Electrocatalytic activity of LaSr_3Fe_3O_(10) and LaSr_3Fe_3O_(10)-GO towards oxygen reduction reaction in alkaline medium
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摘要
Oxygen reduction reaction(ORR) plays a critical role in many energy conversion and storage processes.Therein, a comparative study of the electrocatalytic activity for ORR in 0.1 mol/L KOH solution was conducted using layered perovskite-like LaSr_3 Fe_3 O_(10) and LaSr3 Fe_3 O_(10)-graphene oxide(GO) composite as electrodes. Linear sweep voltammetry(LSV) results show that the LaSr3 Fe_3 O_(10)-GO hybrid exhibits higher current density, a more positive onset potential(-0.15 V vs. Hg/HgO) in comparison with LaSr_3 Fe_3 O_(10).The value of the overall transferred electrons for both catalysts implies a dominant two electron process for ORR. Both catalysts under alkalic conditions exhibit a two-step Tafel slope, suggesting a change in the reaction mechanism for ORR. The composite electrode exhibits a higher ORR current density, but inferior durability performances in relative to the LaSr_3 Fe_3 O_(10) electrode.
Oxygen reduction reaction(ORR) plays a critical role in many energy conversion and storage processes.Therein, a comparative study of the electrocatalytic activity for ORR in 0.1 mol/L KOH solution was conducted using layered perovskite-like LaSr_3 Fe_3 O_(10) and LaSr3 Fe_3 O_(10)-graphene oxide(GO) composite as electrodes. Linear sweep voltammetry(LSV) results show that the LaSr3 Fe_3 O_(10)-GO hybrid exhibits higher current density, a more positive onset potential(-0.15 V vs. Hg/HgO) in comparison with LaSr_3 Fe_3 O_(10).The value of the overall transferred electrons for both catalysts implies a dominant two electron process for ORR. Both catalysts under alkalic conditions exhibit a two-step Tafel slope, suggesting a change in the reaction mechanism for ORR. The composite electrode exhibits a higher ORR current density, but inferior durability performances in relative to the LaSr_3 Fe_3 O_(10) electrode.
Oxygen reduction reaction(ORR) plays a critical role in many energy conversion and storage processes.Therein, a comparative study of the electrocatalytic activity for ORR in 0.1 mol/L KOH solution was conducted using layered perovskite-like LaSr_3 Fe_3 O_(10) and LaSr3 Fe_3 O_(10)-graphene oxide(GO) composite as electrodes. Linear sweep voltammetry(LSV) results show that the LaSr3 Fe_3 O_(10)-GO hybrid exhibits higher current density, a more positive onset potential(-0.15 V vs. Hg/HgO) in comparison with LaSr_3 Fe_3 O_(10).The value of the overall transferred electrons for both catalysts implies a dominant two electron process for ORR. Both catalysts under alkalic conditions exhibit a two-step Tafel slope, suggesting a change in the reaction mechanism for ORR. The composite electrode exhibits a higher ORR current density, but inferior durability performances in relative to the LaSr_3 Fe_3 O_(10) electrode.
引文
1.Zhu L, Ran R, Tade M, Wang W, Shao ZP. Perovskite materials in energy storage and conversion. Asia-PacJ Chem Eng. 2016;11(3):338.
2.Stoerzinger KA, Risch M, Han B, Shao-Horn Y. Recent insights into manganese oxides in catalyzing oxygen reduction kinetics. ACS Catal. 2015:5:6021.
3.Cheng FY, Chen J. Metal-air batteries:from oxygen reduction electrochemistry to cathode catalysts. Chem Soc Rev. 2012;41(6):2172.
4.Meadowcroft DB. Low-cost oxygen electrode materia. Nature. 1970;226(5248):847.
5.Suntivich J, Gasteiger HA, Yabuuchi N, Nakanishi H, Goodenough JB, ShaoHorn Y. Design principles for oxygen-reduction activity on perovskite oxide catalysts for fuel cells and metal-air batteries. Nat Chem. 2011;3(7):546.
