Enzymes feature the concerted operation of multiple components around an active site, leading to exquisite catalytic specificity. Realizing such configurations on synthetic catalyst surfaces remains elusive. Here, we report a nanoparticle/ordered-ligand interlayer that contains a multi-component catalytic pocket for high-specificity CO2 electrocatalysis. The nanoparticle/ordered-ligand interlayer comprises a metal nanoparticle surface and a detached layer of ligands in its vicinity. This interlayer possesses unique pseudocapacitive characteristics where desolvated cations are intercalated, creating an active-site configuration that enhances catalytic turnover by two orders and one order of magnitude against a pristine metal surface and nanoparticle with tethered ligands, respectively. The nanoparticle/ordered-ligand interlayer is demonstrated across several metals with up to 99% CO selectivity at marginal overpotentials and onset overpotentials of as low as 27 mV, in aqueous conditions. Furthermore, in a gas-diffusion environment with neutral media, the nanoparticle/ordered-ligand interlayer achieves nearly unit CO selectivity at high current densities (98.1% at 400 mA cm−2).
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This work was supported by the Director, Office of Science, Office of Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division, of the US Department of Energy under contract no. DE-AC02-05CH11231, FWP CH030201 (Catalysis Research Program). F.Z. and L.-W.W. were supported by Joint Center for Artificial Photosynthesis, a US Department of Energy Energy Innovation Hub, supported through the Office of Science of the US Department of Energy under award no. DE-SC0004993. We used resources of the National Energy Research Scientific Computing Center (NERSC) and resources from National Renewable Energy Laboratory (NREL). H.F. was supported by the Director, Office of Science, Office of Basic Energy Sciences, Division of Chemical, Geological and Biosciences of the US Department of Energy under contract no. DE-AC02-05CH11231, FWP KC0304030 (Solar Photochemistry Research Program). Work at the Molecular Foundry was supported by the Director, Office of Science, Office of Basic Energy Sciences, of the US Department of Energy under contract no. DE-AC02-05CH11231. This research used resources of the Advanced Light Source, which is a US Department of Energy Office of Science User Facility, under contract no. DE-AC02-05CH11231. We thank S. Fakra for assistance with X-ray absorption spectroscopy experiments at Beamline 10.3.2 at the Advanced Light Source. We thank H. Celik and the University of California at Berkeley’s NMR facility in the College of Chemistry for spectroscopic assistance. Instruments in the NMR facility in the College of Chemistry are supported in part by the National Institutes of Health under grant no. S10OD024998. This work made use of the facility at the Lawrence Berkeley National Laboratory Catalysis Laboratory, which is supported by the US Department of Energy, Office of Science, Basic Energy Sciences, under contract no. DE-AC02-05CH11231. Inductively coupled plasma optical emission spectrometry was supported by the Microanalytical Facility, College of Chemistry, University of California, Berkeley. We also thank T. Lin and J. Chan for experimental assistance. D.K. and S.Y. acknowledge support from Samsung Scholarship.
The authors declare no competing interests.
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Kim, D., Yu, S., Zheng, F. et al. Selective CO2 electrocatalysis at the pseudocapacitive nanoparticle/ordered-ligand interlayer. Nat Energy 5, 1032–1042 (2020). https://doi.org/10.1038/s41560-020-00730-4
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