The state of nitrogen in nitrogen-doped graphene(NG)promoting the conversion of molecular oxygen to hydrogen peroxide was investigated.The oxygen reduction reaction(ORR)reactivity of graphitic-N,pyrrolic-N,pyridinic-N...The state of nitrogen in nitrogen-doped graphene(NG)promoting the conversion of molecular oxygen to hydrogen peroxide was investigated.The oxygen reduction reaction(ORR)reactivity of graphitic-N,pyrrolic-N,pyridinic-N in NG was predicted by density functional theory(DFT).A series of NG samples with different contents of these doped nitrogen types were prepared by the low-temperature thermal reduction method and used for the ORR evaluation.The H_(2)O_(2)yield,2e−ORR current efficiency,H_(2)O_(2)selectivity,electron transfer number(n)were systematically studied.The 2e−ORR selectivity was positively correlated with the N content,approaching 100%with increasing N content(0.40 V vs.reversible hydrogen electrode(RHE)),whereas the comparative energy efficiency showed a volcano-type trend related to N content,reaching a maximum of 94%.In addition,N species validation experiments proved the key role of pyrrolic-N in the synthesis of H_(2)O_(2).Compared with a pure graphene catalyst,further contaminant degradation studies on NG electrodes with different pyrrolic-N contents revealed that the lower pyrrolic-N the higher removal of p-nitrophenol(PNP).This work provides insight into the mechanism of ORR on metal-free catalysts and a facile approach to optimize this important environmental catalytic strategy.展开更多
基金the Beijing Natural Science Foundation of China(No.8222061)the National Natural Science Foundation of China(Nos.21872009 and 52070015)the National Key Research and Development Program of China(No.2018YFC1802500).
文摘The state of nitrogen in nitrogen-doped graphene(NG)promoting the conversion of molecular oxygen to hydrogen peroxide was investigated.The oxygen reduction reaction(ORR)reactivity of graphitic-N,pyrrolic-N,pyridinic-N in NG was predicted by density functional theory(DFT).A series of NG samples with different contents of these doped nitrogen types were prepared by the low-temperature thermal reduction method and used for the ORR evaluation.The H_(2)O_(2)yield,2e−ORR current efficiency,H_(2)O_(2)selectivity,electron transfer number(n)were systematically studied.The 2e−ORR selectivity was positively correlated with the N content,approaching 100%with increasing N content(0.40 V vs.reversible hydrogen electrode(RHE)),whereas the comparative energy efficiency showed a volcano-type trend related to N content,reaching a maximum of 94%.In addition,N species validation experiments proved the key role of pyrrolic-N in the synthesis of H_(2)O_(2).Compared with a pure graphene catalyst,further contaminant degradation studies on NG electrodes with different pyrrolic-N contents revealed that the lower pyrrolic-N the higher removal of p-nitrophenol(PNP).This work provides insight into the mechanism of ORR on metal-free catalysts and a facile approach to optimize this important environmental catalytic strategy.
