Zeng Ruijin, Liu Tongyu, Qiu Minghao, Tan Hao, Gu Yu, Ye Na, Dong Zhaoqi, Li Lu, Lin Fangxu, Sun Qiang, Zhang Qinghua, Gu Lin, Luo Mingchuan, Tang Dianping, Guo Shaojun
School of Materials Science and Engineering, Peking University, Beijing 100871, China.
Key Laboratory for Analytical Science of Food Safety and Biology (MOE & Fujian Province), State Key Laboratory of Photocatalysis on Energy and Environment, Department of Chemistry, Fuzhou University, Fuzhou 350108, China.
J Am Chem Soc. 2024 Apr 10;146(14):9721-9727. doi: 10.1021/jacs.3c13827. Epub 2024 Mar 31.
The volumetric density of the metal atomic site is decisive to the operating efficiency of the photosynthetic nanoreactor, yet its rational design and synthesis remain a grand challenge. Herein, we report a shell-regulating approach to enhance the volumetric density of Co atomic sites onto/into multishell ZnCdS for greatly improving CO photoreduction activity. We first establish a quantitative relation between the number of shell layers, specific surface areas, and volumetric density of atomic sites on multishell ZnCdS and conclude a positive relation between photosynthetic performance and the number of shell layers. The triple-shell ZnCdS-Co achieves the highest CO yield rate of 7629.7 μmol g h, superior to those of the double-shell ZnCdS-Co (5882.2 μmol g h) and single-shell ZnCdS-Co (4724.2 μmol g h). Density functional theory calculations suggest that high-density Co atomic sites can promote the mobility of photogenerated electrons and enhance the adsorption of Co(bpy) to increase CO activation (CO → CO* → COOH* → CO* → CO) the S-Co-bpy interaction, thereby enhancing the efficiency of photocatalytic CO reduction.
金属原子位点的体密度对光合纳米反应器的运行效率起着决定性作用，但其合理设计与合成仍然是一个巨大的挑战。在此，我们报道了一种壳层调控方法，以提高多壳层ZnCdS上/内Co原子位点的体密度，从而极大地提高CO光还原活性。我们首先建立了多壳层ZnCdS的壳层数、比表面积与原子位点体密度之间的定量关系，并得出光合性能与壳层数之间呈正相关。三壳层ZnCdS-Co实现了7629.7 μmol g⁻¹ h⁻¹的最高CO产率，优于双壳层ZnCdS-Co（5882.2 μmol g⁻¹ h⁻¹）和单壳层ZnCdS-Co（4724.2 μmol g⁻¹ h⁻¹）。密度泛函理论计算表明，高密度的Co原子位点可以促进光生电子的迁移，并增强Co(bpy)的吸附，以增加CO活化（CO → CO* → COOH* → CO* → CO）以及S-Co-bpy相互作用，从而提高光催化CO还原的效率。
