Acta Phys. -Chim. Sin. ›› 2025, Vol. 41 ›› Issue (11): 100137.doi: 10.1016/j.actphy.2025.100137
• ARTICLE • Previous Articles Next Articles
Work-function-engineered Mo 4d electronic structure modulation in Mo2C MXene cocatalyst for efficient photocatalytic H2 evolution
Ruiyun Liu1, Ping Wang1,*(
), Xuefei Wang1, Feng Chen1, Huogen Yu2,*()
- 1 School of Chemistry, Chemical Engineering and Life Sciences, Wuhan University of Technology, Wuhan 430070, Hubei Province, China
2 Laboratory of Solar Fuel, Faculty of Materials Science and Chemistry, China University of Geosciences, Wuhan 430074, Hubei Province, China
-
Received:2025-06-29Revised:2025-07-22Accepted:2025-07-24Published:2025-09-29 -
Contact:Email: wangping0904@whut.edu.cn (Ping Wang)yuhuogen@cug.edu.cn (Huogen Yu) -
Supported by:the National Natural Science Foundation of China(22472127); the National Natural Science Foundation of China(22178275); the National Natural Science Foundation of China(U22A20147); the Natural Science Foundation of Hubei Province of China(2022CFA001)
Cite this article
Ruiyun Liu, Ping Wang, Xuefei Wang, Feng Chen, Huogen Yu. Work-function-engineered Mo 4d electronic structure modulation in Mo2C MXene cocatalyst for efficient photocatalytic H2 evolution[J]. Acta Phys. -Chim. Sin. 2025, 41(11), 100137. doi: 10.1016/j.actphy.2025.100137
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Fig 1
(A) Graphical illustration ofdesigning MoC-Mo2C MXene for balanced H-ads./des. capacity: (1) Mo2C MXene characterized by strong H-adsorption; (2) MoC with strong H-desorption; (3) MoC-Mo2C MXene with balanced H-ads./des. capacity. (B) Schematic diagram of modulating Mo 4d-orbital electrons of Mo2C MXene via work-function (Wf) induced electron transfer from MoC to Mo2C MXene for balanced H-ads./des. capacity."
Fig 2
(A) Schematic diagram detailing the preparation of MoC-Mo2CTx cocatalyst via a Co-induced molten salt method, (B) simulated charge density difference view, and (C) planar-averaged electron density difference ∆□ (c-axis) between Co and Mo2CTx. (D) XRD patterns of the synthesized samples. (E–J) SEM images of MoC-Mo2CTx(0) (E, F), MoC-Mo2CTx(2) (G, H), and MoC-Mo2CTx(4) (I, J) at different magnifications."
Fig 3
(A) TEM and SAED images, (B) HRTEM image. (C) HAADF-STEM image and (C1, C2) corresponding elemental mapping images of the MoC-Mo2CTx cocatalyst."
Fig 4
(A) Graphical illustration depicting the synthesis steps and photographs of MoC-Mo2CTx/TiO2; (B) XRD patterns and (C) UV-Vis absorption spectra of (a) TiO2, (b) MoC-Mo2CTx(0)/TiO2, (c) MoC-Mo2CTx(2)/TiO2, (d) MoC-Mo2CTx(4)/TiO2."
Fig 5
(A) Photocatalytic H2-evolution rate of various samples; (B) Cycling H2-evolution activity of MoC-Mo2CTx(4)/TiO2."
Fig 6
(A–C) Top view of optimized models for DFT calculations. (D) The calculated work-function (Wf) for MoC and Mo2C MXene. (E) The charge density difference view, (F) planar-averaged electron density difference Δρ (z-axis direction) and charge displacement integral curve, and (G) charge density distributions in MoC-Mo2C MXene. (H and I) High-resolution XPS spectra of Mo 3d (H) and C 1s (I) for (a) MoC-Mo2CTx(2) and (b) MoC-Mo2CTx(4). (J) Schematic diagram of electron-deficient and electron-rich Mo sites formed by electron transfer from MoC to Mo2C MXene."
Fig 7
(A) The partial density of states (PDOS) for the Mo 4d-orbital and calculated d-orbital electrons (Qd), (B) schematic diagram of modulating Mo 4d-orbital center of MoC-Mo2C MXene by Wf-induced electron transfer. (C) PDOS data and (D) crystal orbital Hamilton population (COHP) analysis of H-adsorption on Mo2C MXene, MoC, and MoC-Mo2C MXene. (E) Gibbs free energy (ΔGH*) of H-adsorption on Mo atom at different surfaces and interfaces. (F) Schematic illustration demonstrating Mo 4d-band center regulation to H-ads./des. equilibrium. (G) The mechanism of enhancing HER activity by Wf-induced d-orbital modulation."
Fig 8
(A, B) Calculated work-function (Wf) for (A) the TiO2 (101) surface and (B) the MoC-Mo2C MXene (002) surface. (C) Schematic representation of the electron transfer between TiO2 photocatalyst and MoC-Mo2C MXene cocatalyst."
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