通过晶格氧循环实现高效、选择性和稳定的光催化甲烷偶联制乙烷。
Highly efficient, selective, and stable photocatalytic methane coupling to ethane enabled by lattice oxygen looping.
作者信息
Zhai Guangyao, Cai Lejuan, Ma Jun, Chen Yihong, Liu Zehua, Si Shenghe, Duan Delong, Sang Shuaikang, Li Jiawei, Wang Xinyu, Liu Ying-Ao, Qian Bing, Liu Chengyuan, Pan Yang, Zhang Ning, Liu Dong, Long Ran, Xiong Yujie
机构信息
Key Laboratory of Precision and Intelligent Chemistry, School of Chemistry and Materials Science, Department of Environmental Science and Engineering, National Synchrotron Radiation Laboratory, School of Nuclear Science and Technology, University of Science and Technology of China, Hefei, Anhui 230026, China.
Sustainable Energy and Environmental Materials Innovation Center, Nano Science and Technology Institute, Suzhou Institute for Advanced Research, University of Science and Technology of China, Suzhou, Jiangsu 215123, China.
出版信息
Sci Adv. 2024 Jun 28;10(26):eado4390. doi: 10.1126/sciadv.ado4390.
Light-driven oxidative coupling of methane (OCM) for multi-carbon (C) product evolution is a promising approach toward the sustainable production of value-added chemicals, yet remains challenging due to its low intrinsic activity. Here, we demonstrate the integration of bismuth oxide (BiO) and gold (Au) on titanium dioxide (TiO) substrate to achieve a high conversion rate, product selectivity, and catalytic durability toward photocatalytic OCM through rational catalytic site engineering. Mechanistic investigations reveal that the lattice oxygen in BiO is effectively activated as the localized oxidant to promote methane dissociation, while Au governs the methyl transfer to avoid undesirable overoxidation and promote carbon─carbon coupling. The optimal Au/BiO-TiO hybrid delivers a conversion rate of 20.8 millimoles per gram per hour with C product selectivity high to 97% in the flow reactor. More specifically, the veritable participation of lattice oxygen during OCM is chemically looped by introduced dioxygen via the Mars-van Krevelen mechanism, endowing superior catalyst stability.
光驱动甲烷氧化偶联（OCM）以生成多碳（C）产物是实现增值化学品可持续生产的一种有前景的方法，但由于其固有活性较低，仍然具有挑战性。在这里，我们展示了通过合理的催化位点工程，将氧化铋（BiO）和金（Au）整合到二氧化钛（TiO）基底上，以实现对光催化OCM的高转化率、产物选择性和催化耐久性。机理研究表明，BiO中的晶格氧作为局域氧化剂被有效激活，以促进甲烷解离，而Au则控制甲基转移，避免不希望的过度氧化并促进碳-碳偶联。在流动反应器中，最佳的Au/BiO-TiO复合材料的转化率为每克每小时20.8毫摩尔，C产物选择性高达97%。更具体地说，在OCM过程中晶格氧的真正参与通过引入的双原子氧经由Mars-van Krevelen机理进行化学循环，赋予了优异的催化剂稳定性。
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