High-performance photocatalytic nonoxidative conversion of methane to ethane and hydrogen by heteroatoms-engineered TiO2
Wenqing Zhang, Cen‐Feng Fu, Jingxiang Low, Delong Duan, Jun Ma, Wenbin Jiang, Yihong Chen, Hengjie Liu, Zeming Qi, Ran Long, Yingfang Yao, Xiaobao Li, Hui Zhang, Zhi Liu, Jinlong Yang, Zhigang Zou, Yujie Xiong
Abstract
Abstract 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 4 with lattice oxygen. Here, we propose a heteroatom engineering strategy for highly active, selective and durable photocatalytic NOCM. Demonstrated by commonly used TiO 2 photocatalyst, construction of Pd–O 4 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 C 2 H 6 production at 0.91 mmol g –1 h –1 along with stoichiometric H 2 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.