Supramolecular Porphyrin Cages Assembled at Molecular–Materials Interfaces for Electrocatalytic CO Reduction
- Resource Type
- Article
- Authors
- Gong, Ming; Cao, Zhi; Liu, Wei; Nichols, Eva M.; Smith, Peter T.; Derrick, Jeffrey S.; Liu, Yi-Sheng; Liu, Jinjia; Wen, Xiaodong; Chang, Christopher J.
- Source
- ACS Central Science; September 2017, Vol. 3 Issue: 9 p1032-1040, 9p
- Subject
- Language
- ISSN
- 23747943; 23747951
Conversion of carbon monoxide (CO), a major one-carbon product of carbon dioxide (CO2) reduction, into value-added multicarbon species is a challenge to addressing global energy demands and climate change. Here we report a modular synthetic approach for aqueous electrochemical CO reduction to carbon–carbon coupled products via self-assembly of supramolecular cages at molecular–materials interfaces. Heterobimetallic cavities formed by face-to-face coordination of thiol-terminated metalloporphyrins to copper electrodes through varying organic struts convert CO to C2 products with high faradaic efficiency (FE = 83% total with 57% to ethanol) and current density (1.34 mA/cm2) at a potential of −0.40 V vs RHE. The cage-functionalized electrodes offer an order of magnitude improvement in both selectivity and activity for electrocatalytic carbon fixation compared to parent copper surfaces or copper functionalized with porphyrins in an edge-on orientation.