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Enhanced photocatalytic alkane production from fatty acid decarboxylation via inhibition of radical oligomerization

Abstract

The decarboxylation of bio-derived fatty acids provides a sustainable pathway for the production of alkane products under mild conditions; however, products are generally obtained in low selectivity due to the uncontrollable reactivity of radical intermediates. Here we demonstrate that photogenerated radicals can be rapidly terminated by surface hydrogen species during photocatalytic decarboxylation of fatty acids on a hydrogen-rich surface that is constructed by the interactions between H2 and Pt/TiO2 catalyst, thereby greatly inhibiting oligomerization; Cn1 alkanes can therefore be obtained from bio-derived C12–C18 fatty acids in high yields (≥90%) under mild conditions (30 °C, H2 pressure ≤0.2 MPa) and 365 nm light-emitting dode irradiation. Industrial low-value fatty acid mixtures (namely, soybean and tall oil fatty acids) can be transformed into alkane products in high yields (up to 95%). Our research introduces an efficient biomass-upgrading approach that is enabled by subtle control of the radical intermediate conversion on a heterogeneous surface.

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Fig. 1: A schematic representation of a photocatalytic decarboxylation strategy for the production of alkanes from bio-derived fatty acids.
Fig. 2: Photocatalytic decarboxylation of saturated fatty acids.
Fig. 3: The interaction between H2 and Pt/TiO2 and its influence on the production of Cn1 alkanes.
Fig. 4: Photocatalytic decarboxylation of unsaturated fatty acids and fatty acid mixtures over Pt/TiO2.

Data availability

The data that support the plots within this paper and other findings of this study are available from the corresponding author on reasonable request.

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Acknowledgements

This work was supported by the Strategic Priority Research Program of the Chinese Academy of Sciences (grant no. XDB17000000) and the National Natural Science Foundation of China (grant nos. 21721004, 21690082, 21690084, 21690080, 21711530020).

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Z.H. designed and conducted most of the experiments, and wrote the manuscript. Z.Z. carried out the life-cycle assessment and wrote the manuscript. C.Z. contributed to experiment design and manuscript revisions. J.L. performed the DFT study. H.L., N.L. and J.Z. contributed to product analysis, photoreactor design and mechanism investigation. General guidance, project directing and manuscript revisions were done by F.W.

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Correspondence to Feng Wang.

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Supplementary Information

Supplementary Methods, Discussion, Figs. 1–27, Tables 1–9 and references.

Supplementary Data

Atomic coordinates of the optimized computational models.

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Huang, Z., Zhao, Z., Zhang, C. et al. Enhanced photocatalytic alkane production from fatty acid decarboxylation via inhibition of radical oligomerization. Nat Catal 3, 170–178 (2020). https://doi.org/10.1038/s41929-020-0423-3

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