Creating Frustrated Lewis Pairs in Defective Boron Carbon Nitride for Electrocatalytic Nitrogen Reduction to Ammonia.
Angew Chem Int Ed Engl
; 61(36): e202207807, 2022 Sep 05.
Article
in En
| MEDLINE
| ID: mdl-35789179
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 N2 /15 N2 exchange experiments and density functional theory (DFT) calculations reveal that FLPs can adsorb an N2 molecule to form a six-membered ring intermediate, which enables the cleavage of N2 via a pull-pull effect, thereby significantly reducing the energy barrier to -0.28â
eV. Impressively, BCN achieves a high Faraday efficiency of 18.9 %, an ammonia yield of 20.9â
µg h-1 mg-1 cat. , and long-term durability.
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MEDLINE
Language:
En
Year:
2022
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Article