves four electron transfer
steps:26,58 M(n)c cO–OH + OH− / M(n) + O2 + H2O + e−
Fig. 1 (a) 3D atomic representation of the CP structures for the systems considered in this work. (b) PXRD patterns of (trans,cis)-NiNi (black),
(trans,cis)-NiCo (red), (trans,cis)-NiMn (blue), and (trans,cis)-NiFe (green). (c) PXRD patterns of (cis)-CoCo (black), (cis)-FeMn (red), (cis)-CoFe
(blue), and (cis)-CoNi (green) samples.
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in which M denotes the metal active center of the catalyst and n Grimme's D3 dispersion correction and Becke–Johnson damp-
its formal oxidation state. For each oxidative step, an electron ing.61,62 The Ahlrichs def2-TZVP(-f) basis set was used for all the
can be removed from either the metal or the oxygenated moiety. calculations, unless otherwise specied.63 The role of the envi-
In the latter case, this process does not lead to a change in the ronment was modeled using an implicit solvation scheme (C-
formal oxidation state at the metal center (vide infra). In the PCM).64 The dielectric constant of water was used as a model.
present example, M features a single uncoordinated site that Thermal and entropy corrections were computed at 298 K. This
can be occupied by the incoming OH−. Computational analysis computational protocol is denoted hereaer as B3LYP-D3+C-
(vide infra) revealed that dissociation of a single water molecule PCM(Water)/def2-TZVP(-f). Excited states were calculated at
requires a minimum energy penalty (see Tables S14–S24†). the same level of theory within the TDDFT framework. Unless
Herein, we do not consider the alternative mechanism in which otherwise specied, the Tamm–Dancoff Approximation (TDA)
the O–O bond formation involves the coupling of two separate was used in all TDDFT calculations.
metal-oxo moieties due to the large distance between the metal
nodes in the CP studied in the present work. The procedure 2.3 Synthesis, characterization, electrochemical and
used to obtain the reaction free energies of these steps from the stability measurements
free energies of the intermediates is described in ref. 26 and 58
(see eqn (S1)–(S17)†). The synthesis of homometallic [M1M1(oxo)2(H2O)2] CPs was
To elucidate the electronic structure effects on the catalytic carried out as discussed in ref. 55 and is detailed in Section S3
activity, it is necessary to compute the energies and properties in the ESI.† Novel heterobimetallic [M1M2(oxo)2(H2O)2] CPs
of CPs for all possible spin states [low-spin (LS), intermediate- were synthesized analogously, adjusting the relative amounts of
spin (IS), and high-spin (HS)] and for all reaction intermedi- the two metal precursors, as described in the ESI.† The crystal
ates. Only the spin state with the lowest energy for each inter- structure of representative samples was rened using powder X-
mediate should be considered when drawing reaction free ray diffraction (PXRD) data with the Rietveld method, on the
energy proles. This procedure should be carried out for all the basis of literature crystallographic data.55,56 UV-Vis spectro-
systems investigated in this work in order to draw useful scopic measurements of the solid samples were recorded using
(electronic)structure–activity correlations. Clearly, this requires a Cary4000 (Varian Inc., Palo Alto, California, USA) spectro-
the accurate calculation of hundreds of relative energies in photometer, equipped with a 150 mm integration sphere, which
alkaline solution, which is difficult to achieve with standard uses a barium sulphate tablet as a reference. The spectra are
computational methodologies. processed with the Kubelka–Munk function.
To address this challenge, we developed a cost-effective yet The electrocatalytic properties of these materials for the OER
accurate computational protocol that relies on an “embedded” were investigated in a three-electrode cell containing 1 M KOH
cluster model approach. A molecular cluster model59 was solution at room temperature (see Section S4†). A glassy carbon
dened with two metal centers fully coordinated by water and surface was modied with catalysts via the drop-casting method
oxonato ligands. The environment, i.e., the remaining of the and used as the working electrode. Carbon nanotubes (CNTs)
polymer system and (if present) the water solvent, was treated were introduced to mix with the electrocatalysts to improve
using an implicit solvation approach. The cluster model conductivity. Tafel slopes were obtained from linear sweep
geometry was obtained from the experimental crystal structure voltammetry (LSV) curves recorded at a scan rate of 5 mV s−1
and then optimized at the DFT level. When needed, a series of (Fig. S4†). The stability of CPs under catalytic conditions was
