期刊
CHEMICAL SCIENCE
卷 14, 期 37, 页码 10212-10218出版社
ROYAL SOC CHEMISTRY
DOI: 10.1039/d3sc02793g
关键词
-
This study introduces a novel strategy to synthesize a unique Ag/Ti bimetallic nanocluster, which exhibits exceptional catalytic activity in the electroreduction of CO2. The identification of specific Ag sites with high catalytic activity provides valuable insights for the design of efficient CO2 reduction catalysts.
The accurate identification of catalytic sites in heterogeneous catalysts poses a significant challenge due to the intricate nature of controlling interfacial chemistry at the molecular level. In this study, we introduce a novel strategy to address this issue by utilizing a thiacalix[4]arene (TC4A)-protected Ti-oxo core as a template for loading Ag1+ ions, leading to the successful synthesis of a unique Ag/Ti bimetallic nanocluster denoted as Ti8Ag8. This nanocluster exhibits multiple surface-exposed Ag sites and possesses a distinctive core-shell structure, consisting of a {Ti-4@Ag-8(TC(4)A)(4)} core housing a {Ti2O2@Ag-4(TC4A)(2)} motif and two {Ti@Ag-2(TC4A)} motifs. To enable a comprehensive analysis, we also prepared a Ti2Ag4 cluster with the same {Ti2O2@Ag-4(TC4A)(2)} structure found within Ti8Ag8. The structural disparities between Ti8Ag8 and Ti2Ag4 provide an excellent platform for a comparison of catalytic activity at different Ag sites. Remarkably, Ti8Ag8 exhibits exceptional performance in the electroreduction of CO2 (eCO(2)RR), showcasing a CO faradaic efficiency (FECO) of 92.33% at -0.9 V vs. RHE, surpassing the FECO of Ti2Ag4 (69.87% at -0.9 V vs. RHE) by a significant margin. Through density functional theory (DFT) calculations, we unveil the catalytic mechanism and further discover that Ag active sites located at {Ti@Ag-2(TC4A)} possess a higher e(d) value compared to those at {Ti2O2@Ag-4(TC4A)(2)}, enhancing the stabilization of the *COOH intermediate during the eCO(2)RR. This study provides valuable insights into the accurate identification of catalytic sites in bimetallic nanoclusters and opens up promising avenues for efficient CO2 reduction catalyst design.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据