A new class of electrocatalysts for hydrogen production from water electrolysis: metal monolayers supported on low-cost transition metal carbides.

This work explores the opportunity to substantially reduce the cost of hydrogen evolution reaction (HER) catalysts by supporting monolayer (ML) amounts of precious metals on transition metal carbide substrates. The metal component includes platinum (Pt), palladium (Pd), and gold (Au); the low-cost carbide substrate includes tungsten carbides (WC and W(2)C) and molybdenum carbide (Mo(2)C). As a platform for these studies, single-phase carbide thin films with well-characterized surfaces have been synthesized, allowing for a direct comparison of the intrinsic HER activity of bare and Pt-modified carbide surfaces. It is found that WC and W(2)C are both excellent cathode support materials for ML Pt, exhibiting HER activities that are comparable to bulk Pt while displaying stable HER activity during chronopotentiometric HER measurements. The findings of excellent stability and HER activity of the ML Pt-WC and Pt-W(2)C surfaces may be explained by the similar bulk electronic properties of tungsten carbides to Pt, as is supported by density functional theory calculations. These results are further extended to other metal overlayers (Pd and Au) and supports (Mo(2)C), which demonstrate that the metal ML-supported transition metal carbide surfaces exhibit HER activity that is consistent with the well-known volcano relationship between activity and hydrogen binding energy. This work highlights the potential of using carbide materials to reduce the costs of hydrogen production from water electrolysis by serving as stable, low-cost supports for ML amounts of precious metals.

Self-terminating electrodeposition of Pt on WC electrocatalysts.

Self-terminated electrochemical deposition is used to grow Pt nanoparticles on tungsten monocarbide (WC) from a pH 4 electrolyte of 3 mmol/L K2PtCl4-0.5 mol/L NaCl. An unconventional potentiodynamic deposition program is used where nucleation is promoted at large overpotentials followed by growth termination at still larger overpotentials to yield a high coverage of Pt nanoparticles. Following three deposition cycles between -0.8 VSCE and -0.45 VSCE, the surface is covered by a monolayer equivalent charge of Pt in the form of ≈3 × 1011 particles/cm2 that are ≈6.7 ± 1.1 nm in diameter. The number and size of nanoparticles increase monotonically for five deposition cycles. Area-normalized kinetics for hydrogen evolution (HER) and oxidation (HOR) on Pt-WC were determined in 0.5 mol/L H2SO4. For the lowest surface coverage of Pt nanoparticles on WC, ≈ 0.01, an exchange current density of ≈ 100 mA/cm2 is achieved, comparable to the highest reported values for Pt nanoparticles and ultramicroelectrodes. The area normalized apparent exchange current density decreases with increasing Pt coverage as the relative contribution of point versus planar diffusion decreases. Self-terminated electrodeposition of Pt provides an attractive approach to achieving ultra-low loadings of well-dispersed Pt nanoparticles on a non-precious metal support like WC.

A selective and efficient electrocatalyst for carbon dioxide reduction.

Converting carbon dioxide to useful chemicals in a selective and efficient manner remains a major challenge in renewable and sustainable energy research. Silver is an interesting electrocatalyst owing to its capability of converting carbon dioxide to carbon monoxide selectively at room temperature; however, the traditional polycrystalline silver electrocatalyst requires a large overpotential. Here we report a nanoporous silver electrocatalyst that is able to electrochemically reduce carbon dioxide to carbon monoxide with approximately 92% selectivity at a rate (that is, current) over 3,000 times higher than its polycrystalline counterpart under moderate overpotentials of <0.50 V. The high activity is a result of a large electrochemical surface area (approximately 150 times larger) and intrinsically high activity (approximately 20 times higher) compared with polycrystalline silver. The intrinsically higher activity may be due to the greater stabilization of CO2 (-) intermediates on the highly curved surface, resulting in smaller overpotentials needed to overcome the thermodynamic barrier.

Atomic layer deposition synthesis of platinum-tungsten carbide core-shell catalysts for the hydrogen evolution reaction.

Pt was deposited onto tungsten carbide powders using atomic layer deposition to produce core-shell catalysts for the hydrogen evolution reaction (HER). The Pt loading on these catalysts was reduced nearly ten-fold compared to a bulk Pt catalyst while equivalent HER activities were observed.