In nature, photosynthetic organelles harness solar radiation to produce energy-rich compounds from water and atmospheric CO2 via exquisite supramolecular assemblies. Although artificial photocatalytic cycles have been shown to occur at higher intrinsic efficiencies, the low selectivity and stability in water for multi-electron CO2 reduction hamper their practical applications. The creation of water-compatible artificial photocatalytic systems mimicking the natural photosynthetic apparatus for selective and efficient solar fuel production represents a major challenge. Here we show a highly stable and efficient artificial spherical chromatophore nanomicelle system self-assembled from Zn porphyrin amphiphiles with a Co catalyst in water for CO2-to-methane conversion with a turnover number >6,600 and 89% selectivity over 30 days. The hierarchical self-assembly induced a spherical antenna effect that could facilitate the photocatalytic process with an initial 15% solar-to-fuel efficiency. Furthermore, it has a capability to efficiently reduce atmospheric CO2 into methane with high selectivity in water.
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J.T. acknowledges the funding support from National Key Research and Development Program of China (2022YFA1206200); Shanghai Institute of Organic Chemistry and Shanghai Branch, CAS; Shanghai Rising-Star Program (22QA1411200); and the National Natural Science Foundation of China (no. 22271306). J.T. acknowledges the Marie-Curie Fellowship. I.M. acknowledges the Canada 150 Research Chair and NSERC Discovery Grant. R.Y. acknowledges the funding support from Young Scientists Fund of the National Natural Science Foundation of China (grant no. 21905240); the Shenzhen Research Institute, City University of Hong Kong; the State Key Laboratory of Marine Pollution (SKLMP) Seed Collaborative Research Fund; the Guangdong Basic and Applied Basic Research Fund (2022A1515011333); the Shenzhen Science and Technology Program (JCYJ20220818101204009); Hong Kong Research Grant Council (21300620) and the State Key Laboratory of Marine Pollution Internal Research Fund (SKLMP/IRF/0029). D.L.P. and L.D. thank the University of Hong Kong Development Fund 2013-2014 project ‘New Ultrafast Spectroscopy Experiments for Shared Facilities’. We thank the Shanghai Synchrotron Radiation Facility for providing the BL16B1 and BL10U1 beamline for collecting the synchrotron X-ray scattering data. We acknowledge access and support of the GW4 Facility for High-Resolution Electron Cryo-Microscopy, funded by the Wellcome Trust (202904/Z/16/Z and 206181/Z/17/Z) and BBSRC (BB/R000484/1). We thank Y. Zhang and X. Jin for the useful discussions. We thank M. Sener and D. H. Fackler for permission to use the visual molecular dynamics model in Fig. 1c.
The authors declare no competing interests.
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Yu, J., Huang, L., Tang, Q. et al. Artificial spherical chromatophore nanomicelles for selective CO2 reduction in water. Nat Catal 6, 464–475 (2023). https://doi.org/10.1038/s41929-023-00962-z