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. 2024 Jul 12;9(8):3828–3834. doi: 10.1021/acsenergylett.4c01570

Direct Anchoring of Molybdenum Sulfide Molecular Catalysts on Antimony Selenide Photocathodes for Solar Hydrogen Production

Pardis Adams †, Jan Bühler †, Iva Walz †, Thomas Moehl †, Helena Roithmeyer †, Olivier Blacque †, Nicolò Comini ‡,§, J Trey Diulus ‡,§, Roger Alberto †, Sebastian Siol ∥, Mirjana Dimitrievska ∥, Zbynek Novotny ‡,§,*, S David Tilley †,*
PMCID: PMC11320643  PMID: 39144809

Abstract

graphic file with name nz4c01570_0005.jpg

Molybdenum sulfide serves as an effective nonprecious metal catalyst for hydrogen evolution, primarily active at edge sites with unsaturated molybdenum sites or terminal disulfides. To improve the activity at a low loading density, two molybdenum sulfide clusters, [Mo3S4]4+ and [Mo3S13]2–, were investigated. The Mo3Sx molecular catalysts were heterogenized on Sb2Se3 with a simple soaking treatment, resulting in a thin catalyst layer of only a few nanometers that gave up to 20 mA cm–2 under one sun illumination. Both [Mo3S4]4+ and [Mo3S13]2– exhibit catalytic activities on Sb2Se3, with [Mo3S13]2– emerging as the superior catalyst, demonstrating enhanced photovoltage and an average faradaic efficiency of 100% for hydrogen evolution. This superiority is attributed to the effective loading and higher catalytic activity of [Mo3S13]2– on the Sb2Se3 surface, validated by X-ray photoelectron and Raman spectroscopy.

Rising temperatures and climate variations strain natural and human systems, while an increasing energy gap, heightened by geopolitical tensions, prompts a global shift toward greener energy;1,2 however, the limited adoption of renewable sources, particularly in hydrogen production, underscores the need to explore alternative methods like emerging photoelectrochemical water-splitting technologies.3,4 Antimony selenide (Sb2Se3) has garnered attention for solar water splitting, due to its promising characteristics, including a high absorption coefficient (>105 cm–1), photostability, and cost-effective obtainment and synthesis.5−10 This material shows excellent performance and stability when paired with suitable catalysts. Therefore, the search for active, easy-to-prepare, and versatile catalysts is an essential factor for the long-term success of this material. While platinum is the most commonly used catalyst for the hydrogen evolution reaction (HER) due to its high catalytic activity and minimal overpotential, its scarcity and high cost hinder large-scale deployment. As a non-noble-metal substitute, nickel and nickel alloy catalysts offer competitiveness but are typically limited to alkaline media due to corrosion in acidic environments.11,12 In contrast, molybdenum sulfide (MoSx) stands out for its excellent stability over a wide pH range,13,14 making it a promising HER catalyst for Sb2Se3 and other semiconductor materials such as Cu2O and GaInP.15−19 This catalyst can facilitate reactions in highly acidic conditions (pH 0–1) without protective overlayers such as TiO2.20,21

Various preparation methods have been employed to maximize the density of the reactive sites of the MoSx catalyst. One promising category of these MoSx catalysts is molybdenum sulfide clusters, which, unlike the electrochemically inert basal planes observed in MoS2, have maximized catalytic activity per molybdenum ion with an increased number of active sites for a given geometric surface area.22 Furthermore, it has been observed that the efficiency of the photoabsorber is hindered by the thicker layers of MoS2. However, a thin layer of the molybdenum clusters could fulfill the catalytic requirements, thereby removing any insulation effects from thicker catalyst layers.14

Herein, we report the suitability of versatile and easy-to-deposit catalysts directly on Sb2Se3, which include molybdenum sulfide clusters in different configurations, namely [Mo3S4(H2O)9]Cl4 ([Mo3S4]4+) and (NH4)2[Mo3S13]·2H2O ([Mo3S13]2–). These earth-abundant catalysts can provide up to 20 mA cm–2 at −0.3 V versus reversible hydrogen electrode (RHE) with only a few nanometers thick layers, matching the photocurrents obtained with heterogeneous cocatalysts such as platinum.23 The easy deposition and simplicity of these molecular catalysts make them excellent candidates for translation to other systems such as photocatalytic particles. The stability and loading of these catalysts have been studied by using XPS and Raman.

