Creating Frustrated Lewis Pairs in Defective Boron Carbon Nitride for Electrocatalytic Nitrogen Reduction to Ammonia

Lin, Wenwen; Chen, Hao; Lin, Gaobo; Yao, Siyu; Zhang, Zihao; Qi, Jizhen; Jing, Meizan; Song, Weiyu; Li, Jing; Liu, Xi; Fu, Jie; Dai, Sheng

doi:10.1002/anie.202207807

Creating Frustrated Lewis Pairs in Defective Boron Carbon Nitride for Electrocatalytic Nitrogen Reduction to Ammonia

Journal Article · Tue Jul 26 00:00:00 EDT 2022 · Angewandte Chemie (International Edition)

DOI:https://doi.org/10.1002/anie.202207807· OSTI ID:1877945

Lin, Wenwen ^[1]; Chen, Hao ^[2]; Lin, Gaobo ^[1]; Yao, Siyu ^[3]; Zhang, Zihao ^[3]; Qi, Jizhen ^[4]; Jing, Meizan ^[5]; Song, Weiyu ^[5]; Li, Jing ^[3]; Liu, Xi ^[6]; ^[1]; Dai, Sheng ^[7]

Key Laboratory of Biomass Chemical Engineering of Ministry of Education College of Chemical and Biological Engineering Zhejiang University Hangzhou 310027 China, Institute of Zhejiang University-Quzhou 78 Jiuhua Boulevard North Quzhou 324000 China
College of Chemistry and Chemical Engineering Hunan University Changsha 410082 China
Key Laboratory of Biomass Chemical Engineering of Ministry of Education College of Chemical and Biological Engineering Zhejiang University Hangzhou 310027 China
i-Lab CAS Center for Excellence in Nanoscience Suzhou Institute of Nano-Tech and Nano-Bionics (SINANO) Chinese Academy of Sciences Suzhou 215123 China
State Key Laboratory of Heavy Oil Processing College of Science China University of Petroleum-Beijing Beijing 102249 China
School of Chemistry and Chemical Engineering In situ Center for Physical Sciences Shanghai Jiao Tong University Shanghai 200240 China
Chemical Sciences Division Oak Ridge National Laboratory Oak Ridge TN 37831 USA

Abstract

The electrocatalytic nitrogen reduction reaction (NRR) on metal‐free catalysts is an attractive alternative to the industrial Haber–Bosch process. However, the state‐of‐the‐art metal‐free electrocatalysts still suffer from low Faraday efficiencies and low ammonia yields. Herein, we present a molecular design strategy to develop a defective boron carbon nitride (BCN) catalyst with the abundant unsaturated B and N atoms as Lewis acid and base sites, which upgrades the catalyst from a single “Lewis acid catalysis” to “frustrated Lewis pairs (FLPs) catalysis.” ¹⁴ N ₂ / ¹⁵ N ₂ exchange experiments and density functional theory (DFT) calculations reveal that FLPs can adsorb an N ₂ molecule to form a six‐membered ring intermediate, which enables the cleavage of N ₂ via a pull–pull effect, thereby significantly reducing the energy barrier to −0.28 eV. Impressively, BCN achieves a high Faraday efficiency of 18.9 %, an ammonia yield of 20.9 μg h ⁻¹ mg ⁻¹ _cat. , and long‐term durability.

View Accepted Manuscript (Publisher)

Sponsoring Organization:: USDOE

OSTI ID:: 1877945

Journal Information:: Angewandte Chemie (International Edition), Journal Name: Angewandte Chemie (International Edition) Journal Issue: 36 Vol. 61; ISSN 1433-7851

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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