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A renewable amine for photochemical reduction of CO2

Nature Chemistry volume 3, pages 301–303 (2011)Cite this article

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Abstract

Photochemical reduction of CO2 (to produce formic acid) can be seen both as a method to produce a transportable hydrogen-based fuel and also to reduce levels of CO2 in the atmosphere. However, an often overlooked necessity for photochemical CO2 reduction is the need for a sacrificial electron donor, usually a tertiary amine. Here, we describe a new strategy for coupling the photochemical reduction of CO2 to photochemical water splitting, and illustrate this with a prototype example. Instead of seeking to eliminate the use of an external reducing agent altogether, our alternative strategy makes the reducing agent recyclable. This has two potential advantages over the direct coupling of CO2 reduction and water oxidation. First, it allows the two redox reactions to be carried out with existing chemistry, and second, it permits these reactions to be conducted under mutually incompatible conditions.

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Figure 1: Design of a renewable amine for photochemical reduction of CO2.
Figure 2: Independent synthesis of alkene 10.
Figure 3: Regeneration of amine 9 by hydrogenation of alkene 10, and an unexpected side reaction.
Figure 4: Illustration of the general strategy for coupling of CO2 reduction and water splitting.

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Acknowledgements

This work was supported by the Leverhulme Trust. The Physical Organic Chemistry Centre at Cardiff University was created with a Science and Innovation Award from the Engineering and Physical Sciences Research Council and by a grant from the Strategic Research Infrastructure Fund (SRIF) of the Higher Education Funding Council for Wales (HEFCW). All calculations were performed using the computational facilities of the Advanced Research Computing @ Cardiff (ARCCA) Division, Cardiff University.

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Authors and Affiliations

  1. Physical Organic Chemistry Centre, School of Chemistry, Cardiff University, Main Building, Park Place, Cardiff, CF10 3AT, UK

    Robert D. Richardson, Edward J. Holland & Barry K. Carpenter

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  1. Robert D. Richardson
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  2. Edward J. Holland
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  3. Barry K. Carpenter
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Contributions

B.K.C. directed and coordinated the project. E.J.H. and R.D.R. developed the synthesis of amine 9 and performed the preliminary photochemical studies. R.D.R. and B.K.C. wrote the paper and performed the DFT calculations. R.D.R. developed the authentic synthesis of alkene 10, performed the final photochemical studies and studied the hydrogenation and formation of 17. All authors commented on the paper.

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Correspondence to Barry K. Carpenter.

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The authors declare no competing financial interests.

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Richardson, R., Holland, E. & Carpenter, B. A renewable amine for photochemical reduction of CO2. Nature Chem 3, 301–303 (2011). https://doi.org/10.1038/nchem.1000

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