Enhanced Electrochemical Methanation of Carbon Dioxide at the Single-Layer Hexagonal Boron Nitride/Cu Interfacial Perimeter

Abstract

The electrochemical conversion of CO2 to valuable fuels is a plausible solution to meet the soaring need for renewable energy sources. However, the practical application of this process is limited by its poor selectivity due to scaling relations. Here we introduce the rational design of the monolayer hexagonal boron nitride/copper (h-BN/Cu) interface to circumvent scaling relations and improve the electrosynthesis of CH4. This catalyst possesses a selectivity of >60% toward CH4 with a production rate of 15 μmol·cm–2·h–1 at −1.00 V vs RHE, along with a much smaller decaying production rate than that of pristine Cu. Both experimental and theoretical calculations disclosed that h-BN/Cu interfacial perimeters provide specific chelating sites to immobilize the intermediates, which accelerates the conversion of *CO to *CHO. Our work reports a novel Cu catalyst engineering strategy and demonstrates the prospect of monolayer h-BN contributing to the design of heterostructured CO2 reduction electrocatalysts for sustainable energy conversion.

Structure‐Function Correlation and Dynamic Restructuring of Cu for Highly Efficient Electrochemical CO2 Conversion

“…One demonstration to achieve this goal is the modification of Cu surface with two-dimensional (2D) materials such as graphene and hexagonal-boron nitride (h-BN). [103,104] Our group introduced a rational design of monolayer hexagonalboron nitride/copper (h-BN/Cu) interface to circumvent scaling relations on Cu and improve the electrosynthesis of methane (> 60 % at À 1.0 V RHE ). Both experimental and theoretical calculation disclosed that h-BN/Cu interfacial perimeters provide specific chelating sites to immobilize the intermediates, and thereby accelerate the conversion of *CO to *CHO.…”

“…Both experimental and theoretical calculation disclosed that h-BN/Cu interfacial perimeters provide specific chelating sites to immobilize the intermediates, and thereby accelerate the conversion of *CO to *CHO. [104] In brief, surface modification of Cu electrodes including integrating diverse porphyrin/phthalocyanine-based molecular, 2D structures and polymers is a valid and facile way to tune CO 2 R product distribution. Nevertheless, a deep understanding of CO 2 R on such heterostructures is urgently demanded.…”

“…Extensive efforts have been devoted to enhancing the generation of C 2+ products, however, studies focusing on the conversion from CO 2 to C 1 products, such as methane, are relatively seldom. One demonstration to achieve this goal is the modification of Cu surface with two‐dimensional (2D) materials such as graphene and hexagonal‐boron nitride (h‐BN) [103,104] . Our group introduced a rational design of monolayer hexagonal‐boron nitride/copper (h‐BN/Cu) interface to circumvent scaling relations on Cu and improve the electrosynthesis of methane (>60 % at −1.0 V RHE ).…”

“…Our group introduced a rational design of monolayer hexagonal‐boron nitride/copper (h‐BN/Cu) interface to circumvent scaling relations on Cu and improve the electrosynthesis of methane (>60 % at −1.0 V RHE ). Both experimental and theoretical calculation disclosed that h‐BN/Cu interfacial perimeters provide specific chelating sites to immobilize the intermediates, and thereby accelerate the conversion of *CO to *CHO [104] . In brief, surface modification of Cu electrodes including integrating diverse porphyrin/phthalocyanine‐based molecular, 2D structures and polymers is a valid and facile way to tune CO 2 R product distribution.…”

Hexagonal Boron Nitride Meeting Metal: A New Opportunity and Territory in Heterogeneous Catalysis

“…Theoretical calculation suggests that activation of surface adsorbed O 2 and a two-electron reduction pathway are favored on the h- BNNS/Au interfaces. Monolayer h- BN cover also increases the electrochemical reduction efficiency of CO 2 to CH 4 by 7-fold on the Cu surface …”