In Situ Coupling Strategy for Anchoring Monodisperse Co_9S_8 Nanoparticles on S and N Dual?Doped Graphene as a Bifunctional Electrocatalyst for Rechargeable Zn–Air Battery
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摘要
An in situ coupling strategy to prepare Co_9S_8/S and N dual?doped graphene composite(Co_9S_8/NSG) has been proposed. The key point of this strategy is the function?oriented design of organic compounds. Herein, cobalt porphyrin derivatives with sulfo groups are employed as not only the coupling agents to form and anchor Co_9S_8 on the graphene in situ, but also the heteroatom?doped agent to generate S and N dual?doped graphene. The tight coupling of multiple active sites endows the composite materials with fast electrochemical kinetics and excellent stability for both oxygen reduction reaction(ORR) and oxygen evolution reaction(OER). The obtained electrocatalyst exhibits better activity parameter(ΔE = 0.82 V) and smaller Tafel slope(47.7 mV dec~(-1) for ORR and 69.2 mV dec~(-1) for OER) than commercially available Pt/C and RuO_2. Most importantly, as electrocatalyst for rechargeable Zn–air battery, Co_9S_8/NSG displays low charge–discharge voltage gap and outstanding long?term cycle stability over 138 h compared to Pt/C–RuO_2. To further broaden its application scope, a homemade all?solid?state Zn–air battery is also prepared, which displays good charge–discharge performance and cycle performance. The function?oriented design of N_4?metallomacrocycle derivatives might open new avenues to strategic construction of high?performance and long?life multifunctional electrocatalysts for wider electro?chemical energy applications.
An in situ coupling strategy to prepare Co_9S_8/S and N dual?doped graphene composite(Co_9S_8/NSG) has been proposed. The key point of this strategy is the function?oriented design of organic compounds. Herein, cobalt porphyrin derivatives with sulfo groups are employed as not only the coupling agents to form and anchor Co_9S_8 on the graphene in situ, but also the heteroatom?doped agent to generate S and N dual?doped graphene. The tight coupling of multiple active sites endows the composite materials with fast electrochemical kinetics and excellent stability for both oxygen reduction reaction(ORR) and oxygen evolution reaction(OER). The obtained electrocatalyst exhibits better activity parameter(ΔE = 0.82 V) and smaller Tafel slope(47.7 mV dec~(-1) for ORR and 69.2 mV dec~(-1) for OER) than commercially available Pt/C and RuO_2. Most importantly, as electrocatalyst for rechargeable Zn–air battery, Co_9S_8/NSG displays low charge–discharge voltage gap and outstanding long?term cycle stability over 138 h compared to Pt/C–RuO_2. To further broaden its application scope, a homemade all?solid?state Zn–air battery is also prepared, which displays good charge–discharge performance and cycle performance. The function?oriented design of N_4?metallomacrocycle derivatives might open new avenues to strategic construction of high?performance and long?life multifunctional electrocatalysts for wider electro?chemical energy applications.
An in situ coupling strategy to prepare Co_9S_8/S and N dual?doped graphene composite(Co_9S_8/NSG) has been proposed. The key point of this strategy is the function?oriented design of organic compounds. Herein, cobalt porphyrin derivatives with sulfo groups are employed as not only the coupling agents to form and anchor Co_9S_8 on the graphene in situ, but also the heteroatom?doped agent to generate S and N dual?doped graphene. The tight coupling of multiple active sites endows the composite materials with fast electrochemical kinetics and excellent stability for both oxygen reduction reaction(ORR) and oxygen evolution reaction(OER). The obtained electrocatalyst exhibits better activity parameter(ΔE = 0.82 V) and smaller Tafel slope(47.7 mV dec~(-1) for ORR and 69.2 mV dec~(-1) for OER) than commercially available Pt/C and RuO_2. Most importantly, as electrocatalyst for rechargeable Zn–air battery, Co_9S_8/NSG displays low charge–discharge voltage gap and outstanding long?term cycle stability over 138 h compared to Pt/C–RuO_2. To further broaden its application scope, a homemade all?solid?state Zn–air battery is also prepared, which displays good charge–discharge performance and cycle performance. The function?oriented design of N_4?metallomacrocycle derivatives might open new avenues to strategic construction of high?performance and long?life multifunctional electrocatalysts for wider electro?chemical energy applications.
