Liu Yidan, Ren Xu, Ji Yali, Li Ting, Jia Rongrong, Shi Liyi, Zhou Wenlong, Qiao Xiran, Huang Lei
College of Textile Science and Engineering (International Institute of Silk), Zhejiang Sci-Tech University, Hangzhou 310018, China.
Zhejiang Provincial Key Research Institute of Medical Materials and Tissue Engineering, Hangzhou 311121, China.
Molecules. 2024 Nov 25;29(23):5560. doi: 10.3390/molecules29235560.
Metallic heterostructural nanocrystals (HNCs) hold immense potential in electrocatalytic carbon dioxide reduction reaction (CORR) owing to their abundant active sites and high intrinsic activity. However, a significant challenge still remains in achieving controlled nucleation and growth sites for HNCs on supports and comprehending the influence of the structure-activity relationship on electrocatalytic CORR performance. This work presents a photochemical self-assembly technique without the necessity for reducing agents or facet-specific capping agents. By controlling lattice mismatch and manipulating transfer paths of photo-generated carriers, we can precisely direct the growth sites and nucleation of nanocrystals, enabling the self-assembly of supported core-shell and Janus nanostructures. Compared to Pd(T)@Au core-shell HNCs with the same loading, Pd cube-Au Janus HNCs exhibit significantly enhanced selectivity and stability toward carbon monoxide (CO) production in CORR at less negative potentials. The Pd cube-Au Janus HNC electrocatalyst achieved a Faradaic efficiency (FE) of 92.6 ± 3.5% for CO electroreduction, accompanied by a current density of 72.3 mA·cm at -0.58 V. This work provides an effective strategy for designing advanced supported tandem electrocatalysts to boost the selectivity and durability test of CORR.
金属异质结构纳米晶体（HNCs）因其丰富的活性位点和高本征活性，在电催化二氧化碳还原反应（CORR）中具有巨大潜力。然而，在实现HNCs在载体上的可控成核和生长位点以及理解结构-活性关系对电催化CORR性能的影响方面，仍然存在重大挑战。这项工作提出了一种无需还原剂或特定晶面封端剂的光化学自组装技术。通过控制晶格失配和操纵光生载流子的转移路径，我们可以精确地引导纳米晶体的生长位点和成核，实现负载型核壳和Janus纳米结构的自组装。与相同负载量的Pd(T)@Au核壳HNCs相比，Pd立方体-Au Janus HNCs在CORR中对一氧化碳（CO）生成表现出显著增强的选择性和稳定性，且所需负电位更低。Pd立方体-Au Janus HNC电催化剂在-0.58 V时实现了92.6±3.5%的CO电还原法拉第效率（FE），同时电流密度为72.3 mA·cm 。这项工作为设计先进的负载型串联电催化剂以提高CORR的选择性和耐久性测试提供了一种有效策略。
