血红细胞状氮掺杂多孔碳材料的制备及其氧还原催化性能的研究（英文）
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摘要
以三聚氰胺氰尿酸为氮源和自牺牲模板,葡萄糖为碳源,采用两步法制备了一种高氮含量(9.81%)和高比表面积(631.46m~2/g)的血红细胞状氮掺杂多孔碳材料。该催化剂在碱性电解液中的起始电位和极限电流密度均优于商用20wt%Pt/C催化剂。该催化剂主要是通过四电子途径来催化氧还原反应过程。其优异的催化活性来源于原位掺杂的高含量氮与三维(3D)高比表面积多孔网络结构的协同作用,这有利于活性位点的暴露。有趣的是,氧还原的催化活性很大程度上取决于石墨氮的比例,而不是氮元素的总含量。
A red-blood-cell-like nitrogen-doped porous carbon catalyst with a high nitrogen content(9.81%) and specific surface area(631.46 m~2/g) was prepared by using melamine cyanuric acid and glucose as sacrificial template and carbon source, respectively. This catalyst has a comparable onset potential and a higher diffusion-limiting current density than the commercial 20 wt% Pt/C catalyst in alkaline electrolyte. The oxygen reduction reaction mechanism catalyzed by this catalyst is mainly through a 4 e pathway process. The excellent catalytic activity could origin from the synergistic effect of the in-situ doped nitrogen(up to 9.81%) and three-dimensional(3 D) porous network structure with high specific surface area, which is conducive to the exposure of more active sites. It is interesting to note that the catalytic activity of oxygen reduction strongly depends on the proportion of graphic N rather than the total N content.
A red-blood-cell-like nitrogen-doped porous carbon catalyst with a high nitrogen content(9.81%) and specific surface area(631.46 m~2/g) was prepared by using melamine cyanuric acid and glucose as sacrificial template and carbon source, respectively. This catalyst has a comparable onset potential and a higher diffusion-limiting current density than the commercial 20 wt% Pt/C catalyst in alkaline electrolyte. The oxygen reduction reaction mechanism catalyzed by this catalyst is mainly through a 4 e pathway process. The excellent catalytic activity could origin from the synergistic effect of the in-situ doped nitrogen(up to 9.81%) and three-dimensional(3 D) porous network structure with high specific surface area, which is conducive to the exposure of more active sites. It is interesting to note that the catalytic activity of oxygen reduction strongly depends on the proportion of graphic N rather than the total N content.
引文
[1]GU Ying-ying,ZHAO Li,YANG Ming-yang,XIONG Yi-qiu,WU Zhe,ZHOU Min-jia,YAN Jun.Preparation and characterization of highly photocatalytic active hierarchical Bi OX(X=Cl,Br,I)microflowers for rhodamine Bdegradation with kinetic modelling studies[J].Journal of Central South University,2017,24(4):754-765.
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[14]LIN Hua,CHEN Kang-hua,SHUAI Yi,HE Xuan,GE Ke.Influence of CsNO3 as electrolyte additive on electrochemical property of lithium anode in rechargeable battery[J].Journal of Central South University,2018,25(4):719-728.
[15]LI Jing-sha,CHEN Jia-jie,WANG Hai-yan,REN Yu,LIUKun,TANG You-gen,LIU Min.Fe/N Co-doped carbon materials with controllable structure as highly efficient electrocatalysts for oxygen reduction reaction in Al-air batteries[J].Energy Storage Materials,2017,8:49-58.
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[17]WANG Qi-bin,MA Hong-bo,KONG Xian-guang,ZHANGYi-min.A distributed dynamic mesh model of a helical gear pair with tooth profile errors[J].Journal of Central South University,2018,25(2):287-303.
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[22]WU Qiu-mei,RUAN Jian-ming,ZHOU Zhong-cheng,SANG Shang-bin.Magneli phase titanium sub-oxide conductive ceramic TinO2n-1 as support for electrocatalyst toward oxygen reduction reaction with high activity and stability[J].Journal of Central South University,2015,22(4):1212-1219.