6.Mueller DN, Machala ML, Bluhm H, Chueh WC. Redox activity of surface oxygen anions in oxygen-deficient perovskite oxides during electrochemical reactions.Nat Commun. 2015;6:6097.
7.Chen G, Zhou W, Guan DQ, Sunarso J, Zhu YL, Hu XF, et al. Two orders of magnitude enhancement in oxygen evolution reactivity on amorphous Ba_(0.5)Sr_(0.5)Co_(0.8)Fe_(0.2)O_(3δ)nanofilms with tunable oxidation state. Sci Adv.2017;3(6):e1603206.
8.Zhu YL, Zhou W, Chen YB, Yu J, Xu XM, Su C, et al. Boosting oxygen reduction reaction activity of palladium by stabilizing its unusual oxidation states in perovskite. Chem Mater. 2015;27(8):3048.
9.Chen G, Hu ZW, Zhu YP, Chen ZG, Zhong YJ, Lin HJ, et al. Ultrahigh-performance tungsten-doped perovskites for the oxygen evolution reaction. J Mater Chem A.2018;6(21):9854.
10.Fabbri E, Mohamed R, Levecque P, Conrad O, Kotz R, Schmidt TJ. Composite electrode boosts the activity of Ba_(0.5)Sr_(0.8)Co_(0.8)Fe_(0.2)O_(3-δ)perovskite and carbon toward oxygen reduction in alkaline media. ACS Catal.2014;4(4):1061.
11.Fabbri E, Mohamed R, Levecque P, Conrad O, Kotz R, Schmidt TJ. Unraveling the oxygen reduction reaction mechanism and activity of d-band perovskite electrocatalysts for low temperature alkaline fuel cells. ECS Trans. 2014;64(3):1081.
12.Liang YY, Li YG, Wang HL, Zhou JG, Wang J, Regier T, et al. Co_3O_4 nanocrystals on graphene as a synergistic catalyst for oxygen reduction reaction. Nat Mater.2011;10:780.
13.Kim JH, Kim YN, Lee KT, Manthiram A. Ln(Sr,Ca)3(Fe,Co)3O10 intergrowth oxide cathodes for solid oxide fuel cells. ECS Trans. 2011:35:2137.
14.Takeguchi T, Yamanaka T, Takahashi H, Watanabe H, Kuroki T, Nakanishi H,et al. Layered perovskite oxide:a reversible air electrode for oxygen Evolution/reduction in rechargeable metal-air batteries.J Am Chem Soc. 2013:135:11125.
15.Cui MJ, Zhang GG, Li Q, Liu T. Studies on the structure and oxygen nonstoichiometry of LaSr_3Fe_3O_(10-δ)mixed conductor. J Nanchang Hongkong Univ(Nat Sci). 2007:21:84.
16.Geng DS, Chen Y, Chen YG, Li YL, Li RY, Sun XL, et al. High oxygen-reduction activity and durability of nitrogen-doped graphene. Energy Environ Sci.2011;4(3):760.
17.Hong WT, Risch M, Stoerzinger KA, Grimaud AJL, Suntivich J, Shao-Horn Y.Toward the rational design of non-precious transition metal oxides for oxygen electrocatalysis. Energy Environ Sci. 2015;8:1404.
18.Wang HL, Hao QL, Yang XJ, Lu ID, Wang X. Graphene oxide doped polyaniline for supercapacitors. Electrochem Commun. 2009;11(6):1158.
19.Daems N, Sheng X, Vankelecom IFJ, Pescarmona PP. Metal-free doped carbon materials as electrocatalysts for the oxygen reduction reaction. J Mater Chem A.2014;2:4085.
20.Feng LG, Sun XJ, Yao SK, Liu CP, Xing W, Zhang JJ. 3-electrocatalysts and catalyst layers for oxygen reduction reaction. Electrocatalysts. 2014;26(5):67.