cluster models were generated for the same polymer to mimic tested by continuously cycling the potential from 0.918 to
different coordination environment combinations (vide infra). 1.918 V vs. RHE at a 100 mV s−1 scan rate (Fig. S5†). These
For each of these models, the energy and the optical properties ndings are corroborated by Raman, SEM, and EDX character-
were computed for various spin states at the Density Functional ization, as discussed in the following.
Theory (DFT) level using various exchange correlation func-
tionals and computational settings. The resulting absorption 3. Results and discussion
spectra were compared with those measured experimentally in
the solid state, which served as a calibration point for our 3.1 Geometric and electronic structure of the catalysts
computational protocol (see Fig. S12–S14†). The structures and labels of the synthesized CPs are shown in
Fig. 1a. Depending on the metals used in the synthesis, two
different CP families were identied through X-ray character-
2.2 Computational details ization featuring slightly different coordination environments
All calculations were carried out using the ORCA quantum for the metal ions, in which the nitrogen atoms of the oxonato
chemistry program package based on a development version of ligands are placed in the relative trans or cis position.
ORCA 5.0.3.60 Due the complex electronic structure of the open In the trans environment, the two nitrogen atoms (blue) are
shell transition metal systems investigated in this work, the on opposite faces of the octahedron, while in the cis environ-
trust-region augmented Hessian approach (TRAH-SCF) was ment the two nitrogen atoms are coordinated 90° apart from
used to facilitate the convergence of the SCF iterations in one another with respect to the metal center. Henceforth, we
unrestricted Kohn–Sham calculations. Geometry optimization will denote as (trans,cis)-M1M1 the homometallic polymers
was carried out using the B3LYP functional together with where the trans and the (L)-cis coordination environments
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alternate along the structure, and as (cis)-M1M1 the ones where / p*oxo excitations. For the other samples ((trans,cis)-NiCo,
the nodes show only the (D)-cis coordination environment (M = (trans,cis)-NiMn, (cis)-NiCo, (trans,cis)-NiNi and (cis)-CoCo),
Mn, Fe, Co, Ni). For the heterobimetallic polymers, we will use visible features with lower intensity are observed which can all
the notation (trans,cis)-M1M2 and (cis)-M1M2. These two be attributed to localized d–d transitions. For the Co-containing
families were easily identied by powder X-ray diffraction CPs, such features appear with higher intensity in the experi-
(PXRD) characterization, because they showed different mental spectra compared to the computed spectra.
patterns (Fig. 1b and c). Within each family, the powder It is important to emphasize here that the metal center spin
patterns are only slightly affected by the nature of metal centers, state has a huge inuence on the CP photophysical properties,
thus indicating that the introduction of a second metal ion does inuencing both the intensity and the energy of the key elec-
not lead to any signicant structural variation with respect to tronic transitions (see Fig. S15–S18†). However, the absorption
the homometallic counterparts. Rietveld renements of the spectra computed for the DFT ground state match well with
structure of (cis)-CoCo, (trans,cis)-NiNi, and (trans,cis)-NiMn those experimentally measured. This remarkable agreement
using PXRD data from a conventional diffractometer provided between theory and experiment served as a rst validation of
results in close agreement with the reference structural data.55,56 our computational protocol and allowed us to establish the
The experimental absorption spectra of the solid samples most likely spin state at the metal centers for all the CPs
were compared with those obtained at the DFT level (Fig. 2a and considered in this work.
b). For all systems, computational analysis (see Fig. S25–S30†)
revealed that the band at the highest energy (below 400 nm) is
characterized by electronic transitions from delocalized metal– 3.2 Electrochemical measurements
ligand orbitals to the p* orbital of the oxonato ligand ðp*oxo Þ. In Having established the geometric and electronic structures of
all Fe-containing systems, i.e., (trans,cis)-NiFe, (cis)-CoFe, and the catalysts in their ground state, we moved to the character-
(cis)-MnFe, additional intense absorption features are observed ization of their electrocatalytic properties through cyclic vol-
