Zhang Wenqing, Fu Cenfeng, Low Jingxiang, Duan Delong, Ma Jun, Jiang Wenbin, Chen Yihong, Liu Hengjie, Qi Zeming, Long Ran, Yao Yingfang, Li Xiaobao, Zhang Hui, Liu Zhi, Yang Jinlong, Zou Zhigang, Xiong Yujie
School of Chemistry and Materials Science, and National Synchrotron Radiation Laboratory, University of Science and Technology of China, 230026, Hefei, Anhui, China.
Institute of Energy, Hefei Comprehensive National Science Center, 350 Shushanhu Rd, 230031, Hefei, Anhui, China.
Nat Commun. 2022 May 19;13(1):2806. doi: 10.1038/s41467-022-30532-z.
Nonoxidative coupling of methane (NOCM) is a highly important process to simultaneously produce multicarbons and hydrogen. Although oxide-based photocatalysis opens opportunities for NOCM at mild condition, it suffers from unsatisfying selectivity and durability, due to overoxidation of CH with lattice oxygen. Here, we propose a heteroatom engineering strategy for highly active, selective and durable photocatalytic NOCM. Demonstrated by commonly used TiO photocatalyst, construction of Pd-O in surface reduces contribution of O sites to valence band, overcoming the limitations. In contrast to state of the art, 94.3% selectivity is achieved for CH production at 0.91 mmol g h along with stoichiometric H production, approaching the level of thermocatalysis at relatively mild condition. As a benchmark, apparent quantum efficiency reaches 3.05% at 350 nm. Further elemental doping can elevate durability over 24 h by stabilizing lattice oxygen. This work provides new insights for high-performance photocatalytic NOCM by atomic engineering.
甲烷非氧化偶联（NOCM）是一个同时生产多碳化合物和氢气的极为重要的过程。尽管基于氧化物的光催化为温和条件下的NOCM提供了机会，但由于CH与晶格氧的过度氧化，其选择性和耐久性并不理想。在此，我们提出一种用于高活性、选择性和耐久性光催化NOCM的杂原子工程策略。以常用的TiO光催化剂为例，表面构建的Pd-O降低了O位点对价带的贡献，克服了相关限制。与现有技术相比，在0.91 mmol g h的条件下，CH生成的选择性达到94.3%，同时实现了化学计量的H生成，在相对温和的条件下接近热催化水平。作为基准，在350 nm处表观量子效率达到3.05%。进一步的元素掺杂可以通过稳定晶格氧将耐久性提高到24小时以上。这项工作通过原子工程为高性能光催化NOCM提供了新的见解。