21.Van Brussel M, Kokkinidis G, Hubin A, Buess-Herman C. Oxygen reduction at platinum modified gold electrodes. Electrochim Acta. 2003;48(25):3909.
22.Chen G, Sunarso J, Zhu YP, Yu J, Zhong YJ, Zhou W, et al. Highly active carbon/α-MnO_2 hybrid oxygen reduction reaction electrocatalysts. ChemElectroChem.2016;3(11):1760.
23.Wang YR, Ohnishi R, Yoo E, He P, Kubota J, Domen K, et al. Nano-and microsized TiN as the electrocatalysts for ORR in Li-air fuel cell with alkaline aqueous electrolyte.J Mater Chem. 2012;22(31):15549.
24.Strbac S, Anastasijevic NA, Adzic RR. Oxygen reduction on Au(111)and vicinal Au(332)faces:a rotating disc and disc-ring study. Electrochim Acta.1994;39(7):983.
25.Wu JJ, Zhang D, Wang Y, Wan Y, Hou BR. Catalytic activity of graphene-cobalt hydroxide composite for oxygen reduction reaction in alkaline media. J Power Sources. 2012:198:122.
26.Wu JJ, Wang Y, Zhang D, Hou BR. Studies on the electrochemical reduction of oxygen catalyzed by reduced graphene sheets in neutral media. J Power Sources. 2011;196(3):1141.
27.Sotelo-Mazon P, Gonzalez-Huerta RG, Cabanas-Moreno JG, Solorza-Feria O.Mechanically milled RuxFey electrocatalyst for oxygen reduction in acid media.Int J Electrochem Sci. 2007:2:523.
28.Bursell M, Pirjamali M, Kiros Y. La_(0.6)Ca_(0.4)CoO_3, La_(0.1)Ca_(0.9)MnO_3 and LaNiO_3 as bifunctional oxygen electrodes. Electrochim Acta. 2002;47(10):1651.
29.Shinagawa T, Garcia-Esparza AT, Takanabe K. Insight on Tafel slopes from a microkinetic analysis of aqueous electrocatalysis for energy conversion. Sci Rep.2015:5:13801.
30.Poux T, Bonnefont A, Kerangueven G, Tsirlina GA, Savinova ER. Electrocatalytic oxygen reduction reaction on perovskite oxides:series versus direct pathway.Chem Phys Chem. 2014;15(10):2108.
31.Ponce J, Rehspringer JL, Poillerat G, Gautier JL. Electrochemical study of nickel-aluminium-manganese spinel Ni_xAl_(1-x)Mn_2O_4. Electrocatalytical properties for the oxygen evolution reaction and oxygen reduction reaction in alkaline media. Electrochim Acta. 2011;46(22):3373.
32.Zagal J, Pgez M. Electrocatalytic activity of metal phthalocyanines for oxygen reduction.J Electroanal Chem. 1992;339(1-2):13.
33.Zhu YP, Guo C, Zheng Y, Qiao S. Surface and interface engineering of noblemetal-free electrocatalysts for efficient energy conversion processes. Acc Chem Res. 2017;50(4):915.
34.Han XP, Zhang TR, Du J, Cheng FY, Chen J. Porous calcium-manganese oxide microspheres for electrocatalytic oxygen reduction with high activity. Chem Sci. 2013;4(1):368.
35.Hardin WG, Mefford JT, Slanac DA, Patel BB, Wang X, Dai S, et al. Tuning the electrocatalytic activity of perovskites through active site variation and support interactions. Chem Mater. 2014;26(11):3368.
2.Stoerzinger KA, Risch M, Han B, Shao-Horn Y. Recent insights into manganese oxides in catalyzing oxygen reduction kinetics. ACS Catal. 2015:5:6021.
3.Cheng FY, Chen J. Metal-air batteries:from oxygen reduction electrochemistry to cathode catalysts. Chem Soc Rev. 2012;41(6):2172.