in the 400–600 nm range and they all correspond to Fe-ligand tammetry experiments under alkaline conditions (Fig. 3). It is
Fig. 2 (a) Computed (red) vs. experimental (black) UV/Vis spectra for the heterobimetallic CPs, together with an illustrative scheme of the
electronic configuration of the d orbitals at the metal centers. For the (trans,cis)-M1M2 case, the computed spectrum is the convolution of the
spectra obtained considering both possible cluster environment configurations, i.e., M1(trans)M2(cis) and M1(cis)M2(trans). (b) Computed (red) vs.
experimental (black) UV/Vis spectra for the homometallic CPs, together with an illustrative scheme of the electronic configuration of the
d orbitals in their pseudo-octahedral ligand field.
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important to emphasize that the incorporation of a second rate (Fig. S5†). The gradual decrease in catalytic current indi-
metal in the CP-backbone did not result in any change of its cates the limited stability of CPs under OER electrocatalytic
structure, both in terms of the coordination surrounding of the conditions. However, since the h10 is taken from the rst cycle,
metal center and in the topological structure of the CP, as where no degradation has occurred, the electrocatalytic
conrmed by UV-Vis and PXRD data. Thus, the electrocatalytic performances can be directly related to the electronic structure
performances of CPs can be attributed, to a large extent, to the of the as-synthesized CPs.
intrinsic activity of the active site, which depends on the specic Both the measured overpotentials and the Tafel slopes show
electronic properties of the metal ion (see the note for Fig. S6 a clear catalytic trend, highlighting the direct dependence of the
and S7†). CP activity on the metal nature. Remarkably enough, the most
The electrocatalytic performance of CPs was compared by efficient CPs (i.e., those with a lower overpotential) contain Fe
evaluating their overpotential at a current density of 10 mA ions. In particular, the catalyst with the lowest overpotential is
cm−2 (h10). The h10 for each catalytic system was obtained by (trans,cis)-NiFe (303 mV), which is closely followed by (cis)-CoFe
averaging the values recorded from the rst CV of four inde- (350 mV). These gures well compare with that of the bench-
pendently prepared working electrodes (WEs). As shown in Fig. mark IrO2 (289 mV) electrocatalyst. The excellent OER kinetics
S3,† the excellent overlapping of the CVs of different working of Fe-containing CPs, approaching that of the best performing
electrodes demonstrates the good reproducibility of the cata- materials,65 was further highlighted by their smaller Tafel slope.
lytic system and the accuracy of the results. The stability of CPs For instance, extremely low Tafel slopes of 37.3 and 34.7 mV
under catalytic conditions was tested by continuously cycling dec−1 were obtained for (trans,cis)-NiFe and (cis)-CoFe,
the potential from 0.918 to 1.918 V vs. RHE at a 100 mV s−1 scan respectively. These results suggest that the Fe centers, which are
Fig. 3 (a) Cyclic voltammetry curves for all synthesized CPs in 1 M KOH with a scan rate of 100 mV s−1 (the reverse scan was omitted for clarity).
(b) Experimental overpotentials of CPs obtained at j = 10 mA cm−2. (c) Tafel plots obtained from LSV curves recorded at a 5 mV s−1 scan rate (see
Fig. S3†) and (d) histogram of Tafel slopes.
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present in both systems, feature an intrinsic catalytic activity evidence that the changes observed in the Raman features upon
that is only slightly modulated by ion mixing with different treatment with KOH are associated with water deprotonation.
metals. The fact that homometallic (cis,trans)-NiNi (h10 = This has a strong inuence on the Fe–Owater vibrations, which
500 mV and Tafel slope = 83.8 mV dec−1) and (cis)-CoCo (h = are drastically affected in both energy and intensity.
424 mV and Tafel slope = 64.9 mV dec−1) feature widely It is important to emphasize here that no further changes in
different catalytic activity provides further evidence of the the band shape of the signals are noticeable aer the material
special role of the Fe centers in this context. This nding is has been subjected to 50 CVs, indicating that the catalyst
especially interesting considering that, in most cases of the remains stable under catalytic potentials. Indeed, elemental
electrocatalytic OER on CPs, it is generally assumed that the EDX analysis (Fig. 5 and Table S3†) and SEM images (Fig. S9 and
reaction occurs at the Ni sites whenever Ni ions are present.54 S10†) provide further evidence for the stability of the catalysts,
Interestingly, recent computational studies50,51,66 suggested

