Heron Vrubel

Amorphous Molybdenum Sulfide Films as Catalysts for Electrochemical Hydrogen Production in Water

Amorphous molybdenum sulfide films are efficient hydrogen evolution catalysts in water. The films are prepared via simple electro-polymerization procedures and are characterized by XPS, electron microscopy and electronic absorption spectroscopy. Whereas the precatalysts could be MoS3 or MoS2, the active form of the catalysts is identified as amorphous MoS2. Significant geometric current densities are achieved at low overpotentials (e.g., 15 mA cm−2 at η = 200 mV) using these catalysts. The catalysis is compatible with a wide range of pHs (e.g., 0 to 13). The current efficiency for hydrogen production is quantitative. A 40 mV Tafel slope is observed, suggesting a rate-determining ion+atom step. The turnover frequency per active site is calculated. The amorphous molybdenum sulfide films are among the most active non-precious hydrogen evolution catalysts.

Molybdenum Boride and Carbide Catalyze Hydrogen Evolution in both Acidic and Basic Solutions

Molybdenum boride (MoB) and carbide (Mo2C) are excellent catalysts for electrochemical hydrogen evolution at both pH 0 and pH 14.

Fe, Co, and Ni ions promote the catalytic activity of amorphous molybdenum sulfide films for hydrogen evolution

Molybdenum sulfide materials have been shown as promising non-precious catalysts for hydrogen evolution. This paper describes the study of the promotional effects of certain transition metal ions on the activity of amorphous MoS3 films. Ternary metal sulfide films, M–MoS3 (M = Mn, Fe, Co, Ni, Cu, Zn), have been prepared by cyclic voltammetry of aqueous solutions containing MCl2 and (NH4)2[MoS4]. Whereas the Mn–, Cu–, and Zn–MoS3 films show similar or only slightly higher catalytic activity as the MoS3 film, the Fe–, Co–, and Ni–MoS3 films are significantly more active. The promotional effects of Fe, Co, and Ni ions exist under both acidic and neutral conditions, but the effects are more pronounced under neutral conditions. Up to a 12-fold increase in exchange current density and a 10-fold increase in the current density at an overpotential of 150 mV are observed at pH = 7. It is shown that Fe, Co, and Ni ions promote the growth of the MoS3 films, resulting a high surface area and a higher catalyst loading. These changes are the main contributors to the enhanced activity at pH = 0. However, at pH = 7, Fe, Co, and Ni ions appear to also increase the intrinsic activity of the MoS3 film.

Hydrogen evolution catalyzed by MoS3 and MoS2 particles

Amorphous MoS3 particles are prepared using a simple chemical method. Several deposition techniques are developed to fabricate electrodes loaded with MoS3 particles. These electrodes are highly active for hydrogen evolution. The catalytically active species appear to be reduced molybdenum sulfide that contains disulfide ligands. The MoS3 particles are annealed to form polycrystalline and single crystalline MoS3 and MoS2 particles. These particles, as well as commercial MoS2 micro-crystals, show inferior catalytic activity compared to the amorphous MoS3 particles.

Hydrogen evolution from a copper(I) oxide photocathode coated with an amorphous molybdenum sulphide catalyst

Concerns over climate change resulting from accumulation of anthropogenic carbon dioxide in the atmosphere and the uncertainty in the amount of recoverable fossil fuel reserves are driving forces for the development of renewable, carbon-neutral energy technologies. A promising clean solution is photoelectrochemical water splitting to produce hydrogen using abundant solar energy. Here we present a simple and scalable technique for the deposition of amorphous molybdenum sulphide films as hydrogen evolution catalyst onto protected copper(I) oxide films. The efficient extraction of excited electrons by the conformal catalyst film leads to photocurrents of up to -5.7 mA cm(-2) at 0 V versus the reversible hydrogen electrode (pH 1.0) under simulated AM 1.5 solar illumination. Furthermore, the photocathode exhibits enhanced stability under acidic environments, whereas photocathodes with platinum nanoparticles as catalyst deactivate more rapidly under identical conditions. The work demonstrates the potential of earth-abundant light-harvesting material and catalysts for solar hydrogen production.

Easily-prepared dinickel phosphide (Ni2P) nanoparticles as an efficient and robust electrocatalyst for hydrogen evolution

Polydispersed dinickel phosphide (Ni2P) nanoparticles were synthesized by a simple and scalable solid-state reaction. These nanoparticles are an excellent and robust catalyst for the electrochemical hydrogen evolution reaction, operating in both acidic and basic solutions.

Low-cost industrially available molybdenum boride and carbide as “platinum-like” catalysts for the hydrogen evolution reaction in biphasic liquid systems

Rarely reported low-cost molybdenum boride and carbide microparticles, both of which are available in abundant quantities due to their widespread use in industry, adsorb at aqueous acid-1,2-dichloroethane interfaces and efficiently catalyse the hydrogen evolution reaction in the presence of the organic electron donor - decamethylferrocene. Kinetic studies monitoring biphasic reactions by UV/vis spectroscopy, and further evidence provided by gas chromatography, highlight (a) their superior rates of catalysis relative to other industrially significant transition metal carbides and silicides, as well as a main group refractory compound, and (b) their highly comparable rates of catalysis to Pt microparticles of similar dimensions. Insight into the catalytic processes occurring for each adsorbed microparticle was obtained by voltammetry at the liquid-liquid interface.

Evidence from in situ X-ray absorption spectroscopy for the involvement of terminal disulfide in the reduction of protons by an amorphous molybdenum sulfide electrocatalyst.

The reduction of protons into dihydrogen is important because of its potential use in a wide range of energy applications. The preparation of efficient and cheap catalysts for this reaction is one of the issues that need to be tackled to allow the widespread use of hydrogen as an energy carrier. In this paper, we report the study of an amorphous molybdenum sulfide (MoSx) proton reducing electrocatalyst under functional conditions, using in situ X-ray absorption spectroscopy. We probed the local and electronic structures of both the molybdenum and sulfur elements for the as prepared material as well as the precatalytic and catalytic states. The as prepared material is very similar to MoS3 and remains unmodified under functional conditions (pH = 2 aqueous HNO3) in the precatalytic state (+0.3 V vs RHE). In its catalytic state (−0.3 V vs RHE), the film is reduced to an amorphous form of MoS2 and shows spectroscopic features that indicate the presence of terminal disulfide units. These units are formed concomitantly with the release of hydrogen, and we suggest that the rate-limiting step of the HER is the reduction and protonation of these disulfide units. These results show the implication of terminal disulfide chemical motifs into HER driven by transition-metal sulfides and provide insight into their reaction mechanism.

Hydrogen evolution at polarised liquid/liquid interfaces catalyzed by molybdenum disulfide

Molybdenum disulfide microparticles in suspension in an aqueous acidic solution adsorb at the interface with an organic electrolyte solution containing the reducing agent, decamethylferrocene, to catalyse hydrogen evolution. This catalytic process has been investigated by voltammetry at the water/1,2-dichloroethane interface and by biphasic reactions monitored by gas chromatography and UV-visible spectroscopy.

Electrochemical reduction of CO2 in organic solvents catalyzed by MoO2

MoO2 microparticles act as an active catalyst for the electrochemical reduction of CO2 in organic solvents such as acetonitrile and dimethylformamide. The catalytic activity and product selectivity depend on temperature and water content of the solvent.