中国科学技术大学谢毅团队报道了中间层双活性位点协同调节光催化CoNi₂S₄-In₂O₃途径。研究相关成果发表在2024年9月11日出版的国际学术期刊《美国化学会杂志》。

该文采用具有范德华接触的纳米片复合材料来揭示层间微环境如何影响二氧化碳（CO₂）光还原的产物选择性。引入了具有双活性位点的纳米片复合材料的概念，以操纵键合结构并促进甲醇（CH₃OH）的热力学形成。

作为原型，研究人员制备了纳米片的CoNi₂S₄-In₂O₃复合材料，其中高分辨率透射电子显微镜成像、X射线光电子能谱和ζ电位测试证实了复合材料中In₂O₃纳米片和CoNi₂S₄纳米片之间存在范德华接触，而不是化学键合。

通过原位傅里叶变换红外光谱，所制备的纳米片CoNi₂S₄-In₂O₃复合材料在CO₂光还原过程中检测到关键中间体*CH₃O，而In₂O₃纳米片和CoNi₂S₄纳米片本身并没有显示出这种能力，这进一步得到了密度泛函理论计算的验证。因此，纳米片的CoNi₂S₄-In₂O₃复合材料显示出产生CH₃OH的能力，而CoNi₂S₄和In₂O₃纳米片仅通过CO₂光还原产生一氧化碳产物。

附：英文原文

Title: Regulated Photocatalytic CO2-to-CH3OH Pathway by Synergetic Dual Active Sites of Interlayer

Author: Jiacong Wu, Fei Huang, Qinyuan Hu, Dongpo He, Wenxiu Liu, Xiaodong Li, Wensheng Yan, Jun Hu, Junfa Zhu, Shan Zhu, Qingxia Chen, Xingchen Jiao, Yi Xie

Issue&Volume: September 11, 2024

Abstract: Herein, composites of nanosheets with van der Waals contacts are employed to disclose how the interlayer-microenvironment affects the product selectivity of carbon dioxide (CO2) photoreduction. The concept of composites of nanosheets with dual active sites is introduced to manipulate the bonding configuration and promote the thermodynamic formation of methanol (CH3OH). As a prototype, the CoNi2S4–In2O3 composites of nanosheets are prepared, in which high-resolution transmission electron microscopy imaging, X-ray photoelectron spectroscopy spectra, and zeta potential tests confirm the presence of van der Waals contacts rather than chemical bonding between the In2O3 nanosheets and the CoNi2S4 nanosheets within the composite. The fabricated CoNi2S4–In2O3 composites of nanosheets exhibit the detection of the key intermediate *CH3O during CO2 photoreduction through in situ Fourier transform infrared spectra, while the In2O3 nanosheets and CoNi2S4 nanosheets alone do not show this capability, further verified by the density functional theory calculations. Accordingly, the CoNi2S4–In2O3 composites of nanosheets show the ability to produce CH3OH, whereas the CoNi2S4 and In2O3 nanosheets solely generate carbon monoxide products from CO2 photoreduction.

DOI: 10.1021/jacs.4c09841

Source: https://pubs.acs.org/doi/abs/10.1021/jacs.4c09841