The highly evolved hydrogenase enzymes efficiently catalyze the hydrogen evolution reaction (HER) from water. Detailed structural studies of these enzymes have triggered many research efforts to synthesize their structural mimics based on metal complexes. However, the hydrogen production rates catalyzed by these molecular complexes are still too low to be technologically viable. Here, we report that a tailored PtAu24 nanocluster containing proton relays can efficiently catalyze the HER from water. We compared the electrocatalytic HER activities of Au25 nanoclusters protected with three different ligands, namely, 1-hexanethiolate, 3-mercaptopropionic acid and 3-mercapto-1-propanesulfonic acid, and found that the electrocatalytic activity is closely related with the proton-relaying abilities of the ligands. The core-engineered PtAu24 protected with efficient proton-relaying ligands exhibits unprecedented catalytic activity with a turnover frequency of 127 per second from water at a moderate overpotential of 0.7 V, greatly exceeding the performance of the best molecular catalyst. The atomically precise metal nanoclusters provide a platform for the design and optimization of finely tailored catalysts.
Bibliographical noteFunding Information:
This work was supported by the Korea CCS R&D Center (KCRC) Grant (NRF-2014M1A8A1074219) and the NRF Grants (NRF-2017R1A2B3006651 and 2009-0093823). K. K. acknowledges the support from the NRF Grant (NRF-2017R1A6A3A01008549). Q. T. and D.-e. J. were supported by University of California, Riverside.
© The Royal Society of Chemistry.
All Science Journal Classification (ASJC) codes
- Renewable Energy, Sustainability and the Environment
- Materials Science(all)