Orbital engineering of C3N monolayer to design efficient synergistic sites electrocatalyst for boosting alkaline hydrogen evolution

Zeng, Yamei; Zhang, Xu; Ai, Changzhi; Wang, Caizhuang; Liu, Yipu; Lin, Shiwei

doi:10.1016/j.apsusc.2022.152474

Orbital engineering of C₃N monolayer to design efficient synergistic sites electrocatalyst for boosting alkaline hydrogen evolution

Journal Article · Mon Jan 10 00:00:00 EST 2022 · Applied Surface Science

DOI:https://doi.org/10.1016/j.apsusc.2022.152474· OSTI ID:1875268

Zeng, Yamei ^[1]; Zhang, Xu ^[1]; Ai, Changzhi ^[1]; Wang, Caizhuang ^[2]; Liu, Yipu ^[1]; Lin, Shiwei ^[1]

Hainan Univ., Haikou (China)
Ames Lab., and Iowa State Univ., Ames, IA (United States)

Alkaline water electrolyzer (AWE) is one of the promising technologies for hydrogen production at the industrial level. However, energetic inefficiency and low current density impede the development of AWE. Compared with acidic conditions, the Volmer step in alkaline hydrogen evolution reaction (HER) involves extra water dissociation, whose barrier is one of the most vital reasons for the sluggish kinetics of alkaline HER. Herein, choosing C₃N monolayer as an ideal theoretical model, we design several empty orbitals through intentional metal doping, and further construct synergistic sites on the C₃N monolayer to accelerate both water dissociation and hydrogen adsorption for alkaline HER. Furthermore, the as-designed Be-doped and Cr-doped C₃N monolayers exhibit rather low theoretical overpotential of 0.476 eV and 0.216 eV for alkaline HER, respectively, which are even lower than Pt (1 1 1) surface. Moreover, by comparing the water dissociation behaviors on metal-doped C3N monolayer, we find that the empty orbitals with suitable orientation and energy level are useful for promoting the water dissociation process, indicating that we can use orbital engineering strategy to regulate the adsorption strength between adsorbate and surface site. Consequently, it is reasonable to suggest that our orbital engineering strategy would significantly benefit the design of highly efficient alkaline HER electrocatalysts.

View Accepted Manuscript (DOE)

Research Organization:: Ames Laboratory (AMES), Ames, IA (United States)

Sponsoring Organization:: National Natural Science Foundation of China; USDOE Office of Science (SC)

Grant/Contract Number:: AC02-07CH11358

OSTI ID:: 1875268

Report Number(s):: IS-J 10,700

Journal Information:: Applied Surface Science, Journal Name: Applied Surface Science Vol. 582; ISSN 0169-4332

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Alkaline hydrogen evolution reaction
Bifunctional catalyst
Density functional theory
Orbital engineering
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metal-doped C3N

Orbital engineering of C3N monolayer to design efficient synergistic sites electrocatalyst for boosting alkaline hydrogen evolution

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Orbital engineering of C₃N monolayer to design efficient synergistic sites electrocatalyst for boosting alkaline hydrogen evolution