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[24]WANG Xiao-xia,ZOU Biao,DU Xin-xin,WANG Jian-nong.N-doped carbon nanocages with high catalytic activity and durability for oxygen reduction[J].J Mater Chem A,2015,3(23):12427-12435.
[25]LIU Ming-kai,SONG Yan-fang,HE Si-xin,PAN Ji-sheng,XIA Yong-yao,LIU Tian-xin.Nitrogen-doped graphene nanoribbons as efficient metal-free electrocatalysts for oxygen reduction[J].ACS Appl Mater Interfaces,2014,6(6):4214-4222.
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[27]JIANG Wen-jie,HU Jin-song,ZHANG Xing,JIANG Yan,YU Bin-bin,WEI Zi-dong.In-situ nitrogen-doped nano-porous carbon nanocables as an efficient metal-free catalyst for oxygen reduction reaction[J].J Mater Chem A,2014,2:10154-10160.
[28]CHEN Ping,XIAO Tian-yuan,QIAN Yu-hong,LIShan-shan,YU Shu-hong.A nitrogen-doped graphenecarbon nanotube nanocomposite with synergistically enhanced electrochemical activity[J].Adv Mater,2013,25:3192-3196.
[29]QU De-yang.Investigation of oxygen reduction on activated carbon electrodes in alkaline solution[J].Carbon,2007,45:1296-1301.
[30]WONG Wai-yin,DAUD W R W,MOHAMAD A B,KADHUM A A H,LOH K S,MAJLAN E H.Influence of nitrogen doping on carbon nanotubes towards the structure,composition and oxygen reduction reaction[J].Int JHydrogen Energy,2013,38:9421-9430.
[31]YANG Zhi,NIE Hua-gui,CHEN Xi-an,CHEN Xiao-hua,HUANG Shao-ming.Recent progress in doped carbon nanomaterials as effective cathode catalysts for fuel cell oxygen reduction reaction[J].J Power Sources,2013,236:238-249.
[32]LIU Sheng-wen,ZHANG Hai-min,ZHAO Qian,ZHANGXian,LIU Rong-rong,GE Xiao,WANG Guo-zhong,ZHAOHui-jun,CAI Wei-ping.Metal-organic framework derived nitrogen-doped porous carbon@graphene sandwich-like structured composites as bifunctional electrocatalysts for oxygen reduction and evolution reactions[J].Carbon,2016,106:74-83.
[33]CHEN Ping,WANG Li-kun,WANG Gan,GAO Min-gui,GE Jin,YUAN Wen-jin.Nitrogen-doped nanoporous carbon nanosheets derived from plant biomass:An efficient catalyst for oxygen reduction reaction[J].Energy Environ Sci,2014,7:4095-4103.
[34]QIAN Ying-dan,DU Pan,WU Ping,CAI Chen-xin,GERVASIO D F.Chemical nature of catalytic active sites for the oxygen reduction reaction on nitrogen-doped carbonsupported non-noble metal catalysts[J].J Phys Chem C,2016,120:9884-9896.
[35]YANG Xiao-ling,ZOU Wen-jian,SU Yun-he,ZHU Yi-hua,JIANG Hong-liang,SHEN Jian-hua.Activated nitrogendoped carbon nanofibers with hierarchical pore as efficient oxygen reduction reaction catalyst for microbial fuel cells[J].J Power Sources,2014,266:36-42.
[36]ZHANG Jun-li,CHEN Gao-li,ZHANG Qian,KANG Fei,YOU Bo.Self-assembly synthesis of N-doped carbon aerogels for supercapacitor and electrocatalytic oxygen reduction[J].ACS Appl Mater Interfaces,2015,7:12760-12786.
[37]LIANG Ji,DU Xin,GIBSON C,DU Xi-wen,QIAOShi-zhang.N-doped graphene natively grown on hierarchical ordered porous carbon for enhanced oxygen reduction[J].Adv Mater,2013,25:6226-6231.
[38]SUN Yi-qing,LI Chun,SHI Gao-quan.Nanoporous nitrogen-doped carbon modified graphene as electrocatalyst for oxygen reduction reaction[J].J Mater Chem,2012,22(25):12810-12816.
