TY - JOUR
T1 - Nitrate-to-ammonia conversion with a plasmonic antenna-reactor catalyst
AU - Ou, Weihui
AU - Guo, Ying
AU - Zhong, Jing
AU - Lyu, Fucong
AU - Shen, Junda
AU - Li, Hongkun
AU - Zhang, Shaoce
AU - Li, Zebiao
AU - He, Zhijian
AU - He, Jun
AU - Mo, Quanxi
AU - Zhi, Chunyi
AU - Li, Yang Yang
AU - Lu, Jian
PY - 2025/2/21
Y1 - 2025/2/21
N2 - Electrochemical conversion of nitrate to ammonia is an appealing route to efficiently synthesize ammonia under ambient conditions while reducing environmental nitrate pollutants. However, this approach is obstructed by the limited yield and selectivity of ammonia because the electrochemical nitrate-to-ammonia conversion involves multi-electron/proton transfer and faces competition from the hydrogen evolution reaction. Here, we demonstrate a plasmon-assisted strategy to improve the performance of nitrate-to-ammonia electrochemical conversion by constructing plasmonic antenna-reactor catalysts, where Au and Pd nanoparticles/hydrogen substituted graphdiyne (Pd/HsGDY) work as the light antenna and reaction site, respectively. Plasmonic excitation of Au-Pd/HsGDY catalysts can remarkably accelerate the nitrate reduction, with the yield rate, selectivity, and Faradaic efficiency of ammonia respectively increased by 14.3, 2.1, and 1.8 times under optimal conditions. Mechanistic investigations unveil that Au plasmon-induced hot electrons facilitate nitrate-to-ammonia reaction by regulating the adsorption of reaction intermediates on Pd/HsGDY, wherein the rate-determining step was shifted from nitrate adsorption to *NH protonation and the overall apparent activation was reduced. Moreover, hot electrons suppress the competing hydrogen evolution by enlarging the Gibbs free energy of hydrogen formation. These results open a way to develop desirable catalysts for producing value-added ammonia from environmentally hazardous nitrate by a synergistic combination of electricity and light. © 2024 The Royal Society of Chemistry.
AB - Electrochemical conversion of nitrate to ammonia is an appealing route to efficiently synthesize ammonia under ambient conditions while reducing environmental nitrate pollutants. However, this approach is obstructed by the limited yield and selectivity of ammonia because the electrochemical nitrate-to-ammonia conversion involves multi-electron/proton transfer and faces competition from the hydrogen evolution reaction. Here, we demonstrate a plasmon-assisted strategy to improve the performance of nitrate-to-ammonia electrochemical conversion by constructing plasmonic antenna-reactor catalysts, where Au and Pd nanoparticles/hydrogen substituted graphdiyne (Pd/HsGDY) work as the light antenna and reaction site, respectively. Plasmonic excitation of Au-Pd/HsGDY catalysts can remarkably accelerate the nitrate reduction, with the yield rate, selectivity, and Faradaic efficiency of ammonia respectively increased by 14.3, 2.1, and 1.8 times under optimal conditions. Mechanistic investigations unveil that Au plasmon-induced hot electrons facilitate nitrate-to-ammonia reaction by regulating the adsorption of reaction intermediates on Pd/HsGDY, wherein the rate-determining step was shifted from nitrate adsorption to *NH protonation and the overall apparent activation was reduced. Moreover, hot electrons suppress the competing hydrogen evolution by enlarging the Gibbs free energy of hydrogen formation. These results open a way to develop desirable catalysts for producing value-added ammonia from environmentally hazardous nitrate by a synergistic combination of electricity and light. © 2024 The Royal Society of Chemistry.
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U2 - 10.1039/d4ee03678f
DO - 10.1039/d4ee03678f
M3 - RGC 21 - Publication in refereed journal
SN - 1754-5692
VL - 18
SP - 1673
EP - 1682
JO - Energy and Environmental Science
JF - Energy and Environmental Science
IS - 4
ER -