Nanostructured Hydrotreating Catalysts For Electrochemical Hydrogen Evolution.
Nanostructured Hydrotreating Catalysts For Electrochemical Hydrogen Evolution.
Nanostructured Hydrotreating Catalysts For Electrochemical Hydrogen Evolution.
Progress in catalysis is driven by society’s needs. The development of new electrocatalysts to make
renewable and clean fuels from abundant and easily accessible resources is among the most challenging
and demanding tasks for today’s scientists and engineers. The electrochemical splitting of water into
hydrogen and oxygen has been known for over 200 years, but in the last decade and motivated by the
perspective of solar hydrogen production, new catalysts made of earth-abundant materials have emerged.
Received 20th December 2013 Here we present an overview of recent developments in the non-noble metal catalysts for electrochemical
DOI: 10.1039/c3cs60468c hydrogen evolution reaction (HER). Emphasis is given to the nanostructuring of industrially relevant
hydrotreating catalysts as potential HER electrocatalysts. The new syntheses and nanostructuring approaches
www.rsc.org/csr might pave the way for future development of highly efficient catalysts for energy conversion.
1. Introduction because it is the molecule with the highest energy density per
unit mass, and when combusted in an engine or transformed into
Molecular hydrogen (H2) has been considered as an energy electricity in a fuel cell, it produces only water as the byproduct.
carrier since the beginning of the 1970’s.1 A hydrogen fuel In comparison, carbon-based fuels produce water and CO2.
community has been imagined where excess energy from renew- Although hydrogen is the most abundant element on earth,
able sources is not fed into the grid, but stored in the form of it does not exist as a free molecule, and consequently, efficient
H2 to be later transformed into electricity, used directly as fuel, and sustainable H2 production technologies are required. Today,
or used as a pillar to sustain a future ‘‘methanol economy’’.2,3 most H2 is produced from fossil resources through a steam
The implementation of H2 as an energy carrier is desirable reforming process where steam reacts with hydrocarbons to
give H2 and CO2.4 This H2 production method consumes fossil
fuels and still emits CO2. A clean and renewable method of H2
Laboratory of Inorganic Synthesis and Catalysis, Institute of Chemical Sciences and
Engineering, École Polytechnique Fédérale de Lausanne (EPFL), EPFL-ISIC-LSCI,
production is electrolysis of water using renewable energies, in
BCH 3305, Lausanne, CH 1015, Switzerland. E-mail: [email protected]; particular solar energy (forward direction in Scheme 1).5,6 The
Fax: +41 216939305; Tel: +41 216939781 electrochemical water splitting, first observed in 1789,7,8 is
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potential (overpotential is the difference between the applied 1.1 Electrochemical HER
and thermodynamic potentials of a given electrochemical
Water splitting consists of both OER (eqn (1)) and HER
reaction). Platinum group metals are the most efficient catalysts
(eqn (2)).
for HER, capable of driving significant currents close to the
thermodynamic potential. However, these noble metals are 2H2O(l) - O2(g) + 4H+(aq) + 4e (1)
among the least abundant elements on Earth and are not
sufficiently present to catalyse HER at a scale comparable to 2H+(aq) + 2e - H2(g) (2)
the global energy demand.
The free energy change (DG0) for the conversion of one
This review summarizes the development of heterogeneous
molecule of water into hydrogen and oxygen (Scheme 1)
catalysts made entirely of earth-abundant elements for electro-
under standard temperature and pressure (STP) conditions is
chemical HER. Similar to other heterogeneous catalysts, the
+237.2 kJ per mol of H2. However, extra work is required to
performance of HER catalysts is limited by the density and
expand the gases produced (TDS0), and when this is taken
reactivity of active sites. Furthermore, poor electron transport,
into account, the enthalpy change (DH0 = DG0 + TDS0) is
low surface area and instability under operating conditions are
+286 kJ per mol of H2. These values correspond to a reversible
common pitfalls of these electrocatalysts.9–11 During the last
electrolysis cell voltage of DE0rev,298 = 1.23 V and a thermoneutral
decade, however, significant improvements in efficiency have
(heat is not lost or required) cell voltage of DE0th,298 = 1.48 V for
been achieved through the design of nanostructured catalysts
water splitting. In the ideal case, where TDS0 is supplied by an
that either expose preferentially the most active reaction sites,
external source, the application of only 1.23 V of external potential
or electronically connect a higher number of these sites to the
would be sufficient to start water splitting in an electrochemical
back contact electrode, or both. This strategy is widely applied
cell. In practice, water electrolysis is less efficient and external
to catalysts previously used for the hydrotreating (HDT) of
potentials well above the thermodynamic minimum value of
crude petroleum products.
