Interface Engineering of Earth-Abundant Transition Metals Using Boron Nitride for Selective Electroreduction of CO₂

Journal Article · 01 February 2018 · ACS Applied Materials and Interfaces

DOI: https://doi.org/10.1021/acsami.7b17600 · OSTI ID:1468197

Hu, Guoxiang ^[1]; Wu, Zili  ^[2]; Dai, Sheng  ^[3]; Jiang, De-en  ^[1]

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1. Univ. of California, Riverside, CA (United States). Dept. of Chemistry
2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division. Center for Nanophase Materials Sciences
3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division. Center for Nanophase Materials Sciences; Univ. of Tennessee, Knoxville, TN (United States). Dept. of Chemistry

Two-dimensional atomically thin hexagonal boron nitride (h-BN) monolayers have attracted considerable research interest. In this paper, given the tremendous progress in the synthesis of h-BN monolayers on transition metals and their potential as electrocatalysts, we investigate the electrocatalytic activities of h-BN/Ni, h-BN/Co, and h-BN/Cu interfaces for CO₂ reduction by the first-principles density functional theory. We find that with the h-BN monolayer on the metal, electrons transfer from the metal to the interface and accumulate under the B atoms. By calculating the binding energies of three key intermediates (H, HCOO, and COOH) for hydrogen evolution and CO₂ reduction, we find that H binding on the metal can be significantly weakened by the h-BN monolayer, preventing the hydrogen evolution reaction (HER). However, the binding strength of HCOO is strong on both the metal and h-BN/metal, especially for Ni and Co, promoting the CO₂ reduction channel. On the basis of the free-energy diagrams, we predict that h-BN/Ni and h-BN/Co will have very good electrocatalytic activities for CO₂ reduction to HCOOH, while the competitive HER channel is filtered out by the surface h-BN monolayer. Finally, our study opens a new way for selective electroreduction of CO₂ via the interface engineering of the h-BN/metal system.

• Research Organization: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States); Univ. of California, Riverside, CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)
• Sponsoring Organization: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division
• Grant/Contract Number: AC05-00OR22725; AC02-05CH11231
• OSTI ID: 1468197
• Alternate ID(s): OSTI ID: 1485129
• Journal Information: ACS Applied Materials and Interfaces, Vol. 10, Issue 7; ISSN 1944-8244
• Publisher: American Chemical Society (ACS)Copyright Statement
• Country of Publication: United States
• Language: English