引文
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3 .J.Fu,Z.P.Cano,M.G.Park,A.P.Yu,M.Fowler,Z.W.Chen, Electrically rechargeable zinc?air batteries:progress,challenges, and perspectives. Adv. Mater. 29(7), 1604685(2017). https://doi.org/10.1002/adma.20160 4685
4 .T.T. Wang, Z.K. Kou, S.C. Mu, J.P. Liu, D.P. He et al., 2D dual?metal zeolitic?imidazolate?framework?(ZIF)?derived bifunctional air electrodes with ultrahigh electrochemical properties for rechargeable zinc?air batteries. Adv. Funct.Mater.28(5),1705048(2017).https://doi.org/10.1002/adfm.20170 5048
5 .F.L. Meng, H.X. Zhong, D. Bao, J.M. Yan, X.B. Zhang,In situ coupling of strungCo4N and intertwined N–C fib?ers towards free?standing bifunctional cathode for robust,e cient, and flexible Zn–air batteries. J. Am. Chem. Soc.138 (32),10226–10231(2016).https://doi.org/10.1021/jacs.6b050 46
6 .D.U.Lee,J.Y.Choi,K.Feng,H.W.Park,Z.W.Chen,Advanced extremely durable 3D bifunctional air electrodes for rechargeable zinc?air batteries. Adv. Energy Mater. 4(6),1301389(2014). https://doi.org/10.1002/aenm.20130 1389
7 .H.B. Yang, J. Miao, S.F. Hung, J. Chen, H.B. Tao et al.,Identification of catalytic sites for oxygen reduction and oxy?gen evolution in N?doped graphene materials:development of highly e cient metal?free bifunctional electrocatalyst.Sci. Adv. 2(4), 1501122(2016). https://doi.org/10.1126/sciad v.15011 22
8 .X.P. Han, X.Y. Wu, Y.D. Deng, J. Liu, J. Lu, C. Zhong, W.B.Hu,UltrafinePtnanoparticle?decoratedpyrite?typeCoS2nanosheet arrays coated on carbon cloth as a bifunctional elec?trode for overall water splitting. Adv. Energy Mater. 8(24),1800935(2018). https://doi.org/10.1002/aenm.20180 0935
9 .Z. Chen, A.P. Yu, D. Higgins, H. Li, H.J. Wang, Z.W. Chen,Highly active and durable core?corona structured bifunctional catalyst for rechargeable metal?air battery application. Nano Lett. 12(4), 1946–1952(2012). https://doi.org/10.1021/nl2044327
10 .X.P. Han, X.Y. Wu, C. Zhong, Y.D. Deng, N.Q. Zhao, W.B.Hu,NiCo2S4 nanocrystals anchored on nitrogen?doped carbonnanotubes as a highly e cient bifunctional electrocatalyst for rechargeable zinc?air batteries. Nano Energy 31, 541–550(2017). https://doi.org/10.1016/j.nanoe n.2016.12.008
11 .J. Yin, Y.X. Li, F. Lv, M. Lu, K. Sun et al., Oxygen vacancies dominatedNiS2/CoS2 interface porous nanowires for portable Zn–air batteries driven water splitting devices. Adv. Mater.29 (47), 1704681(2017). https://doi.org/10.1002/adma.201704681
12 .Y.P. Tang, F. Jing, Z.X. Xu, F. Zhang, Y.Y. Mai, D.Q. Wu,Highly crumpled hybrids of nitrogen/sulfur dual?doped gra?phene andCo9S8 nanoplates as e cient bifunctional oxygen electrocatalysts. ACS Appl. Mater. Interfaces 9(14), 12340–12347(2017). https://doi.org/10.1021/acsam i.6b154 61
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19 .J. Guo, X.M. Yan, Q. Liu, Q. Li, X. Xu et al., The synthesis and synergistic catalysis of iron phthalocyanine and its gra?phene?based axial complex for enhanced oxygen reduction.Nano Energy 46, 347–355(2018). https://doi.org/10.1016/j.nanoe n.2018.02.026
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21 .D. Singh, I.I. Soykal, J. Tian, D.V. Deak, J. King, J.T. Miller,U.S. Ozkan, In situ characterization of the growth of CNx carbon nano?structures as oxygen reduction reaction catalysts.J. Catal. 304(11), 100–111(2013). https://doi.org/10.1016/j.jcat.2013.04.008
