Biomimetic Frustrated Lewis Pair Catalysts for Hydrogenation of CO to Methanol at Low Temperatures

Jiejing Zhang; Longfei Li; Xiaofeng Xie; Xue-Qing Song; Henry F Schaefer 3rd

doi:10.1021/acsorginorgau.3c00064

Biomimetic Frustrated Lewis Pair Catalysts for Hydrogenation of CO to Methanol at Low Temperatures

ACS Org Inorg Au. 2024 Jan 31;4(2):258-267. doi: 10.1021/acsorginorgau.3c00064. eCollection 2024 Apr 3.

Authors

Jiejing Zhang¹, Longfei Li¹, Xiaofeng Xie¹, Xue-Qing Song¹, Henry F Schaefer 3rd²

Affiliations

¹ College of Pharmacy, Key Laboratory of Pharmaceutical Quality Control of Hebei Province, Key Laboratory of Medicinal Chemistry and Molecular Diagnosis of Ministry of Education, Hebei University, Baoding 071002, Hebei, P. R. China.
² Center for Computational Quantum Chemistry, University of Georgia, Athens, Georgia 30602, United States.

Abstract

The industrial production of methanol through CO hydrogenation using the Cu/ZnO/Al₂O₃ catalyst requires harsh conditions, and the development of new catalysts with low operating temperatures is highly desirable. In this study, organic biomimetic FLP catalysts with good tolerance to CO poison are theoretically designed. The base-free catalytic reaction contains the 1,1-addition of CO into a formic acid intermediate and the hydrogenation of the formic acid intermediate into methanol. Low-energy spans (25.6, 22.1, and 20.6 kcal/mol) are achieved, indicating that CO can be hydrogenated into methanol at low temperatures. The new extended aromatization-dearomatization effect involving multiple rings is proposed to effectively facilitate the rate-determining CO 1,1-addition step, and a new CO activation model is proposed for organic catalysts.