Surface frustrated Lewis pairs in titanium nitride enable gas phase heterogeneous CO2 photocatalysis

• Published in: Nature communications Vol. 15; no. 1; pp. 10604 - 13
• Main Authors: Zou, Yunjie, Mao, Chengliang, Xu, Mingkai, Xing, Chao, Wang, Ruizhao, Ozin, Geoffrey A., Ling, Lan
• Format: Journal Article
• Language: English
• Published: London Nature Publishing Group UK 05.12.2024; Nature Publishing Group; Nature Portfolio
• Subjects: 140/146; 140/58; 147/137; 147/143; 639/301/299; 639/638/439; 639/638/77/890; Acidic oxides; Basic oxides; Business metrics; Carbon dioxide; Catalysis; Catalysts; Chemical composition; Humanities and Social Sciences; Hydroxides; Lewis acid; Lewis base; Metal nitrides; Metal oxides; Metals; multidisciplinary; Performance measurement; Photoreduction; Platinum; Science; Science (multidisciplinary); Shift reaction; Synergism; Titanium; Titanium nitride; Vapor phases
• ISSN: 2041-1723; 2041-1723
• DOI: 10.1038/s41467-024-54951-2

Gas-phase heterogeneous catalytic CO 2 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 2 in metal nitrides. This study establishes a proof-of-concept that an amine-type photoactive surface frustrated Lewis pair (MNH 2 •••M) can be constructed in titanium nitride (TiN x O y ) when integrated with a nanoscale platinum spillover co-catalyst. This surface frustrated Lewis pair, comprising Ti-NH 2 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-(H 2 N-COO)-Ti, whereby the synergism of Lewis acidic and Lewis basic sites endows it with superior performance indicators compared to TiN x O y alone, as well as conventional platinum supported metal oxides. Heterogeneous surface frustrated Lewis pairs catalysis have been predominantly focused on metal oxide hydroxides. This study instead explores a different chemical composition space by shifting from metal oxides to metal nitrides for CO 2 photoreduction.