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Selective photocatalytic oxidation of methane by quantum-sized bismuth vanadate


The direct oxidation of methane to more desirable, one-carbon oxygenated molecules such as methanol and formaldehyde offers a pathway towards a more sustainable chemical industry as the current commercial reforming process involving two steps features a high carbon footprint and energy consumption. Here, we report the selective photocatalytic oxidation of methane at room temperature using quantum-sized bismuth vanadate nanoparticles as the catalyst and oxygen as a mild oxidant. The reaction offers a high selectivity, of 96.6% for methanol or 86.7% for formaldehyde, under optimum wavelength and intensity of light, reaction time and amount of water solvent. Comprehensive characterizations disclose a multistep reaction mechanism in which the activation of methane by the hydroxyl radical determines the reaction rate. This work broadens the avenue towards the selective conversion of the greenhouse gas methane into desirable chemical products in a sustainable way.

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Fig. 1: Gibbs free energy corresponding to the formation of CH3OOH, CH3OH, HCHO and CO2 from CH4 oxidation at 298 K.
Fig. 2: Synthesis and characterization of q-BiVO4.
Fig. 3: Photocatalytic oxidation of CH4 under different conditions.
Fig. 4: Selective oxidations of CH4.
Fig. 5: Proposed reaction mechanism.
Fig. 6: Stepwise analysis of the reaction mechanism.

Data availability

The data that support the findings of this study are available from the corresponding author upon request.


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This work was sponsored by the ‘Strategic Priority Research Program’ of the Chinese Academy of Sciences (XDA09040100, Z.T.), the National Key Basic Research Program of China (2016YFA0200700, Z.T.), the Frontier Science Key Project of the Chinese Academy of Sciences (QYZDJ-SSW-SLH038, Z.T.), the National Natural Science Foundation of China (21890381 and 21721002, Z.T.), the K.C. Wong Education Foundation (Z.T.) and GuangDong Provincial Public Security Department (GZQC20-PZ11-FD084, D.H.).

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Authors and Affiliations



Y.F. and Z.T. conceived the idea, developed the outline, designed the experiment and compiled the manuscript. Y.F. conducted all the experiments and tests with the assistance of W.Z., X.Q., H.L. Y.J. and Z.S. The project was coordinated by D.H. who also provided critical feedback. L.N. and Z.T. supervised the whole project.

Corresponding authors

Correspondence to Dongxue Han or Zhiyong Tang.

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The authors declare no competing interests.

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Peer review information Nature Sustainability thanks Masahiro Miyauchi, Vitaly Ordomsky, Bryce Sadtler and Zhiguo Yi for their contribution to the peer review of this work.

Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

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Supplementary Information

Supplementary Methods, Figs. 1–43, Tables 1–4 and refs. 1–17.

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Fan, Y., Zhou, W., Qiu, X. et al. Selective photocatalytic oxidation of methane by quantum-sized bismuth vanadate. Nat Sustain 4, 509–515 (2021).

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