Cu-based materials are ideal catalysts for CO_(2) electrocatalytic reduction reaction(CO_(2)RR) into multicarbon products.However,such reactions require stringent conditions on local environments of catalyst surfaces,...Cu-based materials are ideal catalysts for CO_(2) electrocatalytic reduction reaction(CO_(2)RR) into multicarbon products.However,such reactions require stringent conditions on local environments of catalyst surfaces,which currently are the global pressing challenges.Here,a stabilized activation of Cu^(0)/Cu^(+)-onAg interface by N_(2) cold plasma treatment was developed for improving Faradaic efficiency(FE) of CO_(2)RR into C2 products.The resultant Ag@Cu-CuN_x exhibits a C2 FE of 72% with a partial current density of-14.9 mA cm^(-2) at-1.0 V vs.RHE(reversible hydrogen electrode).Combining density functional theory(DFT) and experimental investigations,we unveiled that Cu^(0)/Cu^(+) species can be co ntrollably tu ned by the incorporation of nitrogen to form CuN_x on Ag surface,i.e.,Ag@Cu-CuN_x.This strategy enhances ^(*)CO intermediates generation and accelerates C-C coupling both thermodynamically and kinetically.The intermediates O^(*)C^(*)CO,^(*)COOH,and ^(*)CO were detected by in-situ attenuated total internal reflection surface enhanced infrared absorption spectroscopy(ATR-SEIRAS).The uncovered CO_(2)RR-into-C2 products were carried out along CO_(2)→^(*)COOH→^(*)CO→O^(*)C^(*)CO→^(*)C_(2)H_(3)O→^(*)C_(2)H_(4)O→ C_(2)H_(5)OH(or ^(*)C_(2)H_(3)O→^(*)O+C_(2)H_(4)) paths over Ag@Cu-CuN_x electrocatalyst.This work provides a new approach to design Cu-based electrocatalysts with high-efficiency,mild condition,and stable CO_(2)RR to C2 products.展开更多
文摘基于Sentinel-5P卫星TROPOMI数据,利用随机森林方法反演2018~2020年淮河流域地面NO_(2)浓度,采用推算法获得淮河流域2018~2020年NO_(2)干沉降通量,并通过划分不同集水区(水域、农田、城区和植被覆盖区)估算大气NO_(2)干沉降对淮河流域水体氮素的贡献.结果显示,卫星反演地面NO_(2)浓度与地面站点实测资料一致性较高,相关系数(R)为0.94,平均绝对误差(MAE)为2.7,均方根误差(RSME)为4.1.淮河流域地面NO_(2)浓度和NO_(2)干沉降通量均有明显的季节变化,春夏秋冬4个季节地面NO_(2)平均浓度分别为13.7,12.2,17.6,23.1μg/m^(3);NO_(2)平均干沉降通量分别为1.25,1.13,1.61,2.13kg N/(hm^(2)·a).淮河流域地面NO_(2)浓度和干沉降通量均表现为南北部高,东西部低.农田区域NO_(2)干沉降对流域水体氮素的贡献最大,占比83.47%.2019年淮河流域大气NO_(2)干沉降总量为1.34×10^(5)t,对水体氮素的贡献为1.36×10^(4)t N;2020年大气NO_(2)干沉降总量为1.25×10^(5)t,对水体氮素的贡献为1.18×10^(4)t N.
基金the National Natural Science Foundation of China (21902017)the Foundation of technological innovation and application development of Chongqing (cstc2021jscxmsxm X0308, CSTB2022BSXM-JCX0132)+1 种基金the Youth project of science and technology research program of Chongqing Education Commission of China (KJQN20211107)the Scientific Research Foundation of Chongqing University of Technology (2020ZDZ022, 2021PYZ13)。
文摘Cu-based materials are ideal catalysts for CO_(2) electrocatalytic reduction reaction(CO_(2)RR) into multicarbon products.However,such reactions require stringent conditions on local environments of catalyst surfaces,which currently are the global pressing challenges.Here,a stabilized activation of Cu^(0)/Cu^(+)-onAg interface by N_(2) cold plasma treatment was developed for improving Faradaic efficiency(FE) of CO_(2)RR into C2 products.The resultant Ag@Cu-CuN_x exhibits a C2 FE of 72% with a partial current density of-14.9 mA cm^(-2) at-1.0 V vs.RHE(reversible hydrogen electrode).Combining density functional theory(DFT) and experimental investigations,we unveiled that Cu^(0)/Cu^(+) species can be co ntrollably tu ned by the incorporation of nitrogen to form CuN_x on Ag surface,i.e.,Ag@Cu-CuN_x.This strategy enhances ^(*)CO intermediates generation and accelerates C-C coupling both thermodynamically and kinetically.The intermediates O^(*)C^(*)CO,^(*)COOH,and ^(*)CO were detected by in-situ attenuated total internal reflection surface enhanced infrared absorption spectroscopy(ATR-SEIRAS).The uncovered CO_(2)RR-into-C2 products were carried out along CO_(2)→^(*)COOH→^(*)CO→O^(*)C^(*)CO→^(*)C_(2)H_(3)O→^(*)C_(2)H_(4)O→ C_(2)H_(5)OH(or ^(*)C_(2)H_(3)O→^(*)O+C_(2)H_(4)) paths over Ag@Cu-CuN_x electrocatalyst.This work provides a new approach to design Cu-based electrocatalysts with high-efficiency,mild condition,and stable CO_(2)RR to C2 products.