The Sb2Se3 thin films in Figure 1a form the basis for most of the devices in this study. The films are soaked in either [Mo3S4(H2O)9]Cl4 ([Mo3S4]4+) or (NH4)2[Mo3S13]·2 H2O ([Mo3S13]2–) solution for 12 h to deposit the hydrogen evolution reaction (HER) catalyst. Finally, the films are annealed at 120 °C to improve catalyst adhesion without altering molecular integrity. This was confirmed by Raman measurements which showed identical peaks before and after annealing. The [Mo3S4]4+ illustrated in Figure 1b is synthesized from the reaction of ammonium tetrathiomolybdate with sodium borohydride and HCl in air.24,25 Crystals suitable for single-crystal X-ray diffraction (XRD) were obtained after anion exchange with p-toluenesulfonic acid. The [Mo3S13]2– shown in Figure 1c was synthesized according to procedures developed by Streb and co-workers,26 starting from ammonium heptamolybdate. A reaction with elemental sulfur and ammonium sulfide over 4 days yields the [Mo3S13]2– as dark red crystals suitable for X-ray crystallography. Mimicking the MoS2 catalytically active edge sites,27,28 molybdenum sulfide clusters have a maximum dimension of approximately 0.7 nm with a high ratio of active sites to nonactive ones (e.g., the basal plane in MoS2); therefore, more active species and thus catalytically active sites can be packed on the photoabsorber surface, increasing reactivity with a thinly deposited catalyst layer ranging between 5–30 nm, as observed from the profilometer measurements reported in Table S1.

Figure 1.

Figure 1

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(a) Typical stack of Sb2Se3 samples with a catalyst consisting of an FTO/Ti/Au/Sb2Se3/Mo3Sx configuration. Molecular structure and ellipsoid displacement plots of (b) [Mo3S4]4+ and (c) [Mo3S13]2–. Ellipsoids represent 50% probability. Counterions Cl– for (b), NH4+ for (c) and solvent molecules are omitted for clarity.

First, to investigate each catalyst’s activity in the dark, cyclic voltammetry (CV) cycled from 0.6 to −1.3 V versus RHE for 10 cycles in 1 M H2SO4 electrolyte (pH 0) was conducted for each sample. Figure S1 displays the CV, revealing that [Mo3S13]2– exhibits a lower overpotential (approximately 300 mV less) compared to [Mo3S4]4+ and maintains greater stability in 1 M H2SO4 electrolyte. Tafel plots of the two catalysts are given in Figure S1b. Typically, similar slopes among a family of catalysts in a Tafel plot imply a shared mechanism. However, the observed Tafel slopes for the two molybdenum sulfur clusters [Mo3S13]2– (62 mV/dec) and [Mo3S4]4+ (107 mV/dec) are distinct and indicate different mechanisms for the catalytic reaction.

