Theory assisted design of N-doped tin oxides for enhanced electrochemical CO_2 activation and reduction
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摘要
Clearly understanding the structure-function relationship and rational design of efficient CO_2 electrocatalysts are still the challenges.This article describes the molecular origin of high selectivity of formic acid on N-doped SnO_2 nanoparticles,which obtained via thermal treatment of g-C_3N_4 and SnCl_2·2H_2O precursor.Combined with density functional theory(DFT)calculations,we discover that N-doping effectively introduces oxygen vacancies and increases the charge density of Sn sites,which plays a positive role in CO_2 activation.In addition,N-doping further regulates the adsorption energy of*OCHO,*COOH,*H and promotes HCOOH generation.Benefited from above modulation,the obtained N-doped SnO_2 catalysts with oxygen vacancies(Ov-N-SnO_2)exhibit faradaic efficiency of 93% for C_1 formation,88% for HCOOH production and well-suppression of H_2 evolution over a wide range of potentials.
Clearly understanding the structure-function relationship and rational design of efficient CO_2 electrocatalysts are still the challenges.This article describes the molecular origin of high selectivity of formic acid on N-doped SnO_2 nanoparticles,which obtained via thermal treatment of g-C_3N_4 and SnCl_2·2H_2O precursor.Combined with density functional theory(DFT)calculations,we discover that N-doping effectively introduces oxygen vacancies and increases the charge density of Sn sites,which plays a positive role in CO_2 activation.In addition,N-doping further regulates the adsorption energy of*OCHO,*COOH,*H and promotes HCOOH generation.Benefited from above modulation,the obtained N-doped SnO_2 catalysts with oxygen vacancies(Ov-N-SnO_2)exhibit faradaic efficiency of 93% for C_1 formation,88% for HCOOH production and well-suppression of H_2 evolution over a wide range of potentials.
Clearly understanding the structure-function relationship and rational design of efficient CO_2 electrocatalysts are still the challenges.This article describes the molecular origin of high selectivity of formic acid on N-doped SnO_2 nanoparticles,which obtained via thermal treatment of g-C_3N_4 and SnCl_2·2H_2O precursor.Combined with density functional theory(DFT)calculations,we discover that N-doping effectively introduces oxygen vacancies and increases the charge density of Sn sites,which plays a positive role in CO_2 activation.In addition,N-doping further regulates the adsorption energy of*OCHO,*COOH,*H and promotes HCOOH generation.Benefited from above modulation,the obtained N-doped SnO_2 catalysts with oxygen vacancies(Ov-N-SnO_2)exhibit faradaic efficiency of 93% for C_1 formation,88% for HCOOH production and well-suppression of H_2 evolution over a wide range of potentials.
