Activating Mo2C for methane-to-methanol electrocatalysis through active site formation via dual-metal doping

1. H. Cruchade, I.C. Medeiros−Costa, N. Nesterenko, J.−P. Gilson, L. Pinard, A. Beuque, S. Mintova, Catalytic routes for direct methane conversion to hydrocarbons and hydrogen: current state and opportunities, ACS Catal., 12 (2022) 14533−14558.10.1021/acscatal.2c03747 ↗

2. Carbon−efficient conversion of natural gas and natural−gas condensates to chemical products and intermediate feedstocks via catalytic metal–organic framework (MOF) chemistry10.1039/D2EE01010K ↗

3. Making more from methane10.1126/science.aaw7738 ↗

4. TiO2−facet−dependent effect on methane combustion over Ir/TiO2 catalysts10.1016/S1872-2067(24)60227-5 ↗

5. Electrochemical direct partial oxidation of methane to methanol10.1016/j.joule.2019.10.004 ↗

6. Methane oxidation to methanol10.1021/acs.chemrev.2c00439 ↗

7. Direct conversion of methane to value−added chemicalsover heterogeneous catalysts: challenges and prospects10.1021/acs.chemrev.6b00715 ↗

8. Direct methane conversion under mild condition by thermo−, electro−, or photocatalysis10.1016/j.chempr.2019.05.008 ↗

9. Silica–ceria sandwiched Ni core–shell catalyst for low temperature dry reforming of biogas: coke resistance and mechanistic insights10.1016/j.apcatb.2018.02.041 ↗

10. Core−shell structured Ru−Ni@SiO2: active for partial oxidation of methane with tunable H2/CO ratio10.1016/j.jechem.2017.07.011 ↗

11. Li, Z.; Xiao, Y.; Chowdhury, P. R.; Wu, Z.; Ma, T.; Chen, J. Z.; Wan, G.; Kim, T.−H.;Jing, D.; He, P.; Potdar, P. J.; Zhou, L.; Zeng, Z.; Ruan, X.; Miller, J. T.; Greeley, J. P.; Wu, Y.; Varma, A., Direct methane activation by atomically thin platinum nanolayers on two−dimensional metal carbides, Nat. Catal., 2021, 4, 882−891.10.1038/s41929-021-00686-y ↗

12. Recent advances in dry reforming of methanevia photothermocatalysis

13. Direct conversion of methane to methanol by electrochemical methods10.1016/j.gee.2021.11.007 ↗

14. Advances and fundamental understanding of electrocatalytic methane oxidation10.1002/cctc.202001412 ↗

15. A review on electrocatalytic oxidation of methane to oxygenates10.1039/D0TA03758C ↗

16. Efficient methane electrocatalytic conversion over a Ni−based hollow fiber electrode10.1016/S1872-2067(20)63548-3 ↗

17. Highly selective catalytic oxidation of methane to methanol using Cu–Pd/Anatase10.1039/D4EE02671C ↗

18. Catalytic methane monofunctionalization by an electrogenerated high−valent Pd intermediate10.1021/acscentsci.7b00342 ↗

19. Ma, H.−B.; Sheng, T.; Yu, W.−S.; Ye, J.−Y.; Wan, L.−Y.; Tian, N.; Sun, S.−G.; Zhou, Z.−Y., High catalytic activity of Pt(100) for CH4 electrochemical conversion, ACS Catal.,2019, 9, 10159−10165.10.1021/acscatal.9b02738 ↗

20. Structural dynamic evolution of Pt nanoclusters in ultra−low−temperature methane combustion with nitrous oxide10.1021/acsami.5c00172 ↗

21. Selective oxidation of methane to methanol over Au/H−MOR10.1021/jacs.3c04260 ↗

22. Hydrophobic zeolite modification for in situ peroxide formation in methane oxidation to methanol10.1126/science.aaw1108 ↗

23. Electro−conversion of methane to alcohols on “capsule−like” binarymetal oxide catalysts10.1016/j.apcatb.2020.119572 ↗

24. Alkane activation and oxidation on late−transition−metal oxides: challenges and opportunities10.1021/acscatal.1c00612 ↗

25. Solar cell−powered electrochemical methane−to−methanol conversion with CuO/CeO2 catalysts10.1021/acsenergylett.0c02553 ↗

26. Metal–organic framework−derived IrO2/CuO catalyst for selective oxidation of methane to methanol10.1021/acsenergylett.9b01992 ↗

27. High−selectivity room−temperature partial oxidation of methane to methanol enabled by electrochemical oxygen promotion on IrO2 catalysts10.1038/s41929-025-01363-0 ↗

28. Electrochemical oxidation of methane to methanol on electrodeposited transition metal oxides10.1021/jacs.3c00441 ↗

29. Catalytic combustion of methane: from mechanism and materials properties to catalytic performance10.1021/acscatal.2c03321 ↗