[39]LAI Lin-fei,POTTS J R,ZHAN Da,WANG Liang,POH CK,TANG Chun-hua,GONG Hao,SHEN Ze-xiang,LINJian-yi,RUOFF R S.Exploration of the active center structure of nitrogen-doped graphene-based catalysts for oxygen reduction reaction[J].Energy Environ Sci,2012,5:7936-7942.
[40]LIU Rui-li,WU Dong-qing,FENG Xin-liang,MLLEN K.Nitrogen-doped ordered mesoporous graphitic arrays with high electrocatalytic activity for oxygen reduction[J].Angew Chem Int Ed,2010,122:2619-2623.
[41]WIGGINS-CAMACHO J D,STEVENSON K J.Mechanistic discussion of the oxygen reduction reaction at nitrogen-doped carbon nanotubes[J].J Phys Chem C,2011,115(40):20002-20010.
[42]YANG Wen,FELLINGER T P,Antonietti M.Efficient metal-free oxygen reduction in alkaline medium on high-surface-area mesoporous nitrogen-doped carbons made from ionic liquids and nucleobases[J].J Am Chem Soc,2011,133:206-209.
[43]LI Jing-sha,FU Liang,LUAN Jing-yi,XIE Hua-lin,CHENGFang-yi,TANG You-gen,WANG Hai-yan.A strategy to achieve well-dispersed hollow nitrogen-doped carbon microspheres with trace iron for highly efficient oxygen reduction reaction in Al-air batteries[J].J Electrochem Soc,2018,165:A3766-A3772.
[44]LIU De-pei,FU Liang,HUANG Xiao-bing,LIU Kun,LIJing-sha,XIE Hua-lin,TIAN Jing,WANG Hai-yan,Tang You-gen.Influence of iron source type on the electrocatalytic activity towards oxygen reduction reaction in Fe-N/C for Al-air batteries[J].J Electrochem Soc,2018,165(9):F662-F670.
[45]SONG Jing-ya,REN Yu-rong,LI Jing-sha,HUANGXiao-bing,CHENG Fang-yi,TANG You-gen,Wang Hai-yan.Core-shell Co/CoNx@C nanoparticles enfolded by Co-Ndoped carbon nanosheets as a highly efficient electrocatalyst for oxygen reduction reaction[J].Carbon,2018,138:300-308.
[46]WANG Li-ping,FU Liang,LI Jing-sha,ZENG Xian-guang,XIE Hua-lin,HUANG Xiao-bing,WANG Hai-yan,TANGYou-gen.On an easy way to prepare highly efficient Fe/N-co-doped carbon nanotube/nanoparticle composite for oxygen reduction reaction in Al-air batteries[J].J Mater Sci,2018,53:10280-10291.
[47]LI Jing-sha,ZHOU Nan,SONG Jing-ya,FU Liang,YANJun,TANG You-gen,WANG Hai-yan.Cu-MOF derived Cu/Cu2O nanoparticles and CuNxCy species to boost oxygen reduction activity of ketjenblack carbon in Al-air battery[J].ACS Sus Chem Engin,2018,6:413-421.
[48]LI Fu-zhi,LI Jing-sha,FENG Qiu-ju,YAN Jun,TANGYou-gen,WANG Hai-yan.Significantly enhanced oxygen reduction activity of Cu/CuNxCy co-decorated ketjenblack catalyst for Al-air batteries[J].J Energy Chem,2018,27:419-425.
[2]PENG Hong-jian,XIAO Li-hong,CAO Yuan-ni,LUANXiang-feng.Synthesis and ionic conductivity of Li6La3BiSnO12 with cubic garnet-type structure via solid-state reaction[J].Journal of Central South University,2015,22(8):2883-2886.
[3]DAI Li-ming,XUE Yu-hua,QU Liang-ting,CHOI H J,BAEK J B.Metal-free catalysts for oxygen reduction reaction[J].Chem Rev,2015,115(11):4823-4892.
[4]ZHANG Jin-tao,LI Dai.Heteroatom-doped graphitic carbon catalysts for efficient electrocatalysis of oxygen reduction reaction[J].ACS Catal,2015,5(12):7244-7253.
