Wu Jiacong, Huang Fei, Hu Qinyuan, He Dongpo, Liu Wenxiu, Li Xiaodong, Yan Wensheng, Hu Jun, Zhu Junfa, Zhu Shan, Chen Qingxia, Jiao Xingchen, Xie Yi
Key Laboratory of Synthetic and Biological Colloids, Ministry of Education, School of Chemical and Material Engineering Jiangnan University, Wuxi 214122, China.
Key Laboratory of Precision and Intelligent Chemistry, Hefei National Research Center for Physical Sciences at Microscale, National Synchrotron Radiation Laboratory University of Science and Technology of China, Hefei 230026, China.
J Am Chem Soc. 2024 Sep 25;146(38):26478-26484. doi: 10.1021/jacs.4c09841. Epub 2024 Sep 11.
Herein, composites of nanosheets with van der Waals contacts are employed to disclose how the interlayer-microenvironment affects the product selectivity of carbon dioxide (CO) 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 (CHOH). As a prototype, the CoNiS-InO 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 InO nanosheets and the CoNiS nanosheets within the composite. The fabricated CoNiS-InO composites of nanosheets exhibit the detection of the key intermediate *CHO during CO photoreduction through in situ Fourier transform infrared spectra, while the InO nanosheets and CoNiS nanosheets alone do not show this capability, further verified by the density functional theory calculations. Accordingly, the CoNiS-InO composites of nanosheets show the ability to produce CHOH, whereas the CoNiS and InO nanosheets solely generate carbon monoxide products from CO photoreduction.
在此，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。引入具有双活性位点的纳米片复合材料概念，以操纵键合构型并促进甲醇（CH₃OH）的热力学形成。作为原型，制备了纳米片的CoNiS-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zeta电位测试证实了复合材料中In₂O₃纳米片与CoNiS纳米片之间存在范德华接触而非化学键合。通过原位傅里叶变换红外光谱，制备的纳米片CoNiS-In₂O₃复合材料在CO₂光还原过程中检测到关键中间体*CHO，而单独的In₂O₃纳米片和CoNiS纳米片则没有这种能力，密度泛函理论计算进一步证实了这一点。因此，纳米片的CoNiS-In₂O₃复合材料表现出产生CH₃OH的能力，而CoNiS和In₂O₃纳米片仅从CO₂光还原中产生一氧化碳产物。