30. Electrocatalytic conversion of methane to ethanol by ultrathin WO3 nanosheets: oxygen vacancy engineering

31. Defect engineering in molybdenum−based electrode materials for energy storage10.1016/j.esci.2022.04.005 ↗

32. Doping regulation in transition metal compounds for electrocatalysis10.1039/D1CS00330E ↗

33. Ionic Liquid−TiO2−CuOx composite interfaces combined with gas directional transmission for enhanced electrooxidation of methane to ethanol10.1016/j.apcatb.2025.125411 ↗

34. Density functional theory studies of transition metal carbides and nitrides as electrocatalysts10.1039/D1CS00590A ↗

35. Role and dynamics of transition metal carbides in methane coupling10.1039/D3SC01054F ↗

36. In Situ investigations on structural evolutions during the facile synthesis of cubic α−MoC1–x catalysts10.1021/jacs.2c08979 ↗

37. H2 production from methane reforming over molybdenum carbide catalysts: from surface properties and reaction mechanism to catalyst development10.1021/acscatal.2c04619 ↗

38. Zhang, X.; Zhang, M.; Deng, Y.; Xu, M.; Artiglia, L.; Wen, W.; Gao, R.; Chen, B.; Yao, S.; Zhang, X.; Peng, M.; Yan, J.; Li, A.; Jiang, Z.; Gao, X.; Cao, S.; Yang, C.; Kropf, A. J.; Shi, J.; Xie, J.; Bi, M.; van Bokhoven, J. A.; Li, Y.−W.; Wen, X.; Flytzani−Stephanopoulos, M.; Shi, C.; Zhou, W.; Ma, D., A Stable Low−Temperature H2−Production Catalyst by Crowding Pt on α−MoC. Nature, 2021, 589, 396−401.10.1038/s41586-020-03130-6 ↗

39. Molybdenum carbide: controlling the geometric and electronic structure of noble metals for the activation of O–H and C–H bonds10.1021/acs.accounts.9b00182 ↗

40. Influence of the degree of carburizationon the density of sites and hydrogenating activity of molybdenum carbides10.1006/jcat.2000.2894 ↗

41. Termination−acidity tailoring of molybdenum carbides for alkaline hydrogen evolution reaction10.1038/s41467-025-55854-6 ↗

42. Dual−phased Mo2C/Mo3N2/C nanosheets for efficient electrocatalytic hydrogen evolution10.1039/D2TA09813J ↗

43. Phase‐transition of Mo2C induced by tungsten doping as heterointerface‐rich electrocatalyst for optimizing hydrogen evolution activity

44. High−performance MoC electrocatalyst for hydrogen evolution reaction enabled by surface sulfur substitution10.1021/acsami.1c12143 ↗

45. First−principles calculations and machine learning of hydrogen evolution reaction activity of nonmetallic doped beta−Mo2C support Pt single−atom catalysts

46. Adjacent‐confined pyrolysis for high‐density phase boundaries in Mo2C nanosheets to boost oxygen evolution10.1002/adfm.202401990 ↗

47. Microenvironment reconstitution of highly active Ni single atoms on oxygen−incorporated Mo2C for water splitting

48. Synergistic effect of dual-doped carbon on Mo2C nanocrystals facilitates alkaline hydrogen evolution10.1007/s40820-023-01135-0 ↗

49. Engineering Interfacial Coupling between Mo2C Nanosheets and Co@NC polyhedron for boosting electrocatalytic water splitting and zinc-air batteries

50. Efficiency of ab−initio total energy calculations for metalsand semiconductors using a plane−wave basis set10.1103/PhysRevB.54.11169 ↗

51. Projector augmented−wave method10.1103/PhysRevB.50.17953 ↗

52. Generalized gradient approximation made simple10.1103/PhysRevLett.77.3865 ↗

53. A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT−D) for the 94 elements H−Pu10.1063/1.3382344 ↗

54. A novel hard superconductor obtained in Di−Molybdenum Carbide (Mo2C) with Mo–C octahedral structure10.1016/j.jallcom.2021.160631 ↗

55. First−principles calculation of structural stability and mechanical properties of Cr doped Mo2C carbide

56. Mathew, K.; Sundararaman, R.; Letchworth−Weaver, K.; Arias, T. A.; Hennig, R. G., Implicit Solvation Model for Density−Functional Study of Nanocrystal Surfaces and Reaction Pathways. J. Chem. Phys., 2014, 140, 084106.10.1063/1.4865107 ↗

57. Implicit self−consistent electrolyte model in plane−wave density−functional theory10.1063/1.5132354 ↗

58. Electro−oxidation of methane on platinum under ambient conditions10.1021/acscatal.9b01207 ↗

59. Active oxygen promoted electrochemical conversion of methane on two-dimensional Carbide (MXenes): from stability, Reactivity and Selectivity10.1016/j.jcat.2020.11.008 ↗

60. Origin of the overpotential for oxygen reduction at a fuel−cell cathode10.1021/jp047349j ↗