4.Meadowcroft DB. Low-cost oxygen electrode materia. Nature. 1970;226(5248):847.
5.Suntivich J, Gasteiger HA, Yabuuchi N, Nakanishi H, Goodenough JB, ShaoHorn Y. Design principles for oxygen-reduction activity on perovskite oxide catalysts for fuel cells and metal-air batteries. Nat Chem. 2011;3(7):546.
6.Mueller DN, Machala ML, Bluhm H, Chueh WC. Redox activity of surface oxygen anions in oxygen-deficient perovskite oxides during electrochemical reactions.Nat Commun. 2015;6:6097.
7.Chen G, Zhou W, Guan DQ, Sunarso J, Zhu YL, Hu XF, et al. Two orders of magnitude enhancement in oxygen evolution reactivity on amorphous Ba_(0.5)Sr_(0.5)Co_(0.8)Fe_(0.2)O_(3δ)nanofilms with tunable oxidation state. Sci Adv.2017;3(6):e1603206.
8.Zhu YL, Zhou W, Chen YB, Yu J, Xu XM, Su C, et al. Boosting oxygen reduction reaction activity of palladium by stabilizing its unusual oxidation states in perovskite. Chem Mater. 2015;27(8):3048.
9.Chen G, Hu ZW, Zhu YP, Chen ZG, Zhong YJ, Lin HJ, et al. Ultrahigh-performance tungsten-doped perovskites for the oxygen evolution reaction. J Mater Chem A.2018;6(21):9854.
10.Fabbri E, Mohamed R, Levecque P, Conrad O, Kotz R, Schmidt TJ. Composite electrode boosts the activity of Ba_(0.5)Sr_(0.8)Co_(0.8)Fe_(0.2)O_(3-δ)perovskite and carbon toward oxygen reduction in alkaline media. ACS Catal.2014;4(4):1061.
11.Fabbri E, Mohamed R, Levecque P, Conrad O, Kotz R, Schmidt TJ. Unraveling the oxygen reduction reaction mechanism and activity of d-band perovskite electrocatalysts for low temperature alkaline fuel cells. ECS Trans. 2014;64(3):1081.
12.Liang YY, Li YG, Wang HL, Zhou JG, Wang J, Regier T, et al. Co_3O_4 nanocrystals on graphene as a synergistic catalyst for oxygen reduction reaction. Nat Mater.2011;10:780.
13.Kim JH, Kim YN, Lee KT, Manthiram A. Ln(Sr,Ca)3(Fe,Co)3O10 intergrowth oxide cathodes for solid oxide fuel cells. ECS Trans. 2011:35:2137.
14.Takeguchi T, Yamanaka T, Takahashi H, Watanabe H, Kuroki T, Nakanishi H,et al. Layered perovskite oxide:a reversible air electrode for oxygen Evolution/reduction in rechargeable metal-air batteries.J Am Chem Soc. 2013:135:11125.
15.Cui MJ, Zhang GG, Li Q, Liu T. Studies on the structure and oxygen nonstoichiometry of LaSr_3Fe_3O_(10-δ)mixed conductor. J Nanchang Hongkong Univ(Nat Sci). 2007:21:84.
16.Geng DS, Chen Y, Chen YG, Li YL, Li RY, Sun XL, et al. High oxygen-reduction activity and durability of nitrogen-doped graphene. Energy Environ Sci.2011;4(3):760.
17.Hong WT, Risch M, Stoerzinger KA, Grimaud AJL, Suntivich J, Shao-Horn Y.Toward the rational design of non-precious transition metal oxides for oxygen electrocatalysis. Energy Environ Sci. 2015;8:1404.
18.Wang HL, Hao QL, Yang XJ, Lu ID, Wang X. Graphene oxide doped polyaniline for supercapacitors. Electrochem Commun. 2009;11(6):1158.
