Visible-light-driven coproduction of diesel precursors and hydrogen from lignocellulose-derived methylfurans

Abstract

Photocatalytic hydrogen production from biomass is a promising alternative to water splitting thanks to the oxidation half-reaction being more facile and its ability to simultaneously produce solar fuels and value-added chemicals. Here, we demonstrate the coproduction of H2 and diesel fuel precursors from lignocellulose-derived methylfurans via acceptorless dehydrogenative C−C coupling, using a Ru-doped ZnIn2S4 catalyst and driven by visible light. With this chemistry, up to 1.04 g gcatalyst−1 h−1 of diesel fuel precursors (~41% of which are precursors of branched-chain alkanes) are produced with selectivity higher than 96%, together with 6.0 mmol gcatalyst−1 h−1 of H2. Subsequent hydrodeoxygenation reactions yield the desired diesel fuels comprising straight- and branched-chain alkanes. We suggest that Ru dopants, substituted in the position of indium ions in the ZnIn2S4 matrix, improve charge separation efficiency, thereby accelerating C−H activation for the coproduction of H2 and diesel fuel precursors.

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Fig. 1: Conceptual process diagram for the production of diesel fuels from lignocellulosic waste.
Fig. 2: Characterization of the Ru-ZnIn2S4 photocatalyst.
Fig. 3: Visible-light-driven conversion of 2,5-DMF/2-MF into diesel fuel by photocatalytic dehydrocoupling followed by HDO.
Fig. 4: Mechanistic studies of photocatalytic acceptorless dehydrocoupling by activation of furfuryl (or benzylic) C−H bonds.
Fig. 5: Operando and photophysical characterization of the Ru-ZnIn2S4 photocatalyst.

Data availability

Additional and supporting data are provided in the Supplementary Information. Further data that support the plots within this Article and other findings of this study are available from the corresponding author upon reasonable request.

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Acknowledgements

The authors acknowledge SOLEIL for provision of synchrotron radiation facilities and thank G. Alizon for technical assistance in using beamline SAMBA. The authors also acknowledge financial support from the National Natural Science Foundation of China (21721004, 21690082, 21690084, 21690080), the Strategic Priority Research Program of Chinese Academy of Sciences (XDB17020300, XDB17000000), the National Natural Science Foundation of China (21711530020), the University of Trieste (programme FRA 2018, project INSIDE), the Italian Ministry for University and Research (MIUR, programme FFABR 2017) and the INSTM consortium.

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N.L. and F.W. conceived the research. N.L. conducted most of the experiments in this work, analysed the data and wrote the manuscript. XANES/EXAFS experiments and their discussion were done by T.M., assisted by E.F. T.M., P.F. and E.F. fully revised the manuscript. J.Z. and N.L. designed and fabricated the LED photoreactor. The variation of CPD was measured by W.N., assisted by F.F. J.M.L. carried out the DFT calculations. Transient absorption analysis was done by J.X.L., assisted by S.J. HAADF-STEM and EDX mappings were performed by M.H. Cyclic voltammetry was measured by L.L. Mott–Schottky measurements were done by C.M. T.H. and M.W. added to the discussion and contributed to the preparation of the manuscript. F.W. planned, supervised and led the project.

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Correspondence to Feng Wang.

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Supplementary methods, Supplementary Notes 1-2, Supplementary Tables 1-8, Supplementary Figs. 1–58, Supplementary references

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Luo, N., Montini, T., Zhang, J. et al. Visible-light-driven coproduction of diesel precursors and hydrogen from lignocellulose-derived methylfurans. Nat Energy 4, 575–584 (2019). https://doi.org/10.1038/s41560-019-0403-5

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