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Selective visible-light photocatalysis of acetylene to ethylene using a cobalt molecular catalyst and water as a proton source

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Abstract

The production of polymers from ethylene requires the ethylene feed to be sufficiently purified of acetylene contaminant. Accomplishing this task by thermally hydrogenating acetylene requires a high temperature, an external feed of H2 gas and noble-metal catalysts. It is not only expensive and energy-intensive, but also prone to overhydrogenating to ethane. Here we report a photocatalytic system that reduces acetylene to ethylene with ≥99% selectivity under both non-competitive (no ethylene co-feed) and competitive (ethylene co-feed) conditions, and near 100% conversion under the latter industrially relevant conditions. Our system uses a molecular catalyst based on earth-abundant cobalt operating under ambient conditions and sensitized by either [Ru(bpy)3]2+ or an inexpensive organic semiconductor (metal-free mesoporous graphitic carbon nitride) under visible light. These features and the use of water as a proton source offer advantages over current hydrogenation technologies with respect to selectivity and sustainability.

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Fig. 1: Strategies for producing polymer-grade ethylene.
Fig. 2: Sensitizers and catalyst used in this study for the photoreduction of acetylene to ethylene and their performance.
Fig. 3: Mechanistic analysis for the photoreduction of acetylene to ethylene.
Fig. 4: Photoreduction of the ethylene/acetylene mixture.

Data availability

All the data supporting the findings of this study are available within the Article and its Supplementary Information. Source data are provided with this paper.

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Acknowledgements

This work was supported by the Center for Bio-Inspired Energy Science (CBES), an Energy Frontier Research Center funded by the US Department of Energy, Office of Science, Basic Energy Sciences, under award no. DE-SC0000989. This work made use of the IMSERC facility at Northwestern University, which has received support from the NIH (1S10OD012016-01/1S10RR019071-01A1), the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-1542205), the State of Illinois and the International Institute for Nanotechnology (IIN), and the REACT Core facility at Northwestern University, funded by the US Department of Energy, Catalysis Science programme (DE-SC0001329) for the purchase of the GC-MS instrument. We thank S. Alayoglu and R. López-Arteaga for help with the gas-phase IR and emission lifetime measurements, respectively.

Dedication: We dedicate this work to Sir Fraser Stoddart on the occasion of his 80th birthday.

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Authors

Contributions

F.A., L.Ð. and E.A.W. conceived the project, contributed to the experimental design and wrote the manuscript. E.A.W. directed the research. F.A. and L.Ð. designed and performed the experiments and analysed the results. F.A., L.Ð. and N.S. carried out the GC experiments. L.Ð. and S.I.S. designed and prepared the materials. E.A.W. and S.I.S. secured the funding. All authors contributed to manuscript preparation.

Corresponding author

Correspondence to Emily A. Weiss.

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Competing interests

F.A., L.Ð., E.A.W. and S.I.S. are co-inventors of a patent application (no. PCT/US2022/026732) filed by Northwestern University on the photocatalytic reduction of acetylene to ethylene.

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Nature Chemistry thanks Sven Rau, Tierui Zhang and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary Information

Experimental Section, Supplementary Figs. 1–24, Tables 1–6 and references.

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Underlying measured data

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Arcudi, F., Ðorđević, L., Schweitzer, N. et al. Selective visible-light photocatalysis of acetylene to ethylene using a cobalt molecular catalyst and water as a proton source. Nat. Chem. (2022). https://doi.org/10.1038/s41557-022-00966-5

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