1.23 V are required. Overpotentials are essential to drive the
We will first describe the basic mechanistic considerations
electron transfer processes at significant rates and to overcome
of HER, followed by an introduction to hydrotreating catalysts.
the kinetic barriers imposed by the high activation energies for
We will then describe how nanostructuring of known hydro-
the formation of reaction intermediates on the surface of the
treating catalysts has led to the preparation of increasingly
electrode. Efficient electrocatalysts are materials that lower
efficient hydrogen evolution electrocatalysts. The review does
these overpotentials.
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necessary to increase or decrease the current density by 10-fold. Therefore, a current density of 10 mA cm 2 can be reached with an
The Tafel slopes have been derived theoretically from the Butler– overpotential of only 30 mV.
Volmer equation for three limiting cases.14 (1) If the discharge Fig. 1 shows that hydrogen evolution takes place through an
reaction is fast and H2 is evolved by a rate-determining combi- absorbed hydrogen intermediate. The Gibbs free energy for
nation reaction, a slope of 2.3RT/2F, that is, 29 mV dec 1 at 25 1C hydrogen adsorption (DGH*) on a metal has been proposed to
should be observed. (2) If the discharge reaction is fast and H2 is be a good descriptor of the intrinsic activity of a metal for
evolved by a rate determining ion + atom reaction, the Tafel slope HER.15–18 A plot of exchange current densities against DGH* has
should be 4.6RT/3F, that is, 38 mV dec 1 at 25 1C. (3) If the a volcano shape. Pt group metals are at the summit of the
discharge reaction is slow, then regardless of whether H2 is volcano, having the highest activity and close to zero hydrogen
evolved by the combination reaction or the ion + atom reaction, absorption energy (Fig. 2).
the Tafel slope should be 4.6RT/F, that is, 116 mV dec 1 at 25 1C. The volcano plot reflects the Sabatier principle. Metals to the left
The exchange current density ( j0) is another important of Pt bind hydrogen atoms too strongly, blocking the active site and
kinetic parameter in electrocatalysis that is correlated to the failing to evolve hydrogen. On the other hand, metals to the right of
rate of electron transfer under reversible conditions (that is, at Pt binds hydrogen too weakly, failing to stabilize the intermediate
zero overpotential). The magnitude of the exchange current state and preventing any reaction from taking place. Quantum
density influences the rate of the electrochemical reaction at chemical calculations showed that DGH* is a good descriptor of
other potentials. The Tafel equation can be used to describe the materials that can catalyse HER and applies not only to pure metals,
current–potential relationship at a significant overpotential (Z): but also to alloys, enzymes and transition metal compounds.16,18
Fig. 2 shows the edge site of MoS2 which has a modest DGH* and a
Z = b log( j/j0) (3) high activity for HER. A good deal of work has been done to prepare
MoS2 materials rich in these edge sites, which is a major subject of
where j is the current density, j0 is the exchange current density
this review. The adsorption free energy of hydrogen on the Ni2P (001)
and b is the Tafel slope.
surface has also been calculated by DFT to be 0.31 eV (ref. 19) and
Ideal catalysts have low Tafel slopes and high exchange current
recently a turn over frequency (TOF) of 0.015 s 1 was estimated at Z =
densities. In reality, however, one sometimes has to compare a
100 mV for an active Ni2P HER electrocatalyst.20 The measured TOF
catalyst with a high exchange current density but also a high Tafel
is equivalent to an exchange current density of j0 = 7.2
slope with another catalyst with a lower exchange current density
10 6 A cm 2, assuming an active site density of 1.5 1015 site cm 2.
but also a smaller Tafel slope. Which catalyst is better depends on
The activity of an electrocatalyst is often expressed as a given
the targeted current density. Let’s take as an example two catalysts,
current density at a given overpotential. In addition to the intrinsic
one with an exchange current density of 10 4 A cm 2 and a Tafel
activity which is related to TOF, the current density also depends on
slope of 100 mV dec 1, and the other with a lower exchange current
the loading of catalysts per area and the density of active sites.
density of 10 6 A cm 2 but a Tafel slope of 40 mV dec 1. To achieve
However, the effect of catalyst loading is not considered here.
a current density of 10 mA cm 2, the former catalyst requires
200 mV of overpotential, while the latter requires only 160 mV.
