Role of electronic structure of vanadium oxide cluster in methanol oxidation

To reveal the catalytic activity of neutral vanadium oxide nanoclusters in methanol (CH₃OH) oxidation, quantum chemical simulation of methanol adsorption on V₄O₁₀ cluster and further oxidation to formaldehyde (CH₂O) is performed at DFT PBE level. According to calculation, the cluster has a tetrahedral cage structure with four terminal V=O(t) and six bridging V–O(b)–V fragments. The reaction of methanol and V₄O₁₀ occurs through association and two abstraction stages sequentially. The role of the two oxygens O(t) and O(b) in these processes is shown to be different. Analysis of atomic charges and electron density in V₄O₁₀ allowed to explain the observed patterns and predict the reduction of the activation barrier of rate-determining step of (CH₂O)V₄O₁₀H₂ formation when the V₄O₁₀ has positive charge or titanium is introduced into the cluster’s structure.

1. Piracha S., Zhang Y., Raza A., Li G. Transition metal oxide clusters: advanced electrocatalysts for a sustainable energy future. Chemical Communication, 2024, 3, P. 9918–9929.

2. Wang K., Wu S., Wei S., Ya L. Theoretical study on the electrochemical properties of Ti-modified vanadium-oxide clusters. Inorganic Chemistry, 2025, 64 (32), P. 16413–16422.

3. Kolmanovich D.D., Chukavin N.N., Pivovarov N.A., Khaustov S.A., Ivanov V.K., Popov A.L. Cellular uptake of FITC-labeled Ce0.8Gd0.2O2−x nanoparticles in 2D and 3D mesenchymal stem cell systems. Nanosystems: Physics, Chemistry, Mathematics, 2024, 15 (3), P. 352–360.

4. Yan-Xia Zhao, Xiao-Nan Wu, Jia-Bi Ma, Sheng-Gui He, Xun-Lei Ding. Characterization and reactivity of oxygen-centred radicals over transition metal oxideclusters. Phys. Chem. Chem. Phys., 2011, 13, P. 1925–1938.

5. Sun X.Y., Wang S.D., Chen J.Y., Ma T.M., He S.G., Li X.N. Catalytic Conversion of NO and CO by noble-metal-free copper-vanadium oxide cluster anions CuVO3,4. The Journal of Physical Chemistry Letters, 2024, 15 (35), P. 9043–9050.

6. Zemski K.A., Justes D.R., Castleman A.W. Reactions of group V transition metal oxide cluster ions with ethane and ethylene. The Journal of Physical Chemistry A, 2001, 105, P. 10237–10245.

7. Zhang X., Schwarz H. Generation of gas-phase nanosized vanadium oxide clusters from a mononuclear precursor by solution nucleation and electrospray ionization. Chemistry: A European Journal, 2010, 16, P. 1163–1167.

8. Foltin M., Stueber G.J., Bernstein E.R. On the growth dynamics of neutral vanadium oxide and titanium oxide clusters. The Journal of Chemical Physics, 1999, 111, P. 9577–9586.

9. Calatayud M., Andres J., Beltran A. A systematic density functional theory study of VxO + y and VxOy (X = 2-4, Y = 2-10) systems. The Journal of Physical Chemistry A, 2001, 105, P. 9760–9775.

10. Vyboishchikov S.F., Sauer J. Gas-phase vanadium oxide anions: structure and detachment energies from density functional calculations. The Journal of Physical Chemistry A, 2000, 104, P. 10913–10922.

11. Vyboishchikov S.F., Sauer J. (V2O5)n Gas-Phase Clusters (n = 1-12) Compared to V2O5 Crystal: DFT Calculations. The Journal of Physical Chemistry A, 2001, 105, P. 8588–8598.

12. Archambault P., Wei Y., Peslherbe G. H. Density-functional theory studies of vanadium oxide clusters and their cations. Theoretical Chemistry Accounts, 2021, 140, 127.

13. Feyel S., Dobler J., Schroder D., Sauer J., Schwarz H. Thermal activation of methane by tetranuclear [V4O10]+. Angewandte Chemie International Edition, 2006, 45, P. 4681–4685.

14. Bell R.C., Zemski K.A., Castleman A.W. Gas-phase chemistry of vanadium oxide cluster cations. 3. Reactions with CCl4. The Journal of Physical Chemistry A, 1999, 103, P. 1585–1591.

15. Moore N.A., Mitric R., Justes D.R., Bonacic-Koutecky V., Castleman A.W. Kinetic analysis of the reaction between (V2O5)+n=1,2 and ethylene. The Journal of Physical Chemistry B, 2006, 110 (7), P. 3015–3022.

