Direct non-oxidative dehydrogenation of alkanes produces useful carbon feedstocks and hydrogen fuel. However, breaking the C–H bonds in alkanes typically requires high temperature, stoichiometric oxidants or high-energy ultraviolet light; processes that operate under milder conditions are attractive but tend to have poor efficiency. Here we report Pt/black TiO2 photocatalysts in which Pt species are close to each other but not directly bonded, exhibiting high performance for alkane dehydrogenation in visible to near-infrared light at room temperature. For cyclohexane dehydrogenation, the turnover number for H2 production exceeded 100,000 without any deactivation over 80 reaction cycles, far beyond thermal reactions. For methane, 8.2% conversion was achieved with 65% selectivity to propane, rather than the more common ethane. We propose that methane undergoes intramolecular dehydrogenation to produce a methylene intermediate. For C2+ alkanes, fast dehydrogenation (up to 1,440 µmol g−1 h−1) to the corresponding olefins was realized. Distinct from isolated Pt+ monomers, the collections of Pt+ monomers give better photocatalytic activity and selectivity.
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This work was financially supported by the National Natural Science Foundation of China (grant number 92061105, 21875090), Natural Science Foundation of Jilin Province (20210101121JC, 20210509035RQ) and the Fundamental Research Funds for the Central Universities. The XAFS experiments were conducted in 1W1B beam line of Beijing Synchrotron Radiation Facility. We thank Y. Zhao at Beijing University of Chemical Technology for help with XAFS experiments.
The authors declare no competing interests.
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Nature Energy thanks Jier Huang, Ding Ma, Hisao Yoshida and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.
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Zhang, L., Liu, L., Pan, Z. et al. Visible-light-driven non-oxidative dehydrogenation of alkanes at ambient conditions. Nat Energy 7, 1042–1051 (2022). https://doi.org/10.1038/s41560-022-01127-1