Single‐Atom Molybdenum‐N3 Sites for Selective Hydrogenation of CO2 to CO. Issue 37 (3rd August 2022)

• Record Type: Journal Article
• Authors: Jiang, Yiqiang; Sung, Yunjin; Choi, Changhyeok; Joo Bang, Gi; Hong, Song; Tan, Xinyi; Wu, Tai‐Sing; Soo, Yun‐Liang; Xiong, Pei; Meng‐Jung LI, Molly; Hao, Leiduan; Jung, Yousung; Sun, Zhenyu
• Is Part Of: Angewandte Chemie international edition. Volume 61:Issue 37(2022)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2022-08-03
• Subjects: CO -- CO2 Hydrogenation -- Reverse Water–Gas Shift Reaction -- Single-Atom Molybdenum; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.202203836
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: The design of efficient non‐noble metal catalysts for CO2 hydrogenation to fuels and chemicals is desired yet remains a challenge. Herein, we report that single Mo atoms with a MoN3 (pyrrolic) moiety enable remarkable CO2 adsorption and hydrogenation to CO, as predicted by density functional theory studies and evidenced by a high and stable conversion of CO2 reaching about 30.4 % with a CO selectivity of almost 100 % at 500 °C and very low H2 partial pressure. Atomically dispersed MoN3 is calculated to facilitate CO2 activation and reduces CO2 to CO* via the direct dissociation path. Furthermore, the highest transition state energy in CO formation is 0.82 eV, which is substantially lower than that of CH4 formation (2.16 eV) and accounts for the dominant yield of CO. The enhanced catalytic performances of Mo/NC originate from facile CO desorption with the help of dispersed Mo on nitrogen‐doped carbon (Mo/NC), and in the absence of Mo nanoparticles. The resulting catalyst preserves good stability without degradation of CO2 conversion rate even after 68 hours of continuous reaction. This finding provides a promising route for the construction of highly active, selective, and robust single‐atom non‐precious metal catalysts for reverse water–gas shift reaction. Abstract : Adsorption and hydrogenation of CO2 to CO is reported over single Mo atoms with a MoN3 (pyrrolic) moiety. Density functional theory studies and experimental studies provide additional evidence to support the observed activity. A high and stable conversion of CO2 is attained up to 30.4 % with a 100 % CO selectivity.