The latter catalyst is therefore a better catalyst for this appli- 1.3 Hydrotreating
cation. In comparison, Pt has an exchange current density in the Hydrotreating (HDT) or hydroprocessing refers to a variety of
order of 10 3 A cm 2 and a Tafel slope of 30 mV dec 1 for HER. catalytic hydrogenation processes where heteroatoms
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electrochemistry and photochemistry of MoS2 layered crystals,33 nanoscaled pores (Fig. 4b). This material preferentially exposed
but it was not until Nørskov, Chorkendorff, and co-workers a large fraction of edge sites, which, together with its high
showed in 2005 that the edge sites of MoS2 have a good HER surface area, leads to excellent activity for electrochemical
activity that interest in this type of materials as HER catalysts HER.35 Fig. 4c shows the comparison between these two high-
spurred.16 In that seminal work, Mo-edge sites were identified as surface area approaches. The DG structure shows a higher
active sites for HER; the theoretical free energy of adsorption of exchange current density compared to that of the nanowires
hydrogen on this metallic edge is similar to those of Pt and the but also an increased resistance to electron transfer. Variation
active sites of hydrogenases. This was followed by a study that of the electrode thickness with the electrodeposition time of the
made use of model MoS2 catalysts with controlled size and precursor (from 10 s to 1 min) shows that higher surface area
Published on 13 March 2014. Downloaded by University of Hyderabad on 1/14/2020 10:15:35 AM.
morphology. The study showed that the exchange current electrodes can be obtained with longer times. More material is
density of MoS2 nanocrystals is proportional to the length of deposited and the template is filled. Independently of this, the
edge sites but not to the basal areas in truncated MoS2 hexagons. number of active sites per surface area remains quite constant
Such a study confirmed that the edge site is catalytically active as expected when using a nanostructured template with a
for HER.30 Since then, various material and electrode prepara- constant surface to volume ratio throughout all the nanopores
tion methods have been reported for the optimization of MoS2 (Fig. 4d). Thanks to the higher surface area and the higher edge
catalysts. Five main approaches have been taken (i) increasing density, improvement in the total HER activity is observed.
the surface area; (ii) increasing the number of active sites; (iii) However, MoS2 is a semiconducting material and thicker films
improving the electrical contact from the back contact to the increased electron transport resistance, limiting the overall
active sites; (iv) exfoliation of layered MoS2 and WS2; and (v) electrochemical performance at higher current densities. A current
modification of the catalytic reactivity of the MoS2 edge by density of 10 mA cm 2 requires about 240 mV overpotential,
substitution with transition metals such as Co or Ni to form similar to the core–shell MoO3–MoS2 NW electrode.
bimetallic catalytic sites. Approaches (i) to (iv) aim to increase MoS2 and MoSe2 films with vertically aligned layers have
the number of electronically connected active sites per unit also been synthesised through a kinetically controlled rapid
geometric area; the goal is to increase exchange current density growth method that preferentially exposes the thermodynami-
and move upward in the volcano plot shown in Fig. 2. The last cally less stable edge sites over terrace sites (Fig. 5).36 The
approach aims to reduce the intrinsic free energy of adsorption exchange current density measured has average values of
of hydrogen on the active site; the goal is to move a catalyst 2.2 10 6 A cm 2 for MoS2 and 2.0 10 6 A cm 2 for MoSe2.
horizontally towards the middle of the volcano plot. This last The Tafel slopes are in the range of 105–120 mV dec 1,
approach is beyond the scope of this review, so it will only be indicating that the rate limiting step is the Volmer reaction.
mentioned when coupled to a nanostructuring approach. This material can be partially improved by tuning the substrate
A. Higher surface area electrodes. High-aspect ratio archi- morphology and the choice of the material. This synthetic
tectures have been used to improve the activity per geometric method has been extended to prepare first-row transition metal
area and to maximize the diffusion of protons and molecular dichalcogenide37 and MoSe2 and WSe2 catalysts for HER on
hydrogen. Jaramillo and co-workers reported that vertically- curved and rough surfaces.38
oriented core–shell nanowires (NWs) produced by low-temperature Two dimensional MoS2 nanosheets (NS) with a high active site
sulfidization of MoO3 nanowires have high activity for HER. A density were prepared through a microdomain reaction method.39
current density of 10 mA cm 2, which corresponds to the The nanosheets were synthesized by ball-milling a mixture of
photocurrent density expected for a 12% efficiency solar water MoO3 and S8, followed by annealing at high temperatures.