22.R.G. Cao, R. Thapa, H. Kim, X.D. Xu, M.G. Kim, Q. Li, N.Park, M.L. Liu, J. Cho, Promotion of oxygen reduction by a bio?inspired tethered iron phthalocyanine carbon nanotube?based catalyst. Nat. Commun. 4(3), 2076–2083(2013). https://doi.org/10.1038/ncomm s3076
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2 .Y.G. Li, M. Gong, Y.Y. Liang, J. Feng, J.E. Kim, H.L. Wang,G.S. Hong, B. Zhang, H.J. Dai, Advanced zinc?air batter?ies based on high?performance hybrid electrocatalysts. Nat.Commun. 4(5), 1805–1812(2013). https://doi.org/10.1038/ncomm s2812
3 .J.Fu,Z.P.Cano,M.G.Park,A.P.Yu,M.Fowler,Z.W.Chen, Electrically rechargeable zinc?air batteries:progress,challenges, and perspectives. Adv. Mater. 29(7), 1604685(2017). https://doi.org/10.1002/adma.20160 4685
4 .T.T. Wang, Z.K. Kou, S.C. Mu, J.P. Liu, D.P. He et al., 2D dual?metal zeolitic?imidazolate?framework?(ZIF)?derived bifunctional air electrodes with ultrahigh electrochemical properties for rechargeable zinc?air batteries. Adv. Funct.Mater.28(5),1705048(2017).https://doi.org/10.1002/adfm.20170 5048
5 .F.L. Meng, H.X. Zhong, D. Bao, J.M. Yan, X.B. Zhang,In situ coupling of strungCo4N and intertwined N–C fib?ers towards free?standing bifunctional cathode for robust,e cient, and flexible Zn–air batteries. J. Am. Chem. Soc.138 (32),10226–10231(2016).https://doi.org/10.1021/jacs.6b050 46
6 .D.U.Lee,J.Y.Choi,K.Feng,H.W.Park,Z.W.Chen,Advanced extremely durable 3D bifunctional air electrodes for rechargeable zinc?air batteries. Adv. Energy Mater. 4(6),1301389(2014). https://doi.org/10.1002/aenm.20130 1389
7 .H.B. Yang, J. Miao, S.F. Hung, J. Chen, H.B. Tao et al.,Identification of catalytic sites for oxygen reduction and oxy?gen evolution in N?doped graphene materials:development of highly e cient metal?free bifunctional electrocatalyst.Sci. Adv. 2(4), 1501122(2016). https://doi.org/10.1126/sciad v.15011 22
8 .X.P. Han, X.Y. Wu, Y.D. Deng, J. Liu, J. Lu, C. Zhong, W.B.Hu,UltrafinePtnanoparticle?decoratedpyrite?typeCoS2nanosheet arrays coated on carbon cloth as a bifunctional elec?trode for overall water splitting. Adv. Energy Mater. 8(24),1800935(2018). https://doi.org/10.1002/aenm.20180 0935
9 .Z. Chen, A.P. Yu, D. Higgins, H. Li, H.J. Wang, Z.W. Chen,Highly active and durable core?corona structured bifunctional catalyst for rechargeable metal?air battery application. Nano Lett. 12(4), 1946–1952(2012). https://doi.org/10.1021/nl2044327
10 .X.P. Han, X.Y. Wu, C. Zhong, Y.D. Deng, N.Q. Zhao, W.B.Hu,NiCo2S4 nanocrystals anchored on nitrogen?doped carbonnanotubes as a highly e cient bifunctional electrocatalyst for rechargeable zinc?air batteries. Nano Energy 31, 541–550(2017). https://doi.org/10.1016/j.nanoe n.2016.12.008
11 .J. Yin, Y.X. Li, F. Lv, M. Lu, K. Sun et al., Oxygen vacancies dominatedNiS2/CoS2 interface porous nanowires for portable Zn–air batteries driven water splitting devices. Adv. Mater.29 (47), 1704681(2017). https://doi.org/10.1002/adma.201704681
12 .Y.P. Tang, F. Jing, Z.X. Xu, F. Zhang, Y.Y. Mai, D.Q. Wu,Highly crumpled hybrids of nitrogen/sulfur dual?doped gra?phene andCo9S8 nanoplates as e cient bifunctional oxygen electrocatalysts. ACS Appl. Mater. Interfaces 9(14), 12340–12347(2017). https://doi.org/10.1021/acsam i.6b154 61
