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First-Principles Electrochemical Modeling of Hydrogen Evolution Reaction

Yang, Timothy Tseng Shin (2023) First-Principles Electrochemical Modeling of Hydrogen Evolution Reaction. Doctoral Dissertation, University of Pittsburgh. (Unpublished)

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Green Hydrogen, a clean and renewable energy carrier, is a sought solution for decarbonization and meeting net-zero greenhouse gas emissions by 2050. The central challenge in producing green hydrogen is to improve electrolysis performance via designing low-cost, high-efficient catalysts for hydrogen evolution reaction (HER) – the cathodic reaction in water splitting.
First-principles simulations provide a simple, yet effective, strategy to screen and identify HER catalysts. For the past two decades, the computational hydrogen adsorption free energy, proposed by Nørskov, has been the norm to gauge the exchange current – the electrochemical current that is generated at zero overpotential and is analogous to the reaction rate. However, this model misses a linkage with the fundamentals of electrochemistry and notably leads to inaccurate predictions of experimental measurements.
Our research aims to develop an easy-to-compute model for HER exchange currents building on the Butler-Volmer relation for a one-step, one-charge transfer process. I show that the exchange current is solely a function of the hydrogen adsorption free energy that can be obtained from first-principles methods. Benefiting from an absolute rate constant and the universality of the transfer coefficient, the new model successfully predicts the experimental exchange currents within two-orders of magnitude for various catalysts. This model is further validated by employing a data-driven approach based on experimental cyclic voltammograms – current-potential characteristics obtained from analytical measurements. Beyond Nørskov’s approach, the new model, with its rigorous linkage to theoretical electrochemical methods, not only boosts the prediction accuracy of the exchange current, but also addresses several decades-long controversies in the field.
Using this model in conjunction with first-principles, ab initio thermodynamics, and cluster expansion, I determine the catalytic activity towards hydrogen evolution of several low-cost novel catalysts, focusing on molybdenum carbides (MoyC). The computational screening show that doping with titanium or iridium, and the coupling of MoyC with graphene increase the HER activity of MoyC. These findings are validated experimentally and further confirm the high fidelity of the model. In addition, my overarching theoretical approach for developing the model is transferable to other electrochemical reactions.


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Item Type: University of Pittsburgh ETD
Status: Unpublished
CreatorsEmailPitt UsernameORCID
Yang, Timothy Tseng Shintimothy055050@gmail.comtty20000-0002-5785-0511
ETD Committee:
TitleMemberEmail AddressPitt UsernameORCID
Committee ChairSaidi, Wissam
Committee MemberLee, Jung-Kunjul37@pitt.eduJUL370000-0002-7778-7679
Committee MemberMcKone, James
Committee MemberChmielus,
Date: 14 September 2023
Date Type: Publication
Defense Date: 10 May 2023
Approval Date: 14 September 2023
Submission Date: 6 June 2023
Access Restriction: No restriction; Release the ETD for access worldwide immediately.
Number of Pages: 205
Institution: University of Pittsburgh
Schools and Programs: Swanson School of Engineering > Materials Science and Engineering
Degree: PhD - Doctor of Philosophy
Thesis Type: Doctoral Dissertation
Refereed: Yes
Uncontrolled Keywords: electrochemistry
Date Deposited: 14 Sep 2023 13:38
Last Modified: 14 Sep 2023 13:38

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