splitting device, requires an overpotential of Z10 = 250 mV. The The MoS2 NS possesses a high number of exposed edge sites
Tafel slope is 50–60 mV dec 1 near the onset of current. The and a thickness of only ca. 2 nm, leading to a high edge/basal
substoichiometric MoO3 core provides a high aspect ratio ratio. The highest active site density was obtained for samples
template and enables facile charge transport, while the con- annealed at 550 1C. The geometrical exchange current density is
formal MoS2 shell provides excellent catalytic activity and in the order of 10 5 A cm 2 and the Tafel slope is 68 mV dec 1.
protection against corrosion in strong acids.34 The nanowires A current density of j = 10 mA cm 2 is reached at a 200 mV
were stable over 10 000 cycles of the cycling stability test. Fig. 4a overpotential.
shows a schematic diagram of the core shell electrode. How- An alternative method to increase the number of active sites
ever, in this high-surface-area structure most of the MoS2 basal is to introduce abundant defects on the basal planes during the
planes were parallel to the nanowire axis as observed in the preparation of MoS2. This can lead to the cracking of the basal
coloured TEM image shown in Fig. 4a, resulting in few edge plane and subsequent exposure of additional active edge
sites exposed at the surface of the nanowires, limiting the HER sites.40 To obtain the defect-rich structure, an excess of
activity of this electrode. thiourea was employed not only as a reducing agent for a
B. Higher surface area with preferential exposure of active heptamolybdate precursor, but also as an efficient additive to
edge sites. High-surface area alone is not sufficient if the stabilize the resulting ultrathin nanosheets. The defect-rich
density of catalytically active sites is low. To address this issue, MoS2 ultrathin nanosheet displays a density of active sites that
Jaramillo and co-workers reported a synthetic method to pro- is 13 times higher than that of bulk MoS2. Current densities as
duce a double-gyroid (DG) MoS2 bicontinuous network with high as 13 mA cm 2 are obtained at 200 mV overpotential, with
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Fig. 4 (a) Schematic representation of MoO3–MoS2 core–shell nanowires (NW) for HER. Zoom-in box: coloured TEM image of the internal morphology
of the nanowire. Adapted with permission from ref. 34, copyright 2011, American Chemical Society. (b) Structural model of mesoporous MoS2 with a
double-gyroid (DG) morphology. Zoom-in box: TEM image of double-gyroid MoS2 where [311] and [211] projections of the double-gyroid structure
are observed. The pore-to-pore distance is B7 nm as indicated by the white arrows. (c) Tafel plot of double-gyroid MoS2 (1 min) versus core–shell
MoO3–MoS2 nanowires, showing the 50 mV per decade Tafel slope. (d) Ratios of surface area, density of active sites per surface area and total
HER activity of the various double-gyroid MoS2 films versus the nanowires. Figures (b)–(d) are adapted with permission from ref. 35, copyright 2012,
Nature Publishing Group.
a Tafel slope of 50 mV dec 1. Variation of the crystallization layers and a highly conductive underlying graphene network.43
temperature showed that lower temperature facilitates the The coupling/interaction of MoS2 with GO led to the selective
formation of oxygen-incorporated ultrathin nanosheets.41 The growth of highly dispersed MoS2 nanoparticles on GO. In
nanosheets prepared at lower temperatures have an improved strong contrast to aggregated MoS2 particles grown freely in
conductivity and exhibit simultaneously a high number of solution without GO, the MoS2–RGO hybrid exhibited superior
active sites and a good conductivity.41 Current densities of j = electrocatalytic HER activity relative to other MoS2 catalysts
10 and 126 mA cm 2 are obtained at Z = 180 and 300 mV, (Fig. 6). A Tafel slope of B41 mV dec 1 was obtained suggesting
respectively. These current densities are among the highest for the Volmer–Heyrovsky mechanism for HER. j = 10 mA cm 2 is
single-component MoS2 electrocatalysts. reached with only 140 mV of overpotential. The improved
C. Nanostructuring of electrocatalyst supports to improve activity is partially due to the abundant and accessible edge
electron transport. While electron transport in the catalyst is a sites of dispersed MoS2. A second contribution comes from the
separate process from charge transfer reactions, it affects the enhanced electron transport by coupling graphene sheets to the
global activity of a catalyst and is often reflected on high Tafel less-conductive MoS2 nanoparticles.