[5]LI Jing-sha,CHEN Jia-jie,WAN Hao,XIAO Jin,TANGYou-gen,LIU Min,WANG Hai-yan.Boosting oxygen reduction activity of Fe-N-C by partial copper substitution to iron in Al-air batteries[J].Applied Catalysis B:Environmental,2019,242:209-217.
[6]CHENG Fang-yi,CHEN Jun.Metal-air batteries:From oxygen reduction electrochemistry to cathode catalysts[J].Chem Soc Rev,2012,41:2172-2192.
[7]WEI Da-cheng,LIU Yun-qi,WANG Yu,ZHANGHong-liang,HUANG Li-ping,YU Gui.Synthesis of Ndoped graphene by chemical vapor deposition and its electrical properties[J].Nano Lett,2009,9(5):1752-1758.
[8]SHENG Zhen-huan,SHAO Lin,CHEN Jing-jing,BAOWen-jing,WANG Feng-bin,XIA Xing-hua.Catalyst-free synthesis of nitrogen-doped graphene via thermal annealing graphite oxide with melamine and its excellent electrocatalysis[J].ACS Nano,2011,5(6):4350-4358.
[9]DENG Hai-jing,LI Qian,LIU Jing-jun,WANG Feng.Active sites for oxygen reduction reaction on nitrogen-doped carbon nanotubes derived from polyaniline[J].Carbon,2017,112:219-229.
[10]LI Jing-sha,ZHOU Zhi,LIU Kun,LI Fu-zhi,PENGZhi-guang,TANG You-gen,WANG Hai-yan.Co3O4/Co-N-Cmodified ketjenblack carbon as an advanced electrocatalyst for Al-air batteries[J].Journal of Power Sources,2019,343:30-38.
[11]WANG Zhong-li,XU Dan,XU Ji-jing,ZHANG Xin-bo.Oxygen electrocatalysts in metal-air batteries:From aqueous to nonaqueous electrolytes[J].Chem Soc Rev,2014,43:7746-7786.
[12]CAO Rui-guo,LEE J S,LIU Mei-lin,CHO J.Non-precious catalysts:Recent progress in non-precious catalysts for metal-air batteries[J].Adv Energy Mater,2012,2:816-829.
[13]DING Wei,LI Li,XIONG Kun,WANG Yao,LI Wei,NIEYao,CHEN Si-guo,QI Xue-qiang,WEI Zi-dong.Shape fixing via salt recrystallization:A morphology-controlled approach to convert nanostructured polymer to carbon nanomaterial as a highly active catalyst for oxygen reduction reaction[J].J Am Chem Soc,2015,137:5414-5420.
[14]LIN Hua,CHEN Kang-hua,SHUAI Yi,HE Xuan,GE Ke.Influence of CsNO3 as electrolyte additive on electrochemical property of lithium anode in rechargeable battery[J].Journal of Central South University,2018,25(4):719-728.
[15]LI Jing-sha,CHEN Jia-jie,WANG Hai-yan,REN Yu,LIUKun,TANG You-gen,LIU Min.Fe/N Co-doped carbon materials with controllable structure as highly efficient electrocatalysts for oxygen reduction reaction in Al-air batteries[J].Energy Storage Materials,2017,8:49-58.
[16]WANG Zhi-juan,CAO Xie-hong,PING Jian-feng,WANGYi-xian,LIN Ting-ting,HUANG Xiao,MA Qing-lang,WANG Fu-ke,HE Chao-bin,ZHANG Hua.Electrochemical doping of three-dimensional graphene networks used as efficient electrocatalysts for oxygen reduction reaction[J].Nanoscale,2015,7:9394-9398.
[17]WANG Qi-bin,MA Hong-bo,KONG Xian-guang,ZHANGYi-min.A distributed dynamic mesh model of a helical gear pair with tooth profile errors[J].Journal of Central South University,2018,25(2):287-303.
[18]ZHAI Yun-pu,DOU Yu-qian,ZHAO Dong-yuan,FULVIO PF,MAYES R T,DAI Shen.Carbon materials for chemical capacitive energy storage[J].Adv Mater,2011,23:4828-4850.
