Bottom-up Interfacial Design of Covalent Organic Frameworks for Highly Efficient and Selective Electrocatalysis of CO 2 .

Assembling molecular catalytic centers into crosslinked networks is widely used to fabricate heterogeneous catalysts but they often suffer loss in activity and selectivity accompanied by unclear causes. Here we report a strategy for the construction of heterogeneous catalysts to induce activity and selectivity by bottom-up introduction of segregated electron conduction and mass transport interfaces into the catalytic materials. The catalytic skeletons are designed to possess different π orderings for electron motion and the open channels are tailored to install finely engineered walls for mass transport, so that origins of activity and selectivity are correlated. The resultant covalent organic framework catalysts with ordered π skeletons and solvophobic pores increased activity by two orders of magnitude, enhanced selectivity and energy efficiency by 70-fold, and broadened voltage range, to promote CO transformation under ambient conditions. Our results open a way to precise interfacial design for actionable heterogeneous catalysts for producing feedstocks from CO . This article is protected by copyright. All rights reserved.