An active, stable cubic molybdenum carbide catalyst for the high-temperature reverse water-gas shift reaction

• 成果类型: Article
• 署名作者: Khoshooei, Milad Ahmadi; Wang, Xijun; Vitale, Gerardo; Formalik, Filip; Kirlikovali, Kent O.; Snurr, Randall Q.; Pereira-Almao, Pedro; Farha, Omar K.
• 署名单位: Northwestern University; Northwestern University; University of Calgary; Northwestern University; Wroclaw University of Science & Technology
• 刊物名称: SCIENCE
• ISSN/ISSBN: 0036-8165
• DOI: 10.1126/science.adl1260
• 发表日期: 2024-05-03
• 页码: 540-546
• 关键词: finding saddle-points; co2; hydrogenation; reduction; methanol; TRANSFORMATION; adsorption; metals

摘要

Although technologically promising, the reduction of carbon dioxide (CO2) to produce carbon monoxide (CO) remains economically challenging owing to the lack of an inexpensive, active, highly selective, and stable catalyst. We show that nanocrystalline cubic molybdenum carbide (alpha-Mo2C), prepared through a facile and scalable route, offers 100% selectivity for CO2 reduction to CO while maintaining its initial equilibrium conversion at high space velocity after more than 500 hours of exposure to harsh reaction conditions at 600 degrees C. The combination of operando and postreaction characterization of the catalyst revealed that its high activity, selectivity, and stability are attributable to crystallographic phase purity, weak CO-Mo2C interactions, and interstitial oxygen atoms, respectively. Mechanistic studies and density functional theory (DFT) calculations provided evidence that the reaction proceeds through an H-2-aided redox mechanism.