Zou Yunjie, Mao Chengliang, Xu Mingkai, Xing Chao, Wang Ruizhao, Ozin Geoffrey A, Ling Lan
State Key Laboratory for Pollution Control and Resource Reuse, College of Environmental Science and Engineering, Tongji University, Shanghai, China.
Materials Chemistry and Nanochemistry Research Group, Solar Fuels Cluster, Departments of Chemistry, University of Toronto, 80 Saint George Street, Toronto, ON, Canada.
Nat Commun. 2024 Dec 5;15(1):10604. doi: 10.1038/s41467-024-54951-2.
Gas-phase heterogeneous catalytic CO hydrogenation to commodity chemicals and fuels via surface frustrated Lewis pairs is a growing focus of scientific and technological interest. Traditional gas-phase heterogeneous surface frustrated Lewis pair catalysts primarily involve metal oxide-hydroxides (MOH•••M). An avenue to improve the process performance metrics lies in replacing the Lewis base MOH with a stronger alternative; an intriguing example being the amine MNH in metal nitrides. This study establishes a proof-of-concept that an amine-type photoactive surface frustrated Lewis pair (MNH•••M) can be constructed in titanium nitride (TiNO) when integrated with a nanoscale platinum spillover co-catalyst. This surface frustrated Lewis pair, comprising Ti-NH as the Lewis base and low-valent Ti as the Lewis acid, facilitates the gas-phase light-assisted heterogeneous reverse water-gas shift reaction. The reaction proceeds via a surface-active carbamate intermediate, Ti-(HN-COO)-Ti, whereby the synergism of Lewis acidic and Lewis basic sites endows it with superior performance indicators compared to TiNO alone, as well as conventional platinum supported metal oxides.
通过表面受阻路易斯对将气相多相催化CO加氢转化为商品化学品和燃料是一个日益受到科技关注的焦点。传统的气相多相表面受阻路易斯对催化剂主要涉及金属氢氧化物（MOH•••M）。提高该过程性能指标的一条途径是用更强的替代物取代路易斯碱MOH；一个有趣的例子是金属氮化物中的胺MNH。本研究建立了一个概念验证，即当与纳米级铂溢流助催化剂结合时，可以在氮化钛（TiNO）中构建胺型光活性表面受阻路易斯对（MNH•••M）。这个表面受阻路易斯对，以Ti-NH作为路易斯碱，低价Ti作为路易斯酸，促进了气相光辅助多相逆水煤气变换反应。该反应通过表面活性氨基甲酸盐中间体Ti-(HN-COO)-Ti进行，与单独的TiNO以及传统的铂负载金属氧化物相比，路易斯酸性和路易斯碱性位点的协同作用赋予了它优异的性能指标。