引文
1 Schreier M,Héroguel F,Steier L,Ahmad S,Luterbacher JS,Mayer MT,Luo J,Gr?tzel M.Nat Energy,2017,2:17087
2 Jiang B,Zhang XG,Jiang K,Wu DY,Cai WB.J Am Chem Soc,2018,140:2880-2889
3 Dai L,Qin Q,Wang P,Zhao X,Hu C,Liu P,Qin R,Chen M,Ou D,Xu C,Mo S,Wu B,Fu G,Zhang P,Zheng N.Sci Adv,2017,3:e1701069
4 Lu L,Sun X,Ma J,Zhu Q,Wu C,Yang D,Han B.Sci China Chem,2018,61:228-235
5 Li X,He X,Liu X,He LN.Sci China Chem,2017,60:841-852
6 Qiao J,Liu Y,Hong F,Zhang J.Chem Soc Rev,2014,43:631-675
7 Abanades JC,Rubin ES,Mazzotti M,Herzog HJ.Energy Environ Sci,2017,10:2491-2499
8 Sun Z,Ma T,Tao H,Fan Q,Han B.Chem,2017,3:560-587
9 Koppenol WH,Rush JD.J Phys Chem,1987,91:4429-4430
10 Wen G,Lee DU,Ren B,Hassan FM,Jiang G,Cano ZP,Gostick J,Croiset E,Bai Z,Yang L,Chen Z.Adv Energy Mater,2018,8:1802427
11 Zhang S,Kang P,Meyer TJ.J Am Chem Soc,2014,136:1734-1737
12 Li F,Chen L,Knowles GP,MacFarlane DR,Zhang J.Angew Chem Int Ed,2017,56:505-509
13 Bai X,Chen W,Zhao C,Li S,Song Y,Ge R,Wei W,Sun Y.Angew Chem,2017,129:12387-12391
14 Lei F,Liu W,Sun Y,Xu J,Liu K,Liang L,Yao T,Pan B,Wei S,Xie Y.Nat Commun,2016,7:12697
15 Geng Z,Kong X,Chen W,Su H,Liu Y,Cai F,Wang G,Zeng J.Angew Chem Int Ed,2018,57:6054-6059
16 Martin O,Martín AJ,Mondelli C,Mitchell S,Segawa TF,Hauert R,Drouilly C,Curulla-FerréD,Pérez-Ramírez J.Angew Chem Int Ed,2016,55:6261-6265
17 Zheng Y,Qiao SZ.Nat Chem,2018,10:899-902
18 Chikhale LP,Patil JY,Shaikh FI,Rajgure AV,Pawar RC,Mulla IS,Suryavanshi SS.Mater Sci Semicon Proc,2014,27:121-129
19 Li Q,Wang Z,Zhang M,Hou P,Kang P.J Energy Chem,2017,26:825-829
20 Kim DW,Kim DH,Kim HJ,So HW,Hong MP.Curr Appl Phys,2011,11:S67-S72
21 Liang Y,Li Y,Wang H,Zhou J,Wang J,Regier T,Dai H.Nat Mater,2011,10:780-786
22 Niu P,Zhang L,Liu G,Cheng HM.Adv Funct Mater,2012,22:4763-4770
23 Liu X,Zhou K,Wang L,Wang B,Li Y.J Am Chem Soc,2009,131:3140-3141
24 Fan JCC,Goodenough JB.J Appl Phys,1977,48:3524-3531
25 Kar A,Kundu S,Patra A.J Phys Chem C,2011,115:118-124
26 Choi WK,Jung HJ,Koh SK.J Vacuum Sci Tech A,1996,14:359-366
27 Lin AWC,Armstrong NR,Kuwana T.Anal Chem,1977,49:1228-1235
28 Wang J,Tafen DN,Lewis JP,Hong Z,Manivannan A,Zhi M,Li M,Wu N.J Am Chem Soc,2009,131:12290-12297
29 Rogers C,Perkins WS,Veber G,Williams TE,Cloke RR,Fischer FR.J Am Chem Soc,2017,139:4052-4061
30 Lu Q,Rosen J,Zhou Y,Hutchings GS,Kimmel YC,Chen JG,Jiao F.Nat Commun,2014,5:3242
31 Gattrell M,Gupta N,Co A.J Electroanal Chem,2006,594:1-19
32 Garand E,Wende T,Goebbert DJ,Bergmann R,Meijer G,Neumark DM,Asmis KR.J Am Chem Soc,2010,132:849-856
33 Firet NJ,Smith WA.ACS Catal,2016,7:606-612
34 Baruch MF,Pander Iii JE,White JL,Bocarsly AB.ACS Catal,2015,5:3148-3156