19.Daems N, Sheng X, Vankelecom IFJ, Pescarmona PP. Metal-free doped carbon materials as electrocatalysts for the oxygen reduction reaction. J Mater Chem A.2014;2:4085.
20.Feng LG, Sun XJ, Yao SK, Liu CP, Xing W, Zhang JJ. 3-electrocatalysts and catalyst layers for oxygen reduction reaction. Electrocatalysts. 2014;26(5):67.
21.Van Brussel M, Kokkinidis G, Hubin A, Buess-Herman C. Oxygen reduction at platinum modified gold electrodes. Electrochim Acta. 2003;48(25):3909.
22.Chen G, Sunarso J, Zhu YP, Yu J, Zhong YJ, Zhou W, et al. Highly active carbon/α-MnO_2 hybrid oxygen reduction reaction electrocatalysts. ChemElectroChem.2016;3(11):1760.
23.Wang YR, Ohnishi R, Yoo E, He P, Kubota J, Domen K, et al. Nano-and microsized TiN as the electrocatalysts for ORR in Li-air fuel cell with alkaline aqueous electrolyte.J Mater Chem. 2012;22(31):15549.
24.Strbac S, Anastasijevic NA, Adzic RR. Oxygen reduction on Au(111)and vicinal Au(332)faces:a rotating disc and disc-ring study. Electrochim Acta.1994;39(7):983.
25.Wu JJ, Zhang D, Wang Y, Wan Y, Hou BR. Catalytic activity of graphene-cobalt hydroxide composite for oxygen reduction reaction in alkaline media. J Power Sources. 2012:198:122.
26.Wu JJ, Wang Y, Zhang D, Hou BR. Studies on the electrochemical reduction of oxygen catalyzed by reduced graphene sheets in neutral media. J Power Sources. 2011;196(3):1141.
27.Sotelo-Mazon P, Gonzalez-Huerta RG, Cabanas-Moreno JG, Solorza-Feria O.Mechanically milled RuxFey electrocatalyst for oxygen reduction in acid media.Int J Electrochem Sci. 2007:2:523.
28.Bursell M, Pirjamali M, Kiros Y. La_(0.6)Ca_(0.4)CoO_3, La_(0.1)Ca_(0.9)MnO_3 and LaNiO_3 as bifunctional oxygen electrodes. Electrochim Acta. 2002;47(10):1651.
29.Shinagawa T, Garcia-Esparza AT, Takanabe K. Insight on Tafel slopes from a microkinetic analysis of aqueous electrocatalysis for energy conversion. Sci Rep.2015:5:13801.
30.Poux T, Bonnefont A, Kerangueven G, Tsirlina GA, Savinova ER. Electrocatalytic oxygen reduction reaction on perovskite oxides:series versus direct pathway.Chem Phys Chem. 2014;15(10):2108.
31.Ponce J, Rehspringer JL, Poillerat G, Gautier JL. Electrochemical study of nickel-aluminium-manganese spinel Ni_xAl_(1-x)Mn_2O_4. Electrocatalytical properties for the oxygen evolution reaction and oxygen reduction reaction in alkaline media. Electrochim Acta. 2011;46(22):3373.
32.Zagal J, Pgez M. Electrocatalytic activity of metal phthalocyanines for oxygen reduction.J Electroanal Chem. 1992;339(1-2):13.
33.Zhu YP, Guo C, Zheng Y, Qiao S. Surface and interface engineering of noblemetal-free electrocatalysts for efficient energy conversion processes. Acc Chem Res. 2017;50(4):915.
34.Han XP, Zhang TR, Du J, Cheng FY, Chen J. Porous calcium-manganese oxide microspheres for electrocatalytic oxygen reduction with high activity. Chem Sci. 2013;4(1):368.
35.Hardin WG, Mefford JT, Slanac DA, Patel BB, Wang X, Dai S, et al. Tuning the electrocatalytic activity of perovskites through active site variation and support interactions. Chem Mater. 2014;26(11):3368.
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