As observed in the literature, the concentration of the catalyst solution, and therefore the catalyst loading, influences the performance of the devices.27 To determine the optimum concentration of each catalyst, three different catalyst concentrations were tested. The concentration of the catalyst solution was optimized at 2 mM based on measurements observed in Figure S2. Devices at this concentration outperformed others, particularly between −0.3 and −0.1 V vs RHE in [Mo3S4]4+ and between −0.2 and 0.0 V vs RHE in [Mo3S13]2–. Meanwhile at 3 mM, increased dark current was observed for both catalysts in the range of −0.3 to −0.25 V vs RHE. While these results were reproducible, sample-to-sample variation could account for the slight differences observed. Subsequently, the [Mo3S4]4+ and [Mo3S13]2– catalysts on top of the Sb2Se3 photoabsorber were measured in 1 M H2SO4 (pH 0) under 1 sun illumination, between 0.1 to −0.3 V versus RHE. As observed in Figure 2a, the [Mo3S4]4+ and [Mo3S13]2– catalysts produced 16.0 mA cm–2 and 17.5 mA cm–2 at −0.2 V versus RHE, respectively. With an onset potential of 0.05 V versus RHE, [Mo3S13]2– has a better overall performance than [Mo3S4]4+ with a −0.02 V versus RHE onset. This difference is attributed to the different overpotentials of the two catalysts (Figure S1). This leads to a shift of the JV curve of the [Mo3S4]4+ to more negative potentials, while the [Mo3S13]2– catalyst device exhibits a photocurrent approximately 2.5 mA cm–2 higher at −0.2 V vs RHE compared to the [Mo3S4]4+ catalyst device, as indicated by their J-V curves. Figure 2b illustrates that the [Mo3S13]2– catalyst has a higher incident photon to current conversion efficiency (IPCE) between 400–850 nm at a similar applied potential, indicating less surface recombination and more efficient charge collection compared to [Mo3S4]4+, which suffers from slower charge transfer due to higher overpotential. Both catalysts have similar IPCE in the 850–1100 nm range, as differences in the extinction coefficients of Sb2Se3 affect photon absorption and charge carrier generation. In the 400–850 nm range, a high charge density near the semiconductor-electrolyte interface enhances the [Mo3S13]2– catalyst’s performance. In contrast, the 850–1100 nm range sees charge generation in the semiconductor bulk, resulting in similar IPCE for both. The higher overpotential for [Mo3S4]4+ shown in Figure S1 underscores the [Mo3S13]2– catalyst’s efficiency under conditions of high charge density at the electrolyte interface. The integrated currents in Figure S3 are slightly higher than the values observed in the CV measurements above. The slight discrepancy in values can be attributed to the light intensity dependence of the Sb2Se3 devices, as shown in previous studies.29 Furthermore, the activity of both catalysts was investigated across various pH levels. As shown in Figure S4, both catalysts exhibit a similar trend, performing best at pH 0, although they remain effective at more basic pH levels, as well. This study highlights the flexibility and adaptability of these catalysts in diverse pH environments; however, stability remains limited on FTO.

Figure 2.

Figure 2

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(a) Cyclic voltammetry measurements versus RHE in 1 M H2SO4 under simulated 1 sun illumination (b) IPCE measurements in 1 M H2SO4 at −0.2 V versus RHE under 1% sun-white light bias (c) Faradaic efficiency of [Mo3S4]4+ and [Mo3S13]2– measured at −0.2 V versus RHE under illumination by a white LED light (∼1 sun).

As observed in Figure 2c, high faradaic efficiencies (FE) of up to 100% for the HER were obtained for both samples, as quantified with gas chromatography. [Mo3S13]2– showed a FE of 103 ± 7% (Table S2) after 10 min of 1 sun illumination at an applied potential of −0.2 V versus RHE. Under the same conditions, [Mo3S4]4+ showed varying values with an average FE of 88 ± 17% (Table S3). The larger error for the GC measurements with [Mo3S4]4+ likely results from the lower photocurrent and, therefore, the longer time for the mass transport of hydrogen from the solution to the headspace, where it can be measured by GC.