a signicant activity for the Fe centers in 1D coordination
polymers, MOFs and metal oxides, which would be consistent
with the experimental ndings presented in this work. These
intriguing results deserve a more detailed discussion and
computational analysis.
3.3 Stability analysis

In this section, our aim is to assess the stability of the CPs under
catalytic conditions in order to establish a solid foundation
upon which the exploration of their structure–activity relation-
ship is initiated. Hence, Raman spectra, SEM images and EDX
analysis were carried out in order to characterize the (trans,cis)-
NiFe sample structurally and morphologically.
Initially, matrix effects on the Raman signals were evaluated,
and no changes in the band structure were identied once the
polymer is embedded in the carbon nanotube, as shown in Fig.
S8.† The comparison between the computed Raman spectrum
for our cluster model and the experimental spectrum associated
with the embedded polymer is reported in Fig. 4a. Strikingly,
the computed and experimental spectra exhibit remarkable
similarity, with all experimental features accurately replicated.
The characteristic signals of Ni–O bonding67,68 (474.5 and
544.6 cm−1) and Fe–O/N vibrations69,70 (599.8 cm−1) are
observed. The band centred at 628.7 and 700.5 cm−1 could be
assigned to the displacement of the C–N bond connected to the
Fe atom.71
To assess the stability of the catalyst under operando
conditions, these analyses were repeated on the material under
three different experimental conditions: (i) aer treatment with
a 1 M KOH solution; (ii) aer 1 CV; (iii) aer 50 CVs (Fig. 4b, top
panel).
An obvious change in the structure of the Raman signals was
observed upon treatment with 1 M KOH solution at zero
potential, with several signals showing a remarkable increase in
intensity. This effect could be attributed to the change in the
polarization of the bonds following treatment with KOH, e.g.,
due to partial deprotonation of the H2O molecules coordinated
to the metal centres. To verify this hypothesis, calculations were
run to assess the origin of the change in the shape and intensity
of the Raman peaks aer treatment with KOH. Specically,
Raman spectra were computed by gradually deprotonating the Fig. 4 (a) Experimental Raman spectrum of embedded (trans,cis)-
NiFe (solid black) and the computed one. (b) Top: experimental Raman
water molecules coordinated to the two metals. Fig. 4b (lower
spectra of embedded (trans,cis)-NiFe (solid grey), after KOH treatment
panel) shows the results obtained for the cluster model where (solid red), after 1 CV (solid blue) and after 50 CV (solid green). Bottom:
Fe is coordinated by two OH−. The remarkable agreement computed Raman spectra for (trans,cis)-NiFe (dashed grey) and
between theory and experiment in this case provides strong (trans,cis)-NiFe with two OH− coordinated to Fe (dashed red).
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Fig. 5 EDX elemental analysis of Fe (a1)–(d1) and Ni (a2)–(d2). (a) NTC matrix + (trans,cis)-NiFe untreated; (b) NTC matrix + (trans,cis)-NiFe
treated with KOH; (c) NTC matrix + (trans,cis)-NiFe treated with KOH after 1CV; (d) NTC matrix + (trans,cis)-NiFe treated with KOH after 50 CVs.
demonstrating that there are no particular morphological or While the computed overpotentials are shied to higher
compositional changes in the analysed samples under oper- values than the experimental ones, the overall catalytic trend is
ando conditions. retained, which provides another validation of our computa-
Overall, the combination of experimental and computational tional protocol as well as further evidence for the structural
results provides compelling evidence for catalyst stability under stability of CPs. This is especially remarkable considering the
the experimental conditions. drastically different electronic properties of the metal centers
(vide infra) and the complex nature of the systems investigated
in this work. Again, the most active catalysts contain Fe2+ ions,
3.4 Identication of the active metal centers followed by those incorporating Co2+ and nally by Ni2+.
For CPs featuring different metals (heterobimetallic) and/or In all cases, the rate determining step of the reaction is MOH
coordination environments (cis or trans), the OER mechanism / MO. The only exceptions were found for (cis)-CoFe and (cis)-
was investigated computationally by considering all possible MnFe, for which the MOH / MO and MO / MOOH steps
metal/coordination environment combinations. The combina- feature essentially the same energy. As it will be discussed in the
tion leading to the lower computed overpotential was identied following sections in greater detail, this effect originates from
as the active site of the reaction. The computed and experi- the peculiar electronic properties of the Fe centers.
mental overpotentials for all the systems investigated in this Remarkably enough, spin effects play a fundamental role in
work are compared in Table 1. these systems. Enforcing the same spin conguration at the
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Table 1 Experimental (hexp) and computed (htheory) overpotentials and assignments should be taken with caution. During the OER, the
rate determining step (RDS) for the OER on CPs. The active metal is actual oxidation state of the metal centers is best described in
emphasized in red. Unless otherwise specified, the active metal was
a continuum that ranges from +2 (the electron is removed from
placed in the cis coordination environment
the ligand) to +3 (the electron is removed from the metal), as
hexp htheory discussed in Section 2.1.
CP (eV) (eV) RDS Importantly, our computational results indicate that, once
the active metal node is oxidized, the oxidation of the neigh-
0.30 0.56a MOH / MO
boring metal nodes is disfavored. For example, the potential
0.35 0.52 MO / MOOH required to oxidize nickel(II) to nickel(III) in (trans,cis)-NiFe
0.42 0.59 MO / MOOH increases by ca. 0.2 V aer step (i) on Fe. These results are
consistent with prior experimental studies from the group of

