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Title: Reaction Mechanism for the Hydrogen Evolution Reaction on the Basal Plane Sulfur Vacancy Site of MoS2 Using Grand Canonical Potential Kinetics

Journal Article · · Journal of the American Chemical Society

We develop the grand canonical potential kinetics (GCP-K) formulation based on thermodynamics from quantum mechanics calculations to provide a fundamental basis for understanding heterogeneous electrochemical reactions. Our GCP-K formulation arises naturally from minimizing the free energy using a Legendre transform relating the net charge of the system and the applied voltage. Performing this macroscopic transformation explicitly allows us to make the connection of GCP-K to the traditional Butler-Volmer kinetics. Using this GCP-K based free energy, we show how to predict both the potential and pH dependent chemistry for a specific example, the hydrogen evolution reaction (HER) at a sulfur vacancy on the basal plane of MoS2.We find that the rate-determining steps in both acidic and basic conditions are the Volmer reaction in which the second hydrogen atom is adsorbed from the solution. Using the GCP-K formulation, we show that the stretched bond distances change continuously as a function of the applied potential. This shows that the main reason for the higher activity in basic conditions is that the transition state is closer to the product, which leads to a more favorable Tafel slope of 60 mV/dec. In contrast if the transition state were closer to the reactant, where the transfer coefficient is less than 0.5 we would obtain a Tafel slope of almost 150 mV/dec. Based on this detailed understanding of the reaction mechanism, we conclude that the second hydrogen at the chalcogenide vacant site is the most active toward the hydrogen evolution reaction. Using this as a descriptor, we compare it to the other 2H group VI metal dichalcogenides and predict that vacancies on MoTe2 will have the best performance toward HER.

Research Organization:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC); California Inst. of Technology (CalTech), Pasadena, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
SC0004993
OSTI ID:
1543728
Journal Information:
Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 48 Vol. 140; ISSN 0002-7863
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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An electrocatalytic route for transformation of biomass-derived furfural into 5-hydroxy-2(5 H )-furanone journal January 2019
Graphene/graphene nanoribbon aerogels decorated with S-doped MoSe 2 nanosheets as an efficient electrocatalyst for hydrogen evolution journal January 2019
Awakening Solar Hydrogen Evolution of MoS 2 in Alkalescent Electrolyte through Doping with Co journal June 2019
A fluorescent conjugated polymer photocatalyst based on Knoevenagel polycondensation for hydrogen production journal January 2019
Assembly and Redox-Rich Hydride Chemistry of an Asymmetric Mo2S2 Platform journal July 2020
The Holy Grail in Platinum‐Free Electrocatalytic Hydrogen Evolution: Molybdenum‐Based Catalysts and Recent Advances journal June 2019

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