Covalent organic frameworks comprising cobalt porphyrins for catalytic CO₂ reduction in water

Song Lin; Christian S Diercks; Yue-Biao Zhang; Nikolay Kornienko; Eva M Nichols; Yingbo Zhao; Aubrey R Paris; Dohyung Kim; Peidong Yang; Omar M Yaghi; Christopher J Chang

doi:10.1126/science.aac8343

Covalent organic frameworks comprising cobalt porphyrins for catalytic CO₂ reduction in water

Science. 2015 Sep 11;349(6253):1208-13. doi: 10.1126/science.aac8343. Epub 2015 Aug 20.

Authors

Affiliations

¹ Department of Chemistry, University of California, Berkeley, CA 94720, USA. Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USA.
² Department of Chemistry, University of California, Berkeley, CA 94720, USA. Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USA.
³ Department of Chemistry, University of California, Berkeley, CA 94720, USA. Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USA. School of Physical Science and Technology, ShanghaiTech University, Shanghai, 201210, China.
⁴ Department of Chemistry, University of California, Berkeley, CA 94720, USA.
⁵ Department of Materials Science and Engineering, University of California, Berkeley, CA 94720, USA.
⁶ Department of Chemistry, University of California, Berkeley, CA 94720, USA. Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USA. Department of Materials Science and Engineering, University of California, Berkeley, CA 94720, USA. Kavli Energy Nanoscience Institute, Berkeley, CA 94720, USA.
⁷ Department of Chemistry, University of California, Berkeley, CA 94720, USA. Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USA. Kavli Energy Nanoscience Institute, Berkeley, CA 94720, USA. King Fahd University of Petroleum and Minerals, Dhahran 34464, Saudi Arabia. yaghi@berkeley.edu chrischang@berkeley.edu.
⁸ Department of Chemistry, University of California, Berkeley, CA 94720, USA. Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USA. Howard Hughes Medical Institute, University of California, Berkeley, CA 94720, USA. Department of Molecular and Cell Biology, University of California, Berkeley, CA 94720, USA. yaghi@berkeley.edu chrischang@berkeley.edu.

PMID: 26292706
DOI: 10.1126/science.aac8343

Abstract

Conversion of carbon dioxide (CO2) to carbon monoxide (CO) and other value-added carbon products is an important challenge for clean energy research. Here we report modular optimization of covalent organic frameworks (COFs), in which the building units are cobalt porphyrin catalysts linked by organic struts through imine bonds, to prepare a catalytic material for aqueous electrochemical reduction of CO2 to CO. The catalysts exhibit high Faradaic efficiency (90%) and turnover numbers (up to 290,000, with initial turnover frequency of 9400 hour(-1)) at pH 7 with an overpotential of -0.55 volts, equivalent to a 26-fold improvement in activity compared with the molecular cobalt complex, with no degradation over 24 hours. X-ray absorption data reveal the influence of the COF environment on the electronic structure of the catalytic cobalt centers.

Publication types

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