0.42 0.60 b
MOH / MO
Prof. Peter Strasser,72 which demonstrated the presence of
0.43 0.69 MOH / MO a large fraction of reduced Ni(II) in Ni–Fe catalysts at catalytic
0.46 0.68 MOH / MO potential. For this reason, in the OER proles shown in Fig. 6,
the oxidation state of the neighboring metal nodes was kept
0.49 0.86 MOH / MO
constant thorough the reaction at the value it has in the catalyst
0.50 0.94c MOH / MO ground state (+2).
For these systems, the rate determining step is the PCET
a
For the OER on the Fe site htheory = 0.56 eV for both cis and trans leading to the formation of the MO intermediate. This is the
coordination environments. For the OER on the Ni site, htheory =
0.95 eV. b If the electronic structure of the active site is constrained to most common situation among the catalysts studied in this
4
Co(II), htheory = 0.92 eV. c If the electronic structure of the active site work. Importantly, different metals show different evolution of
is constrained to 3Ni(II), htheory = 1.27 eV. the electronic conguration along the reaction path.
The OER on (cis)-CoCo is characterized by multiple spin
metal center along the reaction prole introduces a huge error transitions along the reaction path (see Fig. 6a). Step (i) leads to
in the overpotential estimate, which amounts to ca. 0.3 eV for a change in both the formal oxidation state and the spin
both (trans,cis)-NiNi and (cis)-CoCo. In the former, neglecting conguration of the active metal, which goes from Co(d7)/HS in
spin transitions even leads to a change in the estimated rate Co(III) to Co(d6)/LS in Co(III)–OH. Aer the subsequent rate
determining step of the reaction from MOH / MO to M / determining step (ii), the metal assumes a Co(d6)/IS congura-
MOH. Importantly, (trans,cis)-NiFe and (trans,cis)-NiNi feature tion with two unpaired electrons, while one additional unpaired
almost identical overpotentials when the reaction takes place at electron is located at the oxygen [Co(III)c–cO]. Importantly, this
the Ni(cis) site. This provides further evidence that cooperativity step is associated with a signicant shortening of the key Co–O
effects between different metal centers are, to a large extent, bond distance from 1.86 Å [Co(III)–OH] to 1.63 Å [Co(III)c–cO],
either independent from the metal nature or negligible for the which is accompanied by a corresponding increase in the Co–O
CPs considered in this work, consistent with the experimental Mayer bond order from 0.91 to 1.71. These results suggest that
ndings discussed above. In addition, the results obtained for for (cis)-CoCo the adsorption energy of the oxygen containing
(trans,cis)-NiFe for different metal sites suggest that the Fe ligand increases from MOH to MO. To a large extent, this effect
nodes (in either cis or trans congurations) are indeed the active is responsible for the low overpotential computed for this
sites of the reaction, which is again consistent with experi- system, consistent with the experimental ndings. The subse-
mental observations. Interestingly, the cis/trans nature of the quent step (iii) leads to a Co(d6)/LS metal with no unpaired
coordination environment has a negligible effect on the over- electrons [Co(III)–OOH]. Both the Co–O distance and the Mayer
potential (therefore, unless otherwise specied, only the cis bond order in Co(III)–OOH are similar to those obtained for
coordination environment is considered in the subsequent Co(III)–OH, being 1.88 Å and 0.89, respectively. Finally, step (iv)
calculations). It can thus be concluded that in heterobimetallic regenerates the catalyst and releases O2.
CPs one transition metal acts as the main active site while the The OER on (trans,cis)-NiFe shows a different evolution of
other has a structural role. the electronic structure of the metal center along the reaction
path. As discussed above, the active site in this case is the Fe
center, which invariably assumes the highest possible spin
3.5 Metal electronic structure evolution along the reaction conguration (Fig. 6b). Step (i) in this case does not change
prole signicantly either the oxidation state or the electronic struc-
