Molecular Iridium Complexes in Metal-Organic Frameworks Catalyze CO2 Hydrogenation via Concerted Proton and Hydride Transfer

Bing An; Lingzhen Zeng; Mei Jia; Zhe Li; Zekai Lin; Yang Song; Yang Zhou; Jun Cheng; Cheng Wang; Wenbin Lin

doi:10.1021/jacs.7b10922

Molecular Iridium Complexes in Metal-Organic Frameworks Catalyze CO₂ Hydrogenation via Concerted Proton and Hydride Transfer

J Am Chem Soc. 2017 Dec 13;139(49):17747-17750. doi: 10.1021/jacs.7b10922. Epub 2017 Nov 30.

Authors

Bing An¹, Lingzhen Zeng¹, Mei Jia¹, Zhe Li¹, Zekai Lin², Yang Song², Yang Zhou¹, Jun Cheng¹, Cheng Wang¹, Wenbin Lin^{1

2}

Affiliations

¹ Collaborative Innovation Center of Chemistry for Energy Materials, State Key Laboratory of Physical Chemistry of Solid Surfaces, Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University , Xiamen 361005, P. R. China.
² Department of Chemistry, University of Chicago , 929 East 57th Street, Chicago, Illinois 60637, United States.

PMID: 29179548
DOI: 10.1021/jacs.7b10922

Abstract

Molecular iridium catalysts immobilized in metal-organic frameworks (MOFs) were positioned in the condensing chamber of a Soxhlet extractor for efficient CO₂ hydrogenation. Droplets of hot water seeped through the MOF catalyst to create dynamic gas/liquid interfaces which maximize the contact of CO₂, H₂, H₂O, and the catalyst to achieve a high turnover frequency of 410 h^-1 under atmospheric pressure and at 85 °C. H/D kinetic isotope effect measurements and density functional theory calculations revealed concerted proton-hydride transfer in the rate-determining step of CO₂ hydrogenation, which was difficult to unravel in homogeneous reactions due to base-catalyzed H/D exchange.

Publication types

Research Support, U.S. Gov't, Non-P.H.S.
Research Support, Non-U.S. Gov't