Due to conversion equilibrium between solvent and H- and O-containing adsorbates, the true surface state of a catalyst under a particular electrochemical condition is often overlooked in electrocatalysis research. Herein, by using surface Pourbaix analysis, we show that many electrocatalytically active transition metal X-ides (e.g., oxides, nitrides, carbides, and hydroxides) tend to possess the surface states different from their pristine stoichiometric forms under the pH and potential of interest due to water dissociation or generation. Summarizing the density functional theory calculated surface Pourbaix diagrams of 14 conditionally stable transition metal X-ide materials, we found that some of these surfaces tend to be covered by O-containing adsorbates at a moderate or high potential, while vacancies or H-covered surfaces may form at a low potential. These results suggest the possibility of poisoning or creation of surface sites beyond the pristine surface, implying that the surface state under reaction conditions (pH and potentials) needs to be considered before the identification and analysis of active sites of a transition metal X-ide catalyst. In addition, we provide an explanation of the observed theory and experiment discrepancy that some transition metal X-ides are “more stable in experiment than in theory.” Based on our findings, we conclude that analyzing the surface state of transition metal X-ide electrocatalysts by theoretical calculations (e.g., surface Pourbaix diagram analysis), in situ/operando and post-reaction experiments are indispensable to accurately understand the underlying catalytic mechanisms.
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28 March 2023
Research Article|
March 22 2023
The surface states of transition metal X-ides under electrocatalytic conditions
Special Collection:
Chemical Physics of Electrochemical Energy Materials
Heng Liu
;
Heng Liu
(Data curation, Formal analysis, Investigation, Writing – original draft, Writing – review & editing)
1
Advanced Institute for Materials Research (WPI-AIMR), Tohoku University
, Sendai 980-8577, Japan
2
Department of Chemical Engineering, The University of Manchester
, Oxford Road M13 9PL, United Kingdom
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Xue Jia;
Xue Jia
(Formal analysis, Funding acquisition, Investigation)
1
Advanced Institute for Materials Research (WPI-AIMR), Tohoku University
, Sendai 980-8577, Japan
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Ang Cao
;
Ang Cao
(Data curation, Formal analysis, Investigation)
3
Catalysis Theory Center, Department of Physics, Technical University of Denmark
, 2800 Lyngby, Denmark
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Li Wei
;
Li Wei
a)
(Formal analysis, Funding acquisition, Investigation, Resources, Validation, Writing – review & editing)
4
School of Chemical and Biomolecule Engineering, The University of Sydney
, Darlington 2006, NSW, Australia
a)Authors to whom correspondence should be addressed: l.wei@sydney.edu.au; carmine.dagostino@manchester.ac.uk; and li.hao.b8@tohoku.ac.jp
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Carmine D’agostino
;
Carmine D’agostino
a)
(Formal analysis, Funding acquisition, Investigation, Supervision, Writing – review & editing)
2
Department of Chemical Engineering, The University of Manchester
, Oxford Road M13 9PL, United Kingdom
5
Dipartimento di Ingegneria Civile, Chimica, Ambientale e dei Materiali (DICAM), Alma Mater Studiorum–Università di Bologna
, Via Terracini, 28, 40131 Bologna, Italy
a)Authors to whom correspondence should be addressed: l.wei@sydney.edu.au; carmine.dagostino@manchester.ac.uk; and li.hao.b8@tohoku.ac.jp
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Hao Li
Hao Li
a)
(Conceptualization, Data curation, Formal analysis, Funding acquisition, Investigation, Methodology, Project administration, Resources, Software, Supervision, Validation, Visualization, Writing – original draft, Writing – review & editing)
1
Advanced Institute for Materials Research (WPI-AIMR), Tohoku University
, Sendai 980-8577, Japan
a)Authors to whom correspondence should be addressed: l.wei@sydney.edu.au; carmine.dagostino@manchester.ac.uk; and li.hao.b8@tohoku.ac.jp
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a)Authors to whom correspondence should be addressed: l.wei@sydney.edu.au; carmine.dagostino@manchester.ac.uk; and li.hao.b8@tohoku.ac.jp
Note: This paper is part of the JCP Special Topic on Chemical Physics of Electrochemical Energy Materials.
J. Chem. Phys. 158, 124705 (2023)
Article history
Received:
February 19 2023
Accepted:
March 07 2023
Citation
Heng Liu, Xue Jia, Ang Cao, Li Wei, Carmine D’agostino, Hao Li; The surface states of transition metal X-ides under electrocatalytic conditions. J. Chem. Phys. 28 March 2023; 158 (12): 124705. https://doi.org/10.1063/5.0147123
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