Benchmarking Phases of Ruthenium Dichalcogenides for Electrocatalysis of Hydrogen Evolution: Theoretical and Experimental Insights

Abstract

The hydrogen evolution reaction (HER) is a significant cathode step in electrochemical devices, especially in water splitting, but developing efficient HER catalysts remains a great challenge. Herein, comprehensive density functional theory calculations are presented to explore the intrinsic HER behaviors of a series of ruthenium dichalcogenide crystals (RuX2, X = S, Se, Te). In addition, a simple and easily scaled production strategy is proposed to synthesize RuX2 nanoparticles uniformly deposited on carbon nanotubes. Consistent with theoretical predictions, the RuX2 catalysts exhibit impressive HER catalytic behavior. In particular, marcasite‐type RuTe2 (RuTe2‐M) achieves Pt‐like activity (35.7 mV at 10 mA cm−2) in an acidic electrolyte, and pyrite‐type RuSe2 presents outstanding HER performance in an alkaline media (29.5 mV at 10 mA cm−2), even superior to that of commercial Pt/C. More importantly, a RuTe2‐M‐based proton exchange membrane (PEM) electrolyzer and a RuSe2‐based anion exchange membrane (AEM) electrolyzer are also carefully assembled, and their outstanding single‐cell performance points to them being efficient cathode candidates for use in hydrogen production. This work makes a significant contribution to the exploration of a new class of transition metal dichalcogenides with remarkable activity toward water electrolysis.

Rational Design of Better Hydrogen Evolution Electrocatalysts for Water Splitting: A Review

“…The possibility that AEM electrolysis can use non‐noble metal oxides compared to PEM electrolysis represents a significant advantage for AEM over PEM in terms of significantly reducing associated costs. [ 294 ] However, given the current lack of commercially available AEM, the development of ionic conductive polymers without any aromatic groups to further enhance the transport of water and ions has the potential to drive large‐scale commercial applications of AEM electrolysis.…”

Screening and Understanding Lattice Silicon‐Controlled Catalytically Active Site Motifs from a Library of Transition Metal‐Silicon Intermetallics

“…Fortunately, high-throughput density functional theory (DFT) calculations are becoming powerful enough to quickly predict catalytic properties and speed up the search for novel catalysts. [6][7][8][9] The high-throughput screening of highperforming catalysts is often dependent upon the simple and efficient thermodynamic descriptor (e.g., hydrogen adsorption energy (ΔG H* ) for hydrogen-evolving electrocatalysts), [10][11][12][13] which requires DFT calculations of surface adsorption properties of key intermediate species on surface active sites. For a desirable catalyst with the optimized local atomic structures, their surface active sites could bind the key reaction intermediates neither too strongly nor too weakly (also known as Sabatier principle).…”

Transition metal dichalcogenides as catalysts for the hydrogen evolution reaction: The emblematic case of “inert” ZrSe2 as catalyst for electrolyzers

“…Currently, to the best of our knowledge, despite the impressive catalytic activity claimed and experimentally demonstrated for the TMDs, there are no commercial water electrolyzers based on these materials. In fact, only some proof‐of‐concept electrolyzers have been reported using, for example, MoS 2 , [ 46–49 ] RuTe 2 , [ 50 ] FeS 2 [ 51 ] and NbS 2 [ 52 ] as cathode materials. Such aspects indicate the need to systematically validate the use of TMDs as HER‐EC into practical electrolyzers to advance the technologies for the electrochemical hydrogen production.…”