The free energy diagrams for the OER on (cis)-CoCo, (trans,cis)- ture of the metal, which can be described as Fe(d6)/HS for both
NiFe and (trans,cis)-NiNi are shown in Fig. 6, together with M [Fe(II)] and MOH [Fe(II)c cOH]. In contrast, the rate deter-
a graphical representation of the corresponding variations in mining step (ii) oxidizes the metal to Fe(d5)/HS [Fe(III)c–cO].
the metal electronic structure along the reaction prole. For the Consistent with the (cis)-CoCo case, this step is associated with
sake of clarity, the formal oxidation state and the estimated spin a signicant shortening of the Fe–O bond (1.86 Å / 1.63 Å) and
multiplicity at the metal centers are shown in Fig. 6. However, with an increase in the Fe–O Mayer bond order (1.0 / 1.8).
since electrons are typically removed from orbitals that are Again, these results are consistent with an increase in the ligand
delocalized between the metal and the ligand, such adsorption energy in the rate determining step of the reaction,
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and hence with the low overpotential experimentally measured. leaving the metal center largely unaltered in its Ni(d7)/LS state
Step (iii) gives back Fe(d6)/HS [Fe(II)–OOH], a M–O bond [Ni(III)c–cO]. These results differ from those just discussed for
distance of 1.90 Å and a Mayer bond order of 0.93. The last step different active metals, in which the metal is either oxidized or
regenerates the catalysts and releases O2. promoted to a different spin state in the rate determining step.
The variations in the electronic structure of Ni during the Remarkably enough, only slight variations in the Ni–O
OER on (trans,cis)-NiNi are especially interesting (Fig. 6c). Step distances and bond orders were observed in this case; the Ni–O
(i) in this case removes one electron from the metal center, bond decreases from 1.84 Å in MOH to 1.78 Å in MO, which is
leading to a Ni(d7) metal with a single unpaired electron [Ni(III)– accompanied by a minor increase in the Ni–O Mayer bond order
OH]. The free reaction energy for this step amounts to 1.97 V, (0.89 / 0.92). These results suggest that for (trans,cis)-NiNi the
indicating that ligand absorption in this system is compara- ligand adsorption energy does not increase signicantly on
tively less favorable than in (cis)-Co and (trans,cis)-NiFe. The going from MOH to MO, in striking contrast to the other cases
subsequent rate determining step (ii) oxidizes the axial ligand, discussed above. This observation is consistent with the larger
Fig. 6 OER free energy profile (left) and spin density evolution along the reaction path (right) for (a) (cis)-CoCo, (b) (trans,cis)-NiFe and (c)
(trans,cis)-NiNi. To facilitate the chemical interpretation of the results, the metal oxidation state and local spin configuration are also reported.
They were determined using Mulliken spin populations (they were rounded up to the nearest integer). The free energies for the other catalysts
considered in this work can be found in Tables S14–S24.†
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computed and experimental overpotentials for (trans,cis)-NiNi. hypothesis is that inducing a change in the electronic structure
Finally, the Ni center in MOOH can be described as Ni(d8) with of the metal along the energy prole, e.g., through appropriate
two unpaired electrons [Ni(II)c cO–OH]. Interestingly, the Ni–O ligand design strategies, could in principle inuence the rela-
distance in MOOH amounts to 2.22 Å, while the corresponding tive adsorption energies of the oxygen-containing ligands, thus
Mayer bond order is just 0.26. These results suggest an breaking the relationship between the free energies of the
extremely weak ligand adsorption energy in MOOH for this intermediates along the reaction prole.
system, which is consistent with the computed free energy For (cis)-CoCo and (trans,cis)-NiFe, this is not the case. The
variation for step (iv). metal centers in these systems feature the same electronic
structure in both MOH and MOOH, i.e., Co(d6)/LS and Fe(d6)/
HS for (cis)-CoCo and (trans,cis)-NiFe, respectively. In addi-