slopes. As MoS2 is a semiconductor, the low conductivity of Our group prepared a hybrid catalyst system containing
such catalysts might limit their catalytic performance. Our conductive carbon particles (Vulcans) and amorphous
group show this is the case for several amorphous molybdenum MoS3 particles. Compared to MoS3 alone, the hybrid catalyst
sulphide catalysts.42 Coupling MoS2 with a highly conductive exhibited faster electron transport, manifested by a lower Tafel
substrate should alleviate this problem. slope (36 mV dec 1 instead of about 60 mV dec 1) and the
Dai and co-workers reported a selective solvothermal syn- absence of a line-feature in the Nyquist plot of the impedance
thesis of MoS2 on reduced graphene oxide (RGO) sheets. The spectrum.42 The latter was identified as a signature for slow
resulting MoS2–RGO hybrid material consists of thin MoS2 electron transport in porous materials.
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Fig. 10 (a) SEM picture of Mo2C nanowires. (b) TEM picture of a nanowire
revealing assemblies of smaller discrete Mo2C nanoparticles. (c) HER
polarization curves of the material itself (E) and of the carbon supported
Fig. 9 (a) SEM image of Mo2C microparticles. (b) HER polarization curves catalyst (&) in 0.5 M H2SO4 with loadings of 210 mg cm 2. Reprinted with
(10th) of MoB and Mo2C at pH 0 and 14. Scan rate = 1 mV s 1. MoB, pH 0, permission from ref. 64, copyright 2013, RSC Publishing.
2.5 mg cm 2 (----); MoB, pH 14, 2.3 mg cm 2 (——); Mo2C, pH 0,
1.4 mg cm 2 (—); and Mo2C, pH 14, 0.8 mg cm 2 (—m—). The iR drop was
corrected. Reprinted with permission from ref. 62, copyright 2012, Wiley-VCH.
current density of 10 mA cm 2 at Z = 152 mV. The Tafel
slope is 55 mV dec 1 and the exchange current density is
The overpotential to reach 10 mA cm 2 is 200 mV in acid and 1.4 10 5 A cm 2 in 0.1 M HClO4.63 This activity is much
190 mV in base. The Tafel slope is about 55 mV dec 1.62 The higher than the bulk Mo2C used as a reference in the same
discrepancy of the activity of Mo2C reported in these two study, and is considerably higher than the Mo2C microparticles
studies (one by us and the other one by Schröder) is surprising used in our earlier study. The long term stability of the Mo2C/
and might be due to different sources of Mo2C, or different CNT catalyst was confirmed by 3000 cycles of potential sweeps.
methods of electrode preparation, or both. The porosity of the nanocatalyst itself has been reported to
As discussed in Section 2.1, the electrocatalytic activity of a enhance HER catalysis by Liu, Tang, and co-workers.64 Nano-
given material might be improved if the density of exposed active porous Mo2C nanowires were synthesized by pyrolysis of a
sites in the material is increased. Reducing the particle size of the MoOx–amine hybrid precursor under an inert atmosphere.
catalyst to the nanometer scale is an efficient approach in this The high aspect ratio nanowires are several micrometers in
context. A second approach is to use a porous and conductive length and 80–150 nm in width (Fig. 10a). HRTEM shows these
support such as carbon nanotubes to improve the conductivity of nanowires are composed of discrete nanoparticles of 10–15 nm
the catalytic system and to favour the dispersion of the catalyst. (Fig. 10b). The catalyst exhibits excellent HER activity. In 0.5 M
Decreasing the d-band center of Mo2C is an additional method H2SO4, j = 10 mA cm 2 at Z = 130 mV and j = 60 mA cm 2 at Z =
to enhance its catalytic activity. These approaches have been 200 mV are reached with a Tafel slope of 53 mV dec 1 (Fig. 10c).
pursued to improve the HER activity of Mo2C. This superior activity of np-Mo2C NWs was attributed to their
Using carbon black and carbon nanotubes (CNTs) as supports, large surface areas, nanosized crystallites and nanoporosity.