35 Gao D,Zhou H,Cai F,Wang D,Hu Y,Jiang B,Cai WB,Chen X,Si R,Yang F,Miao S,Wang J,Wang G,Bao X.Nano Res,2017,10:2181-2191
2 Jiang B,Zhang XG,Jiang K,Wu DY,Cai WB.J Am Chem Soc,2018,140:2880-2889
3 Dai L,Qin Q,Wang P,Zhao X,Hu C,Liu P,Qin R,Chen M,Ou D,Xu C,Mo S,Wu B,Fu G,Zhang P,Zheng N.Sci Adv,2017,3:e1701069
4 Lu L,Sun X,Ma J,Zhu Q,Wu C,Yang D,Han B.Sci China Chem,2018,61:228-235
5 Li X,He X,Liu X,He LN.Sci China Chem,2017,60:841-852
6 Qiao J,Liu Y,Hong F,Zhang J.Chem Soc Rev,2014,43:631-675
7 Abanades JC,Rubin ES,Mazzotti M,Herzog HJ.Energy Environ Sci,2017,10:2491-2499
8 Sun Z,Ma T,Tao H,Fan Q,Han B.Chem,2017,3:560-587
9 Koppenol WH,Rush JD.J Phys Chem,1987,91:4429-4430
10 Wen G,Lee DU,Ren B,Hassan FM,Jiang G,Cano ZP,Gostick J,Croiset E,Bai Z,Yang L,Chen Z.Adv Energy Mater,2018,8:1802427
11 Zhang S,Kang P,Meyer TJ.J Am Chem Soc,2014,136:1734-1737
12 Li F,Chen L,Knowles GP,MacFarlane DR,Zhang J.Angew Chem Int Ed,2017,56:505-509
13 Bai X,Chen W,Zhao C,Li S,Song Y,Ge R,Wei W,Sun Y.Angew Chem,2017,129:12387-12391
14 Lei F,Liu W,Sun Y,Xu J,Liu K,Liang L,Yao T,Pan B,Wei S,Xie Y.Nat Commun,2016,7:12697
15 Geng Z,Kong X,Chen W,Su H,Liu Y,Cai F,Wang G,Zeng J.Angew Chem Int Ed,2018,57:6054-6059
16 Martin O,Martín AJ,Mondelli C,Mitchell S,Segawa TF,Hauert R,Drouilly C,Curulla-FerréD,Pérez-Ramírez J.Angew Chem Int Ed,2016,55:6261-6265
17 Zheng Y,Qiao SZ.Nat Chem,2018,10:899-902
18 Chikhale LP,Patil JY,Shaikh FI,Rajgure AV,Pawar RC,Mulla IS,Suryavanshi SS.Mater Sci Semicon Proc,2014,27:121-129
19 Li Q,Wang Z,Zhang M,Hou P,Kang P.J Energy Chem,2017,26:825-829
20 Kim DW,Kim DH,Kim HJ,So HW,Hong MP.Curr Appl Phys,2011,11:S67-S72
21 Liang Y,Li Y,Wang H,Zhou J,Wang J,Regier T,Dai H.Nat Mater,2011,10:780-786
22 Niu P,Zhang L,Liu G,Cheng HM.Adv Funct Mater,2012,22:4763-4770
23 Liu X,Zhou K,Wang L,Wang B,Li Y.J Am Chem Soc,2009,131:3140-3141
24 Fan JCC,Goodenough JB.J Appl Phys,1977,48:3524-3531
25 Kar A,Kundu S,Patra A.J Phys Chem C,2011,115:118-124
26 Choi WK,Jung HJ,Koh SK.J Vacuum Sci Tech A,1996,14:359-366
27 Lin AWC,Armstrong NR,Kuwana T.Anal Chem,1977,49:1228-1235
28 Wang J,Tafen DN,Lewis JP,Hong Z,Manivannan A,Zhi M,Li M,Wu N.J Am Chem Soc,2009,131:12290-12297
29 Rogers C,Perkins WS,Veber G,Williams TE,Cloke RR,Fischer FR.J Am Chem Soc,2017,139:4052-4061
30 Lu Q,Rosen J,Zhou Y,Hutchings GS,Kimmel YC,Chen JG,Jiao F.Nat Commun,2014,5:3242
31 Gattrell M,Gupta N,Co A.J Electroanal Chem,2006,594:1-19
32 Garand E,Wende T,Goebbert DJ,Bergmann R,Meijer G,Neumark DM,Asmis KR.J Am Chem Soc,2010,132:849-856
33 Firet NJ,Smith WA.ACS Catal,2016,7:606-612
34 Baruch MF,Pander Iii JE,White JL,Bocarsly AB.ACS Catal,2015,5:3148-3156
35 Gao D,Zhou H,Cai F,Wang D,Hu Y,Jiang B,Cai WB,Chen X,Si R,Yang F,Miao S,Wang J,Wang G,Bao X.Nano Res,2017,10:2181-2191