Electrochemical nitrite reduction reaction(NO_(2)^(-)RR) is a potential sustainable route for regulating the nitrogen cycle and ambient ammonia(NH_(3)) synthesis.However,it remains a challenge to precisely regulate th...Electrochemical nitrite reduction reaction(NO_(2)^(-)RR) is a potential sustainable route for regulating the nitrogen cycle and ambient ammonia(NH_(3)) synthesis.However,it remains a challenge to precisely regulate the reaction pathways and inhibit competing reactions(e.g.hydrogenolysis) for efficient and selective NH_(3) production in an aqueous solution environment.Here,we utilize the Schottky barrier-induced surface electric field to construct high-density electron-deficient Pd nanoparticles by modulating the N content in the carbon carrier to promote the enrichment and immobilization of NO_(2)^(-)on the electrode surface,which ensures the ultimate selectivity for NH_(3).With these properties,Pd@N_(0.14)C with the highest N content achieved excellent catalytic performance for the reduction of NO_(2)^(-)to NH_(3) with the 100% Faraday efficiency at-0.5 and-0.6 V vs,reversible hydrogen electrode(RHE) for NH_(3) production,which was significantly better than Pd/C and Pd@N_(x)C samples with lower N content.This study opens new avenues for rational construction of efficient electrocatalysts for nitrite removal and NH_(3) electrosynthesis.展开更多
Ambient electrochemical nitrite(NO_(2)^(-))reduction is viewed as an effective and sustainable approach for simul-taneously removing NO_(2)^(-)and producing ammonia(NH_(3)).However,the complex multi-electron transfer ...Ambient electrochemical nitrite(NO_(2)^(-))reduction is viewed as an effective and sustainable approach for simul-taneously removing NO_(2)^(-)and producing ammonia(NH_(3)).However,the complex multi-electron transfer steps involved in the NO_(2)^(-)reduction reaction(NO_(2)^(-)RR)lead to sluggish kinetics and low product selectivity toward NH_(3),underscoring the need for NH_(3)synthesis electrocatalysts with high activity and durability.Herein,we report amorphous indium-tin oxide sputtered on a TiO_(2)nanobelt array on a Ti plate(ITO@TiO_(2)/TP)as a 3D NH_(3)-producing catalyst for the NO_(2)^(-).In 0.5 M LiClO_(4)with 0.1 M NO_(2)^(-),it shows greatly boosted NO_(2)^(-)RR activity toward NH_(3)production,with excellent selectivity,achieving a large NH_(3)yield of 411.3μmol h^(-1)cm^(-2)and a high Faradaic efficiency of 82.6%.It also shows high durability for continuous electrolysis.A Zn-NO_(2)^(-)battery with ITO@TiO_(2)/TP cathode offers an NH_(3)yield of 23.1μmol h^(-1)cm^(-2)and a peak power density of 1.22 m.展开更多
文摘Electrochemical nitrite reduction reaction(NO_(2)^(-)RR) is a potential sustainable route for regulating the nitrogen cycle and ambient ammonia(NH_(3)) synthesis.However,it remains a challenge to precisely regulate the reaction pathways and inhibit competing reactions(e.g.hydrogenolysis) for efficient and selective NH_(3) production in an aqueous solution environment.Here,we utilize the Schottky barrier-induced surface electric field to construct high-density electron-deficient Pd nanoparticles by modulating the N content in the carbon carrier to promote the enrichment and immobilization of NO_(2)^(-)on the electrode surface,which ensures the ultimate selectivity for NH_(3).With these properties,Pd@N_(0.14)C with the highest N content achieved excellent catalytic performance for the reduction of NO_(2)^(-)to NH_(3) with the 100% Faraday efficiency at-0.5 and-0.6 V vs,reversible hydrogen electrode(RHE) for NH_(3) production,which was significantly better than Pd/C and Pd@N_(x)C samples with lower N content.This study opens new avenues for rational construction of efficient electrocatalysts for nitrite removal and NH_(3) electrosynthesis.
基金This work was supported by the National Natural Science Foundation of China(No.22072015).
文摘Ambient electrochemical nitrite(NO_(2)^(-))reduction is viewed as an effective and sustainable approach for simul-taneously removing NO_(2)^(-)and producing ammonia(NH_(3)).However,the complex multi-electron transfer steps involved in the NO_(2)^(-)reduction reaction(NO_(2)^(-)RR)lead to sluggish kinetics and low product selectivity toward NH_(3),underscoring the need for NH_(3)synthesis electrocatalysts with high activity and durability.Herein,we report amorphous indium-tin oxide sputtered on a TiO_(2)nanobelt array on a Ti plate(ITO@TiO_(2)/TP)as a 3D NH_(3)-producing catalyst for the NO_(2)^(-).In 0.5 M LiClO_(4)with 0.1 M NO_(2)^(-),it shows greatly boosted NO_(2)^(-)RR activity toward NH_(3)production,with excellent selectivity,achieving a large NH_(3)yield of 411.3μmol h^(-1)cm^(-2)and a high Faradaic efficiency of 82.6%.It also shows high durability for continuous electrolysis.A Zn-NO_(2)^(-)battery with ITO@TiO_(2)/TP cathode offers an NH_(3)yield of 23.1μmol h^(-1)cm^(-2)and a peak power density of 1.22 m.