3.6 Breaking linear scaling relationships tion, no signicant variations were observed in the metal–
The results just described emphasize that variations in the ligand distance and bond order between these two intermedi-
electronic structure of the metal center have a huge impact on ates. Consistent with the discussion above, the free energy
the intermediate adsorption energies and hence on the catalyst difference between these intermediates is indeed fairly close to
efficiency. We believe that this effect can be exploited in prac- 3.2 eV for both catalysts, being 3.27 eV and 3.52 eV for (cis)-
tical applications. CoCo and (trans,cis)-NiFe, respectively. The excellent perfor-
For example, it has been shown26,27 that the energies of the mance of (trans,cis)-NiFe originates from the fact that the free
MOH and MOOH intermediates are strongly related, displaying energy of the MO intermediate lies exactly halfway between
a linear correlation over a large number of systems with those of MOH and MOOH, and hence the two MOH / MO and
different nature and properties. The chemical origin of this MO / MOOH steps require exactly the same energy.
effect has been attributed to the bond order conservation In contrast, (trans,cis)-NiNi shows a different metal elec-
principle.73 The linear correlation implies that the free energy tronic structure for MOH [Ni(d7) with one unpaired electron]
difference between those intermediates is roughly constant, and MOOH [Ni(d8) with two unpaired electrons]. Remarkably
and in fact it typically amounts to ca. 3.2 eV (the exact value enough, the energy difference between the MOH and MOOH
might change depending on the specic exchange correlation intermediates in this case is just 2.90 eV, which is lower than
functional employed for the calculations).26,27 As each step in that computed for all the other systems investigated in this
the OER mechanism has a thermodynamic limit of 1.23 eV, it work. In this case, this partial breaking in the linear scaling
poses a theoretical limit of 0.3–0.4 V (3.2–1.23 × 2 eV) to the relationships does not lead to a lower overpotential due to the
minimal overpotential that can be obtained for the OER. Our large reaction free energies associated with steps (i) and (ii). For
step (ii), this effect originates from the peculiar electronic
structure of the MO intermediate in this system (see the
discussion above), which is closer in energy to MOOH than to
MOH. However, these results conrm our assumption that
variations in the electronic structure of the metal center can in
principle be exploited to break the linear scaling relationships
between the OER intermediates.
To explore the validity of these ndings over a broader set of
systems, we report in Fig. 7 the relative energy between the
MOOH and MOH intermediates, as well as its decomposition
into the free energy associated with the MOH / MO and MO /
MOOH steps for all the CPs investigated in this work.
Based on these data, three main considerations can be
drawn concerning the relationship between the metal electronic
structure in coordination polymers and their catalytic activity:
(i) The electronic interaction between different metal centers
has a weak inuence on the free energy proles and hence on
the catalytic activity, consistent with the experimental results
discussed above. Thus, ion mixing has mainly a structural effect
in the systems considered here. However, the use of ligands
with different electronic and geometric properties could have
Fig. 7 Free energy difference between the MOOH and MOH inter- a deep impact on metal–metal cooperativity, and hence
mediates as well as its decomposition into the MOH / MO (orange different ligand/metal combinations should be explored in
bar) and MO / MOOH (blue bar) reaction free energies. The hori- future studies.
zontal black lines represent the ideal case in which both steps have the
(ii) When the active site is Fe, the MOH / MO and MO /
same energy. The dashed violet horizontal line represents the theo-
retical value for the energy difference between MOOH and MOH MOOH steps always feature essentially the same energy, as in
obtained from linear scaling relationships. The active metal is the ideal catalyst case. This effect originates from electronic
emphasized in red. structure effects modulating the ligand adsorption energies in
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these systems. This seems to be the main effect responsible for activity. It was found that spin transitions lower the over-
the greater efficiency for the electrocatalytic OER on Fe- potential by as much as 0.3 eV and that electronic structure
containing CPs, consistent with the experimental observation. effects modulating the ligand adsorption energy are crucial to
(iii) The only system featuring a free energy difference increase catalyst efficiency. Finally, we demonstrated that
between the MOOH and MOH intermediates that is lower than a change in the electronic structure of the metal along the
the 3.2 eV limit is (trans,cis)-NiNi, which is also the only system energy prole can be used to break the linear scaling relation-
