He Ying, Wang Zhuoyue, Cao Aihui, Xu Xiao, Li Junqiang, Zhang Bo, Kang Longtian
Fujian Science & Technology Innovation Laboratory for Optoelectronic Information of China, Fuzhou, Fujian 350108, PR China; Key Laboratory of Design and Assembly of Functional Nanostructures, and Fujian Provincial Key Laboratory of Nanomaterials, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002, PR China; University of Chinese Academy of Sciences, Chinese Academy of Sciences, Beijing 100049, PR China; China Chengda Engineering Co., Ltd., Chengdu 610041, PR China.
Fujian Science & Technology Innovation Laboratory for Optoelectronic Information of China, Fuzhou, Fujian 350108, PR China; Key Laboratory of Design and Assembly of Functional Nanostructures, and Fujian Provincial Key Laboratory of Nanomaterials, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002, PR China.
J Colloid Interface Sci. 2023 May 15;638:123-134. doi: 10.1016/j.jcis.2023.01.100. Epub 2023 Jan 23.
The zinc-based photocatalysts for CO reduction have attracted increasing attention, however, usually exhibit low CO-to-CH selectivity. Here, the graphene oxide (GO)-coated zinc tetraphenylporphyrin (ZnTPP/GO) nanocomposites are successfully synthesized through a simple method. It is found that with the increase of GO content, the crystallinity of ZnTPP nanocrystals enhances with the size decrease, and then the light absorption can easily match with the solar spectrum. The optimal ZnTPP/GO sample exhibits the CH evolution rate of 41.6 μmol g h and CH selectivity of >95%, which are higher than those of ZnTPP nanocrystals (7.8 μmol g h and 50.3%). The systematic characterizations confirm that the generation of axial coordinated ZnOC bonds between ZnTPP and GO plays a key role in the formation of ZnTPP/GO nanostructure and their synergic effect on photocatalytic CO reduction. The encapsulation of GO on ZnTPP nanocrystals not only promotes the CO adsorption, interfacial reaction, and stability, but also accelerates the separation of photoinduced carriers on ZnTPP (0.1 ps vs. 425.9 ps), the transportation from ZnTPP to GO (2.3 ps vs. 83.6 ps), and their final enrichment on GO. This work provides a new strategy to apply graphene and organic nanomaterials in artificial photosynthesis.
用于CO还原的锌基光催化剂已引起越来越多的关注，然而，它们通常表现出较低的CO到CH选择性。在此，通过一种简单的方法成功合成了氧化石墨烯（GO）包覆的四苯基卟啉锌（ZnTPP/GO）纳米复合材料。研究发现，随着GO含量的增加，ZnTPP纳米晶体的结晶度提高，尺寸减小，进而光吸收能更容易与太阳光谱匹配。最优的ZnTPP/GO样品表现出41.6 μmol g h的CH生成速率和>95%的CH选择性，高于ZnTPP纳米晶体（7.8 μmol g h和50.3%）。系统表征证实，ZnTPP与GO之间轴向配位的ZnOC键的生成在ZnTPP/GO纳米结构的形成及其对光催化CO还原的协同效应中起关键作用。GO包覆在ZnTPP纳米晶体上不仅促进了CO吸附、界面反应和稳定性，还加速了光生载流子在ZnTPP上的分离（0.1 ps对425.9 ps）、从ZnTPP到GO的传输（2.3 ps对83.6 ps）以及它们最终在GO上的富集。这项工作为将石墨烯和有机纳米材料应用于人工光合作用提供了一种新策略。