Chen et al. prepared Mo2C nanoparticles with an average size of The large surface area and small crystallite size bring about a
12 nm.63 The particles were synthesized by the carburization of higher number of exposed active sites. The porosity also pre-
carbon-supported ammonium molybdate. The particles are vents the aggregation of the catalyst. The stability of the catalyst
well dispersed with no aggregation, resulting in a high density was also confirmed in a 1000-cycle potential cycling experiment.
of available active sites, and improved electronic conductivity. For comparison, the catalytic activity of both commercial and
The authors also proposed that the anchoring of Mo2C on the synthetic Mo2C microparticles was measured. At Z = 200 mV, j is
carbon support downshifts the d-band center of molybdenum below 10 mA cm 2 for the Mo2C microparticles.
which decreases the hydrogen binding energy.63 Consequently, The catalytic activity of np-Mo2C NWs was further enhanced
the Mo2C particles supported on CNTs (Mo2C/CNTs) reach a by mixing the nanowires with commercial Vulcans carbon.64
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3. Conclusions
In summary, recent developments of electrocatalysts of HER
have profited from the knowledge acquired in the study of
hydrotreating catalysts and the understanding of reactivity
trends on transition metal surfaces. HDT and HER catalysts
rely on the exposure of specific sites capable of adsorbing and
Fig. 13 (a) TEM image of Ni2P nanoparticles. (b) Polarization data for three
desorbing hydrogen with low energetic barriers. In this review,
individual Ni2P electrodes (loading 1 mg cm 2) in 0.5 M H2SO4, along with we have highlighted a number of HDT catalysts that are also
glassy carbon, Ti foil, and Pt in 0.5 M H2SO4, for comparison. (c) Corre- active for HER. Moreover, we have presented different nano-
sponding Tafel plots for the Ni2P and Pt electrodes. Reprinted with structuring approaches to improve the activity of electrocata-
permission from ref. 20, copyright 2013, American Chemical Society.
lysts. Table 1 summarizes some of the state-of-the-art materials.
MoS2 nanosheets with a high ratio of edge to basal sites
for hydrogen removal from Ni2P. Recently, Popczun et al. reported grown on a conductive graphene scaffold are capable of driving
that nanostructured nickel phosphides are indeed active electroca- 10 mA cm 2 at Z = 140 mV. MoS2 nanofilms prepared by Li
talysts for HER in acidic solutions.20 They synthesized uniformly intercalation can achieve j = 100 mA cm 2 at Z = 220 mV.53 Other
distributed and multifaceted nanoparticles of Ni2P which have an HDT catalysts have also shown high activity. State-of-the-art Mo2C
average grain size of 17 nm (Fig. 13a). When deposited on Ti, the can drive 10 and 80 mA cm 2 at overpotentials of 125 and 200 mV,
Ni2P nanoparticles showed a high activity in 0.5 M H2SO4: j = 10 mA respectively.64 Moreover, these catalysts are active and stable in
cm 2 at Z = 115 mV (Fig. 13b). The nanostructuring allowed the both basic and acidic media. Nanostructured Ni2P can deliver
exposure of numerous active sites on the desired facet (001) where 20 and 100 mA cm 2 at Z = 130 and 180 mV, respectively.20
the ensemble effect could take place. Interestingly, the Tafel slopes The challenge of producing hydrogen at a scale comparable to
changed at different overpotentials: it is 46 mV dec 1 between our energy demands is great and the response of the scientific
25 mV to 125 mV, and 81 mV dec 1 between 150 mV and community has been swift. Computational tools have been effec-
200 mV (Fig. 13c). There was a small degradation of catalytic activity. tively applied to the development of HER electrocatalysts. An
After 500 potential sweeps, the overpotential required to reach improved understanding of catalysis has allowed us to move away
10 mA cm 2 increased from 115 mV to 140 mV.20 However, this from a traditional trial-and-error approach to purposely construct
might be associated with the stability of the Ti–Ni2P assembly rather nanostructured materials. Impressive advances have been made
than the stability of Ni2P itself. in the last few years and this trend is expected to continue. A
repertoire of non-precious and highly active HER catalysts will be
2.6 Miscellaneous available in the near future. Although none of such catalysts
might outperform Pt in terms of activity, they are valid Pt
A few other materials have been investigated for both HDT and
replacements when cost and availability are taken into account.
HER reactions. FeP has been tested for HDO79 and HER.