for which the electronic structure of the metal center changes ship between the energies of the MOH and MOOH intermedi-
on going from MOH to MOOH. Hopefully, the electronic ates, which currently poses a theoretical lower bound to the
structure effects of this kind could be exploited in practical experimental overpotential. We believe that our study provides
applications to circumvent the theoretical limit for the electro- the basis to exploit such electronic structure effects in water
catalytic OER. Novel design strategies should be explored to splitting technologies through appropriate ligands.
selectively stabilize specic reaction intermediates along the
reaction prole, e.g., by modulating the electron-donating Data availability
ability of the ligand. Efforts to exploit such electronic structure
effects are currently underway in our laboratory. The computational and experimental procedures as well as all
the relevant data generated and analysed in this study are
4. Conclusions available in the manuscript and its ESI.† Additional raw and
unprocessed data are available from the corresponding author
This work provides evidence for the notion that electronic on reasonable request.
structure effects, such as spin transitions or variations in the
transition metal oxidation state during the electrocatalytic OER, Author contributions
play a fundamental role in determining the reaction efficiency;
manipulating the electronic structure of the reaction interme- L. B. performed all the calculations. L. B. prepared most of the
diates with appropriate design strategies could pave the way for gures in the Article. G. M. R. conceptualized and synthesized
the development of new catalysts with lower overpotentials. A all catalysts. I. D. A. and G. M. R. tested their catalytic perfor-
systematic exploitation of (electronic) structure–property rela- mances. A. M. G. and L. L. performed UV-vis, Raman, SEM and
tionships in hydrogen production technologies is hampered by EDX measurements and analyzed the data preparing the graphs
the complexity of the catalytic system, which limits the ability of and Figures. R. V. performed PXRD characterization. L. B. and
current experimental and computational methodologies to G. B. wrote the original dra of the manuscript with input from
provide detailed information into the evolution of the metal all authors. All authors discussed the results and contributed to
electronic structure during the reaction. the nal version of the manuscript. G. M. R. and G. B. directed
In the case study presented here, we discussed one- the study.
dimensional coordination polymers of earth-abundant metals,
which are characterized by active sites with well-dened Conflicts of interest
geometric and electronic properties that can be readily corre-
lated with their oxygen evolution electrocatalytic activity. In There are no conicts to declare.
particular, we focused on one-dimensional coordination poly-
mers in which metal ions (Ni2+, Co2+, and Fe2+), in a pseudo- Acknowledgements
octahedral environment, bearing two oxonato bridging
ligands and two water molecules in the rst coordination This work has been funded by the European Union – NextGe-
sphere. Both homometallic and novel heterobimetallic CPs nerationEU under the Italian Ministry of University and
were synthesized and their oxygen evolution electrocatalytic Research (MUR) National Innovation Ecosystem grant
activity under alkaline conditions was determined experimen- ECS00000041 – VITALITY. We acknowledge the Università degli
tally. The electronic structure of catalysts and reaction inter- Studi di Perugia and MUR for support within the project
mediates was characterized combining spectroscopic Vitality, PON – Ricerca e Innovazione – DM 1062, and Fondo
measurements with an experimentally validated computational Ricerca di Ateneo, edizione 2021. We also thank the Fondazione
protocol. Perugia (project 21101 and 2022.0405) for supporting our
The acquired mechanistic information suggests that in this research.
case the OER involves a single metal center. The most active
centers are Fe2+ ions, followed by Co2+ and nally by Ni2+. Ion References
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Metal Complex Role in HER and OER

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Chemical

Harnessing the electronic structure of active metals

to lower the overpotential of the electrocatalytic

Cite this: DOI: 10.1039/d3sc05891c

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hydrogen production eﬃciency, leading to high overpotentials.3

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asymmetric unit contains one metal ion exhibiting a slightly (i)

and their utilization as electrocatalysts. They were designed to

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Interestingly, recent computational studies50,51,66 suggested

3.3 Stability analysis

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consistent with prior experimental studies from the group of

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HS for (cis)-CoCo and (trans,cis)-NiFe, respectively. In addi-

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