Expediting Oxygen Evolution by Optimizing Cation and Anion Complexity in Electrocatalysts Based on Metal Phosphorous Trichalcogenides

Abstract

Purposely changing the rate‐determining step (RDS) of oxygen evolution reaction (OER) remains a major challenge for enhancing the energy efficiency of electrochemical splitting of water. Here we show that the OER RDS can be regulated by simply varying the cation and anion complexity in a family of the metal phosphorous trichalcogenide electrocatalysts (MPT3, where M=Fe, Ni; T=S, Se), achieving an exceptionally high OER activity in (Ni,Fe)P(S,Se)3, as demonstrated by its ultra‐low Tafel slope (34 mV dec−1) and a very low overpotential compared to many relevant OER catalysts. This is strongly supported by density functional theory calculations, which showed that this catalyst has a nearly optimal OER activity descriptor value of ΔG(O*)−ΔG(OH*)=1.5 eV. We also found that the activity descriptor is proportional to a newly proposed cation/anion complexity index that consists of pairwise contributions from cation‐anion bonds in a catalyst compound, revealing the pivotal role of the cation‐anion interactions in determining the catalyst performance and providing a simple way for predicting catalytic activities.

Shining light on layered metal phosphosulphide catalysts for efficient water electrolysis: preparation, promotion strategies, and perspectives

“…Therefore, the changes in the structure and surface state of MPS 3 -based electrocatalysts during water splitting should be understood through in situ analysis methods (such as in situ infrared spectra, in situ Raman, in situ XRD, in situ TEM, etc.). At the same time, computer simulations are necessary 106 (DFT calculations, molecular dynamics simulations, etc.). The catalytic mechanism should be deeply analyzed in terms of both experimental and theoretical aspects.…”

“…). At the same time, computer simulations are necessary 106 (DFT calculations, molecular dynamics simulations, etc .). The catalytic mechanism should be deeply analyzed in terms of both experimental and theoretical aspects.…”

The Guest Doping Effects of Fe on Bimetallic NiCo Layered Double Hydroxide for Enhanced Electrochemical Oxygen Evolution Reaction: Theoretical Screening and Experimental Verification

“…[22] Moreover, owing to the limitation of spatial resolution and the intricate task of quantifying atom-molecule interactions, the designing of advanced electrocatalysts and the exploration of atomistic effects on catalytic performance through experimental discipline remain challenges. [23,24] It is foreseeable that the pre-theoretical screening on atomic scale combined with the experimental characterization on the designated foreign species modified binary transition-metal-based LDHs would eliminate many unnecessary trial and error processes, while simultaneously providing comprehensive elucidation into the relationship of structureactivity.…”

3D nanostructured Ce-doped CoFe-LDH/NF self-supported catalyst for high-performance OER

“…Hence, several feasible optimization and modification strategies have been proposed, including designing nanostructures (such as hollow nanoprisms, 19 nanospheres, 20 and nanowires 21 ) to increase the active surface area, using hybridization to accelerate charge transfer, adjusting the binding energy between catalysts and reaction intermediates. 22 More importantly, the doping of cations 23 and anions 24 helps to adjust the local electronic structure and build more adsorption sites. Recent studies disclosed that the doping of rare earth elements can improve oxygen vacancies, optimize electron binding affinity, accelerate electron transfer rate, and enhance the adsorption of intermediates by reactants.…”