13 .H.X. Zhong, K. Li, Q. Zhang, J. Wang, F.L. Meng, Z.J. Wu,J.M. Yan, X.B. Zhang, In situ anchoring ofCo9S8 nanoparti?cles on N and S co?doped porous carbon tube as bifunctional oxygen electrocatalysts. NPG Asia Mater. 8(9), e308(2016).https://doi.org/10.1038/am.2016.132
14 .S.S. Li, P.P. Cheng, J.X. Luo, D. Zhou, W.M. Xu, J.W. Li,R.C. Li, D.S. Yuan, High?performance flexible asymmetric supercapacitorbasedonCoAl?LDHandrGOelectrodes.Nano?Micro Lett. 9(3), 31(2017). https://doi.org/10.1007/s4082 0?017?0134?8
15 .X.L. Huang, R.Z. Wang, D. Xu, Z.L. Wang, H.G. Wang et al.,Batteries:homogeneous CoO on graphene for binder?free and ultralong?life lithium ion batteries. Adv. Funct. Mater. 23(35),4345–4353(2013). https://doi.org/10.1002/adfm.20120 3777
16 .Z.L. Wang, X.F. Hao, Z. Jiang, X.P. Sun, D. Xu, J. Wang, H.X.Zhong, F.L. Meng, X.B. Zhang, C and N hybrid coordination derived Co–C–N complex as a highly e cient electrocatalyst for hydrogen evolution reaction. J. Am. Chem. Soc. 137(48),15070–15073(2015). https://doi.org/10.1021/jacs.5b090 21
17 .Q. Wang, P.P. Zhang, Q.Q. Zhuo, X.X. Lv, J.W. Wang, X.H.Sun, Direct synthesis of co?doped graphene on dielectric sub?strates using solid carbon sources. Nano?Micro Lett. 7(4),368 –373(2015). https://doi.org/10.1007/s4082 0?015?0052?6
18 .H.G.Wang,Y.H.Wang,Y.H.Li,Y.C.Wan,Q.Duan,Exceptional electrochemical performance of nitrogen?doped porouscarbonforlithiumstorage.Carbon82,116–123(2015). https://doi.org/10.1016/j.carbo n.2014.10.041
19 .J. Guo, X.M. Yan, Q. Liu, Q. Li, X. Xu et al., The synthesis and synergistic catalysis of iron phthalocyanine and its gra?phene?based axial complex for enhanced oxygen reduction.Nano Energy 46, 347–355(2018). https://doi.org/10.1016/j.nanoe n.2018.02.026
20 .H.G. Wang, C. Jiang, C.P. Yuan, Q. Wu, Q. Li, Q. Duan,Complexingagentengineeredstrategyforanchoring SnO2 nanoparticles on sulfur/nitrogen co?doped graphene for superior lithium and sodium ion storage. Chem. Eng.J.332(15),237–244(2018).https://doi.org/10.1016/j.cej.2017.09.081
21 .D. Singh, I.I. Soykal, J. Tian, D.V. Deak, J. King, J.T. Miller,U.S. Ozkan, In situ characterization of the growth of CNx carbon nano?structures as oxygen reduction reaction catalysts.J. Catal. 304(11), 100–111(2013). https://doi.org/10.1016/j.jcat.2013.04.008
22.R.G. Cao, R. Thapa, H. Kim, X.D. Xu, M.G. Kim, Q. Li, N.Park, M.L. Liu, J. Cho, Promotion of oxygen reduction by a bio?inspired tethered iron phthalocyanine carbon nanotube?based catalyst. Nat. Commun. 4(3), 2076–2083(2013). https://doi.org/10.1038/ncomm s3076
23 .K. Ariga, Y. Lvov, T. Kunitake, Assembling alternate dye?polyion molecular films by electrostatic layer?by?layer adsorp?tion. J. Am. Chem. Soc. 119(9), 2224–2231(1997). https://doi.org/10.1021/ja963 442c
24 .W.Q. Zheng, N. Shan, L.X. Yu, X.Q. Wang, Fluorescence and EPR properties of porphyrins and metalloporphyrins. Dyes Pigments 77(1), 153–157(2008). https://doi.org/10.1016/j.dyepi g.2007.04.007
25 .H. Xu, P. Wu, C. Liao, C.G. Lv, Z.Z. Gu, Controlling the morphology and optoelectronic properties of graphene hybrid materials by porphyrin interactions. Chem. Commun. 50(64),8951–8954(2014). https://doi.org/10.1039/C4CC0 3458A
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