Yamazaki Yuki, Tomoyasu Yuki, Kawawaki Tokuhisa, Negishi Yuichi
Department of Applied Chemistry, Faculty of Science, Tokyo University of Science 1-3 Kagurazaka, Shinjuku-ku Tokyo 162-8601 Japan.
Carbon Value Research Center, Research Institute for Science & Technology, Tokyo University of Science 2641 Yamazaki Noda Chiba 278-8510 Japan.
Nanoscale Adv. 2025 Feb 12;7(6):1518-1523. doi: 10.1039/d4na01045k. eCollection 2025 Mar 11.
The photocatalytic carbon dioxide (CO) reduction reaction (CORR), which reduces CO to various useful chemical compounds by light, has attracted attention to achieve carbon neutrality. In photocatalytic CORR, it is effective to load metal nanoparticles (NP) as cocatalysts on the surface of semiconductor photocatalysts to improve their activity and selectivity. In this study, we used ultrafine metal nanoclusters (NC) with a particle size of about 1 nm as cocatalysts to clarify the effect of surface ligands on the activity and selectivity of the photocatalytic CORR. As a result, it was shown that the introduction of hydrophobic ligands to the Au NC cocatalyst suppresses the competing hydrogen evolution reaction, thereby increasing the selectivity of CORR. In addition, the hydrophobic ligand-protected Au NC cocatalysts exhibited 66 times higher CO evolution rates per Au-loading weights than the Au NP cocatalysts with a particle size of about 7 nm. These results provide crucial insights into the creation of highly active metal NC cocatalysts for photocatalytic CORR.
光催化二氧化碳（CO）还原反应（CORR）通过光照将CO还原为各种有用的化合物，在实现碳中和方面受到了关注。在光催化CORR中，在半导体光催化剂表面负载金属纳米颗粒（NP）作为助催化剂来提高其活性和选择性是有效的。在本研究中，我们使用粒径约为1nm的超细金属纳米团簇（NC）作为助催化剂，以阐明表面配体对光催化CORR活性和选择性的影响。结果表明，向Au NC助催化剂中引入疏水性配体可抑制竞争性析氢反应，从而提高CORR的选择性。此外，疏水性配体保护的Au NC助催化剂每Au负载量的CO析出速率比粒径约为7nm的Au NP助催化剂高66倍。这些结果为制备用于光催化CORR的高活性金属NC助催化剂提供了关键见解。
