Title: Cooperative copper centres in a metal–organic framework for selective conversion of CO₂ to ethanol

Authors:

Bing An, Zhe Li, Yang Song, Jingzheng Zhang, Lingzhen Zeng, Cheng Wang*, Wenbin Lin

Abstract:

Selective conversion of CO₂ to ethanol is of great interest but presents a significant challenge in forming a C–C bond while keeping a C–O bond intact throughout the process. Here, we report cooperative Cu^Isites on a Zr₁₂ cluster of a metal–organic framework (MOF) for selective hydrogenation of CO₂ to ethanol. With the assistance of an alkali cation, the spatially proximate Zr₁₂-supported Cu^I centres activate hydrogen via bimetallic oxidative addition and promote C–C coupling to produce ethanol. The Cs⁺-modified MOF catalyst, in 10 hours, produces ethanol with >99% selectivity and a turnover number (based on all Cu atoms) of 4,080 in supercritical CO₂, with 30 MPa of CO₂ and 5 MPa of H₂ at 85 °C, or a turnover number of 490 at 2 MPa of CO₂/H₂ (1/3) and 100 °C. Our work highlights the potential of using MOFs as a tunable platform to design earth-abundant metal catalysts for CO₂ conversion.

Published: 01 July 2019

Full Link: https://www.nature.com/articles/s41929-019-0308-5