The lower FE can also be attributed to the lower stability and faster degradation of the [Mo3S4]4+ species. On the other hand, some of the [Mo3S13]2– samples were stable for over 1.5 h under harsh working conditions with high FE. This can be observed in Table S4, where FE measurements at different times are presented. CV measurements of the bare Sb2Se3 photocathode without catalysts (Figure S5a) were measured under illumination with light chopping, which showed negligible dark currents and no photocurrent. [Mo3S4]4+ catalyst, which is insoluble in pure H2O (in contrast to [Mo3S13]2–), was dissolved in 1 M HCl. To test the effects of the HCl solution, a bare Sb2Se3 was soaked in HCl which showed performance similar to that of the bare Sb2Se3 device (Figure S5a). The only observable difference is that the oxidation and reduction peaks seen in bare Sb2Se3 are considerably reduced in magnitude, implying that the HCl may have an etching property, removing oxides from the surface of the Sb2Se3 as previously studied.29 As Pt is the benchmark catalyst for HER, a bare Sb2Se3 film was deposited with 2 nm of Pt and measured under illumination by light chopping. As shown in Figure S4b, the dark current observed with the Pt catalyst is considerably increased compared with that of the bare Sb2Se3 alone. However, no photocurrent is observed with the Pt catalyst. (The Pt catalyst is known to be most effective on the Sb2Se3 when combined with a TiO2 overlayer, which was not investigated in this work.) The stability of each molybdenum sulfide cluster as a catalyst was investigated by measuring them through 60 cycles of CV at 10 mV s–1 between 0.1 V to −0.3 V versus RHE, corresponding to 80 min of measurement time (Figure S6). The [Mo3S13]2– shows an improved onset and current in the first 5 cycles, then stabilizes for 20 cycles, and then starts to degrade slowly. Furthermore, chronoamperometric stability tests were conducted to evaluate the long-term stability of the catalysts (Figure S6c). The [Mo3S13]2– catalyst exhibits a characteristic stability curve similar to that of the CV sweeps. The initial improvement in the current can be attributed to an increase in activity resulting from the partial exchange of disulfide ligands with aqua ligands. This substitution affects the kinetics of the hydrogen evolution reaction, making it more favorable. However, a complete exchange of disulfides for aqua ligands can lead to decreased activity due to the loss of these hydrogen evolution active sites leading to very high free energies of the Volmer step.30,31 In contrast, the [Mo3S4]4+ catalyst shows only degradation with time, with the film (Au, Sb2Se3 and catalyst) peeling off after approximately 2 h, rendering longer stability tests impossible. A partial peeling also occurs with the [Mo3S13]2– catalyst, contributing to the decrease in current, which could imply that the catalyst is not the limiting factor in such stability tests. This catastrophic failure is likely due to aggressive bubble formation penetrating beneath the film, which must be addressed and optimized for further long-term stability studies.

To assess the potential morphological effects of molybdenum catalysts on the Sb2Se3 surface, scanning electron microscopy (SEM) images were obtained (Figure S7). Differences observed between bare Sb2Se3 and catalyst-treated samples were attributed to the etching treatment before catalyst soaking, consistent with prior studies.29 SEM images after PEC measurements showed no noticeable differences in the morphology of the films. As different films were measured for each image, the differences in grain size can be attributed to sample-to-sample or even region-to-region variation. Atomic force microscopy (AFM) studies (Figure S8) further confirmed no discernible changes in the sample’s surface morphology due to catalyst deposition. Ultraviolet–visible-near-infrared diffuse reflectance spectroscopy (UV–vis-NIR DRS) provided insights into the surface properties of samples pre and post catalyst deposition. Figure S9a shows similar reflectance spectra for bare Sb2Se3 and Sb2Se3 with [Mo3S4]4+, while Figure S9b reveals increased reflectance in the blue region for [Mo3S13]2–, corresponding to a faint brown color observed after [Mo3S13]2– deposition. Raman measurements with 488, 532, and 785 nm excitation wavelengths were performed on bare Sb2Se3, Sb2Se3/[Mo3S4]4+ clusters as a catalyst, and Sb2Se3/ [Mo3S13]2– (Figure 3). Raman measurements with 488 and 532 nm excitation wavelengths reveal clear patterns belonging to the [Mo3S4]4+ and [Mo3S13]2– phases, as shown in Figures 3a and 3b, respectively. This behavior is expected, as both 488 and 532 nm lasers have penetration depths corresponding to about 50 and 100 nm, respectively. This reduces the ratio of Sb2Se3/[Mo3S4]4+, and Sb2Se3/[Mo3S13]2– probed volumes, rendering these laser excitations more sensitive to detecting clusters on the surface of Sb2Se3. In the spectra of Sb2Se3 with [Mo3S4]4+ clusters, intense Raman peaks at 354, 440, 456, and 493 cm–1 are observed, which are not featured in the Raman spectra measured on the reference Sb2Se3 with both 488 and 532 nm excitations. These peak positions are in good agreement with the Raman peak positions of [Mo3S4]4+ reported in the literature.32 Furthermore, in the Raman spectra of Sb2Se3 with [Mo3S13]2– clusters, peaks at 285, 329, 360, 385, 453, 518, and 552 cm–1 in addition to peaks belonging to the Sb2Se3 phase were identified. These peaks are in good agreement with the Raman peak positions of [Mo3S13]2– phase reported in the literature.33 The comparison of Raman spectra measured with 785 nm does not reveal any significant differences in the spectral features, including intensity, width, and position of Raman peaks among the three samples. Only Raman peaks corresponding to the Sb2Se3 phase are observed at this wavelength, as shown in Figure 3c.23 This indicates that the presence of [Mo3S4]4+ and [Mo3S13]2– clusters on the surface of Sb2Se3 do not induce any structural changes in the Sb2Se3 layer. This was corroborated by XRD measurements (Figure S10), showing no changes in crystal orientation before and after catalyst depositions. Additionally, observation of the Raman peaks belonging to the [Mo3S4]4+ and [Mo3S13]2– phases are not expected for this excitation wavelength, as the probed volume of Sb2Se3 material is about 50 times higher than the probed volume of either [Mo3S4]4+ or [Mo3S13]2–. Furthermore, the stability and integrity of the molecular catalysts were confirmed by measuring Raman spectra after PEC measurements. As observed in Figure S11, the fingerprint regions for both catalysts are still visible at 532 nm after PEC measurements.