Motivated by the enhancement of catalytic activity brought by
nanostructuring, Zhang and co-workers synthesized nanopor- 4. Outlook
ous FeP nanosheets by reaction of an inorganic–organic hybrid
Fe18S25–TETAH (TETAH = protonated triethylenetetramine) Looking ahead, many challenges in the development of HER
nanosheets with trioctylphosphine at an elevated temperature.82 catalysts remain. While all catalysts cited here are made of
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2
0.1–0.2 mg cm
Mo2C Microparticles 1–3 mm 190 54 3.8 1 M KOH 62
800 mg cm 2
Mo2C Carbon-nanotube-supported nanoparticles 7–15 nm 152 55 14 0.1 M HClO4 63
2 mg cm 2
Mo2C Carbon-supported porous nanowires 10–15 nm 125 54 N/A 0.5 M H2SO4 64
made of discrete nanoparticles 210 mg cm 2
NiMoNx Carbon-supported nanosheets 4–15 nm N/A 36 240 0.1 M HClO4 66
250 mg cm 2
Co0.6Mo1.4N2 Nanocrystallites 80 nm 200 N/A 230 0.1 M HClO4 67
240 mg cm 2
Mo1Soy-RGO Superimposed RGO sheets made 1–7 nm 109 63 37 0.1 M HClO4 65
of crystalline stripes 470 mg cm 2
(Mo2C)
W2C Microspheres 2–5 mm 190 118 281 1 M H2SO4 74
N/A
W2C Nanoparticles 16.5 nm 200 N/A N/A 0.1 M H2SO4 75
263 mg cm 2
WC Nanocrystals 5.6 nm 125 84 350 0.5 M H2SO4 77
1 mg cm 2
Fe-WCN Spherical nanoparticles 10–20 nm 220 47 N/A 0.05 M H2SO4 78
400 mg cm 2
Ni2P Hollow spherical nanoparticles 17 nm 115 46 33 0.5 M H2SO4 20
1 mg cm 2
FeP Nanosheets 10 nm 240 67 N/A 0.5 M H2SO4 82
280 mg cm 2
earth-abundant elements, they are not necessarily cheap to Conductive substrates such as graphene have high light absorp-
make as sophisticated and costly procedures are often involved. tion coefficients; thick HER catalysts block a great part of the
Likewise, nanostructuring is mostly limited to the preparation incident light. Both are detrimental to photoelectrocatalysis.
of a small amount of material in a laboratory scale. Scale-up of Processing at a high temperature could damage the photo-
synthetic methods needs to be addressed before considering absorber material inducing changes in morphology, reducing
realistic application. In parallel to this, a HER catalyst should the density of charge carriers, or creating trap and recombination
be evaluated according to the target application. The produc- sites on the surface of the photoelectrode. Physical adsorption of
tion of hydrogen in an electrolyzer requires a catalyst to deliver catalysts by drop-casting or self-assembly is a simple and poten-
current densities in the order of 1000 mA cm 2; on the other tially scalable method for the deposition of catalysts on photo-
hand, hydrogen production from a photoelectrochemical (PEC) electrodes. However, the injection of excited electrons into the
cell requires a catalyst to deliver a current density of only HER catalysts can be hindered if a proper electronic contact is not
10 mA cm 2. The latter application is the most cited driver created between the photoabsorber and the electrocatalyst.
for the current development in HER electrocatalysts. The Orthogonalization of light absorbance and fuel production
integration of electrocatalysis into photoelectrochemical (PEC) in high-aspect ratio photoelectrodes is an attractive approach to
cells is not straightforward. In this sense, a number of new direct solar water splitting. In this context, electrodeposition, photo-
challenges become evident, and two of them are listed here. electrodeposition and methods such as ALD and CVD that allow the
(1) Additional stability issues. In PEC applications, the electro- conformal coating of the photoelectrode with an electrocatalyst are
catalyst has to be stable under illumination (reductive) conditions, attractive methods for the preparation of HER catalysts.
but it also need to be stable in the dark where the open cell
potential of the photoelectrode could become very oxidative and,
thus, oxidative corrosion is a major decomposition pathway. Acknowledgements
(2) The catalyst should not absorb or refract light in the
visible range and should have an adequate electric contact This work is supported by a starting grant from the European
with the underlying photoabsorbing semiconductor. Many of Research Council under the European Community’s Seventh
the nanostructuring strategies summarized here are not easily Framework Programme (FP7 2007–2013)/ERC Grant agreement
adapted to the preparation of PEC water splitting devices. no. 257096.
This journal is © The Royal Society of Chemistry 2014 Chem. Soc. Rev., 2014, 43, 6555--6569 | 6567
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