16. Zemski K.A., Justes D.R., Castleman A.W. Reactions of group V transition metal oxide cluster ions with ethane and ethylene. The Journal of Physical Chemistry A, 2001, 105, P. 10237–10245.

17. Blanco-Bonilla F., Estevez R., Lo´pez-Tenllado F.J., Luna D., Bautista F.M. Selective oxidation of methanol to green oxygenates on vanadiumaluminum phosphate based catalysts. Catalysis Today, 2024, 430, 114517(13).

18. Boehn B., Weißbach A. Krisponeit J.-O., Flege J.I., Falta J., Gregoratti L., Amati M., Zeller P., Imbihl R. Phase separation within vanadium oxide islands under reaction conditions: methanol oxidation at vanadium oxide films on Rh(111). The Journal of Physical Chemistry C, 2022, 126 (45), P. 19101–19112.

19. Broomhead W.T., Tian W., Herrera J.E., Chin Y-H.C. Kinetic coupling of redox and acid chemistry in methanol partial oxidation on vanadium oxide catalysts. ACS Catalysis. 2022, 12, P. 11801–11820.

20. Forzatti P., Tronconi E., Elmi A.S., Busca G. Methanol oxidation over vanadia-based catalysts. Applied Catalysis A: General, 1997, 157, P. 387– 408.

21. Feng Dong, Scott Heinbuch, Yan Xie, Jorge J Rocca, Elliot R Bernstein. Reaction of neutral vanadium oxide clusters with methanol. J. Phys. Chem. A, 2009, 113, P. 3029–3040.

22. Kaichev V.V., Popova G.Y., Chesalov Y.A., Saraev A.A., Zemlyanov D.Y., Beloshapkin S.A., Knop-Gericke A., Schlogl R., Andrushkevich T.V., Bukhtiyarov V.I. Selective oxidation of methanol to form dimethoxymethane and methyl formate over a monolayer V2O5/TiO2 catalyst. Journal of Catalysis, 2014, 311, P. 59–70.

23. Kaichev V.V., Popova G.Ya., Chesalov Yu.A., Saraev A.A., Andrushkevich T.V., Bukhtiyarov V.I. Active component of supported vanadium catalysts in the selective oxidation of methanol. Kinetics and Catalysis, 2016, 57 (1), P. 82–94.

24. Perdew J.P., Burke K., Ernzerhof M. Generalized gradient approximation made simple. Physical Review Letters, 1996, 77, P. 3865–3868.

25. Dyall K.G. An exact separation of the spin-free and spin-dependent terms of the Dirac–Coulomb–Breit hamiltonian. The Journal of Chemical Physics, 1994, 100, P. 2118–2127.

26. Laikov D.N. A new class of atomic basis functions for accurate electronic structure calculations of molecules. Chemical Physical Letters, 2005, 416, P. 116–120.

27. Schlegel H.B. Optimization of Equilibrium Geometries and Transition Structures. Journal of Computational Chemistry, 1982, 3, P. 214–218.

28. Gonzalez C., Schlegel H.B. An improved algorithm for reaction path following. The Journal of Chemical Physics, 1989, 90, P. 2154–2161.

29. Laikov, D.N., Ustynyuk Y.A. PRIRODA-04: A quantum-chemical program suite. New possibilities in the study of molecular systems with the application of parallel computing. Russian Chemical Bulletin, 2005, 54, P. 820–826.

30. Bandurist P.S., Pichugina D.A. Effect of stabilizing ligand on the catalytic properties of copper sulfide nanoclusters in CO oxidation. Kinetics and Catalysis, 2024, 65, P. 347–355.

31. Kotolevich Y., Pakrieva E., Kolobova E., Far´ıas M.H., Bogdanchikova N., Corte´s C.V., Pichugina D., Nikitina N., Carabineiro S.A.C., Pestryakov A. Effect of the metal deposition order on structural, electronic and catalytic properties of TiO2-supported bimetallic Au-Ag catalysts in 1-octanol selective oxidation. Catalysts, 2021, 11 (7), P. 1–18.

32. Kolyadenkov A.R., Pichugina D.A., Stakheev A.Y. Structures and stability of small bimetallic In–Pd and Ag–Pd clusters: a DFT investigation. Mendeleev Communications, 2026, 36, P. 267–269.

33. Dobler J., Pritzsche M., Sauer J. Oxidation of methanol to formaldehyde on supported vanadium oxide catalysts compared to gas phase molecules. Journal of the American Chemical Society, 2005, 127, P. 10861–10866.