Figure 3.

Figure 3

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(a) Raman spectra of a typical bare Sb2Se3 sample, Sb2Se3 + [Mo3S4]4+ and Sb2Se3 + [Mo3S13]2– at laser excitation wavelengths of (a) 488, (b) 532 nm, and (c) 785 nm.

While the mechanism of action of molybdenum sulfide catalysts is still debated, there are currently two fundamentally different theories of how HER occurs on Mo3Sx. One is a “molybdenum based” catalysis while the other is “sulphur based”.18 In the molybdenum-based catalysis, unsaturated Mo sites (originating from the loss of terminal disulfides in [Mo3S13]2–) serve as both a redox-active element and a site for substrate binding. In this system, molybdenum hydride is generated which is then protonated to liberate H2.32 Meanwhile, in the sulfur-based system, disulfides play the dual role of proton binder and redox-active component.35 In both theories, a molecular system would mean that there are more active sites per unit area for H2 evolution as the concentration of unsaturated Mo sites in both [Mo3S4]4+ and [Mo3S13]2– and terminal disulfides in [Mo3S13]2– are higher compared to MoS2 thin films. Based on the electrochemical and X-ray photoelectron spectroscopy (XPS) results in this study, it is hypothesized that both H2 evolution mechanisms are in action in conjunction as there are no terminal disulfides in the [Mo3S4]4+ clusters; however, the higher activity of [Mo3S13]2– is likely due to the contributions from the disulfide based hydrogen evolution leading to a better performance.36Figures 4a and 4b substantiate a conformal [Mo3S13]2– layer with at least 6 nm thickness (which is the approximate probing depth of the Se 3d line in this measurement). This is indicated by the absence of the Sb2Se3 substrate in the Sb 3d and Se 3d spectra of both the pristine and post-PEC films. Conversely, the pristine [Mo3S4]4+ layer is thinner (and/or not conformal) and appears to decrease further after PEC measurements, as evidenced by the visible Sb 3d and Se 3d signals. These findings suggest a homogeneous deposition of [Mo3S13]2– across the substrate, as the absence of substrate emission implies uniform coverage. Figures 4c and 4d highlight the distinction between the two catalysts. The Mo 3d spectra indicate differing oxidation states for the [Mo3S4]4+ and [Mo3S13]2– catalysts. The pristine [Mo3S13]2– catalyst shows the presence of molybdenum in Mo4+ form, while the post-PEC [Mo3S13]2– catalyst reveals a shift in molybdenum’s core level, indicating an oxidation state of Mo6+, accompanied by a MoO3 peak. This implies the loss of some disulfides, exposing unsaturated Mo sites and enabling molybdenum-based catalysis in conjunction with the sulfur-based catalysis. Meanwhile, the S 2p spectrum of [Mo3S13]2– initially shows a high concentration of disulfides (S22–), which decreases slightly post-PEC measurements. Conversely, the Mo 3d signals for [Mo3S4]4+ remain unchanged but decrease in intensity post-PEC measurements. The [Mo3S4]4+ S 2p peaks represent only sulfide bonds (S2–), diminishing in intensity post-PEC measurements. NAPXPS measurements in Figure S12 illustrate a similar trend but must be interpreted with caution due to the high signal-to-noise ratio. They indicate that more catalysts could be loaded on the surface of Sb2Se3 in the case of [Mo3S13]2– compared to that of [Mo3S4]4+ during the same soaking time and concentration. This was based on the smaller Se 3s substrate peak and more prominent Mo and S peaks for [Mo3S13]2–. The Se 3s substrate peak remained constant during exposure to water vapor, indicating stability. This effect was corroborated by Figure S12c and d, where Se 3d peaks were observed for [Mo3S4]4+ but not for [Mo3S13]2–. Furthermore, [Mo3S13]2– clusters initially displayed the expected stoichiometry, but this changed under operation, as evidenced in Figure S12b. The spectra indicated that the coverage of [Mo3S13]2– was initially very high, but after CV cycles, the Mo coverage dropped but did not entirely disappear. After CV measurements at different potentials, a chemical shift toward higher binding energy for Mo 3d was observed.

Figure 4.

Figure 4

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XPS spectra (a) Sb 3d (b) Se 3d (c) Mo 3d and (d) S 2p for bare and catalyzed samples measured before and after photoelectrocatalysis. Dashed reference lines are extracted from the NIST database.34

In summary, two molybdenum sulfide cluster species, [Mo3S4]4+ and [Mo3S13]2–, were thoroughly examined as cocatalysts on Sb2Se3 for photoelectrochemical hydrogen evolution. These clusters piqued interest due to their augmented active sites in comparison to MoS2 which possesses a catalytically inert basal plane. Throughout this study, it was discovered that [Mo3S13]2– excelled as a catalyst when a thin layer was deposited on Sb2Se3. Remarkably, even a few tens of nanometers of catalyst deposited by soaking exhibited remarkable stability, as observed via XPS after extended use. Paired with Sb2Se3, this catalyst achieved up to 100% faradaic efficiency and a current density of 17.5 mA cm–2 at −0.2 V versus RHE. With additional refinement and the application of previously established treatments such as AgNO3 treatment and sulfurization, this catalyst, when applied to Sb2Se3, can potentially demonstrate exceptional performance and improved stability.

Acknowledgments

This work was supported by the University of Zurich, URPP LightChEC, and SNF Project # 184737. J.B. acknowledges funding from the University of Zurich (UZH Candoc Grant, grant no. [FK-23-093]). J.T.D. acknowledges funding from the European Union’s Horizon 2020 under MCSA Grant No. 801459, FP-RESOMUS.

Supporting Information Available

The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsenergylett.4c01570.

  • Experimental methods and materials; additional electrochemical measurements, overpotential, Tafel slopes, stability and concentration optimization, integrated currents, pH studies, control experiments; gas chromatography (GC) and Faradaic efficiencies, calibration curve and data; morphological characterization methods, scattering electron microscopy (SEM) and atomic force microscopy (AFM); Ultraviolet–visible-near-infrared diffuse reflectance spectroscopy (UV–vis-NIR DRS); near ambient pressure X-ray photoelectron spectroscopy (NAPXPS); Raman spectroscopy; single crystal and thin film X-ray diffraction (XRD) (PDF)

  • CIF files for compounds in Figures S14 and S15 (ZIP)

The authors declare no competing financial interest.

Supplementary Material

nz4c01570_si_001.pdf (1.8MB, pdf)
nz4c01570_si_002.zip (909KB, zip)

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