[19]YAN Jing,MENG Hui,XIE Fang-yan,YUAN Xiao-li,YUWen-dan,LIN Wo-rong,OUYANG Wen-peng,YUANDing-sheng.Metal-free nitrogen-doped hollow mesoporous graphene-analogous spheres as effective electrocatalyst for oxygen reduction reaction[J].J Power Source,2014,245:772-778.
[20]NIU Wen-han,LI Li-gui,LIU Xiao-jun,WANG Nan,LIU Ji,ZHOU Wei-jia,TANG Zheng-hua,CHEN Shao-wei.Mesoporous N-doped carbons prepared with thermally removable nanoparticle templates:An efficient electrocatalyst for oxygen reduction reaction[J].J Am Chem Soc,2015,137:5555-5562.
[21]NIE Yao,LI Li,WEI Zi-dong.Recent advancements in Pt and Pt-free catalysts for oxygen reduction reaction[J].Chem Soc Rev,2015,44:2168-2201.
[22]WU Qiu-mei,RUAN Jian-ming,ZHOU Zhong-cheng,SANG Shang-bin.Magneli phase titanium sub-oxide conductive ceramic TinO2n-1 as support for electrocatalyst toward oxygen reduction reaction with high activity and stability[J].Journal of Central South University,2015,22(4):1212-1219.
[23]MALDONADO S,STEVENSON K J.Influence of nitrogen doping on oxygen reduction electrocatalysis at carbon nanofiber electrodes[J].J Phys Chem B,2005,109:4707-4716.
[24]WANG Xiao-xia,ZOU Biao,DU Xin-xin,WANG Jian-nong.N-doped carbon nanocages with high catalytic activity and durability for oxygen reduction[J].J Mater Chem A,2015,3(23):12427-12435.
[25]LIU Ming-kai,SONG Yan-fang,HE Si-xin,PAN Ji-sheng,XIA Yong-yao,LIU Tian-xin.Nitrogen-doped graphene nanoribbons as efficient metal-free electrocatalysts for oxygen reduction[J].ACS Appl Mater Interfaces,2014,6(6):4214-4222.
[26]YU Ding-shan,ZHANG Qiang,DAI Li-ming.Highly efficient metal-free growth of nitrogen-doped single-walled carbon nanotubes on plasma-etched substrates for oxygen reduction[J].J Am Chem Soc,2010,132(43):15127-15129.
[27]JIANG Wen-jie,HU Jin-song,ZHANG Xing,JIANG Yan,YU Bin-bin,WEI Zi-dong.In-situ nitrogen-doped nano-porous carbon nanocables as an efficient metal-free catalyst for oxygen reduction reaction[J].J Mater Chem A,2014,2:10154-10160.
[28]CHEN Ping,XIAO Tian-yuan,QIAN Yu-hong,LIShan-shan,YU Shu-hong.A nitrogen-doped graphenecarbon nanotube nanocomposite with synergistically enhanced electrochemical activity[J].Adv Mater,2013,25:3192-3196.
[29]QU De-yang.Investigation of oxygen reduction on activated carbon electrodes in alkaline solution[J].Carbon,2007,45:1296-1301.
[30]WONG Wai-yin,DAUD W R W,MOHAMAD A B,KADHUM A A H,LOH K S,MAJLAN E H.Influence of nitrogen doping on carbon nanotubes towards the structure,composition and oxygen reduction reaction[J].Int JHydrogen Energy,2013,38:9421-9430.
[31]YANG Zhi,NIE Hua-gui,CHEN Xi-an,CHEN Xiao-hua,HUANG Shao-ming.Recent progress in doped carbon nanomaterials as effective cathode catalysts for fuel cell oxygen reduction reaction[J].J Power Sources,2013,236:238-249.
[32]LIU Sheng-wen,ZHANG Hai-min,ZHAO Qian,ZHANGXian,LIU Rong-rong,GE Xiao,WANG Guo-zhong,ZHAOHui-jun,CAI Wei-ping.Metal-organic framework derived nitrogen-doped porous carbon@graphene sandwich-like structured composites as bifunctional electrocatalysts for oxygen reduction and evolution reactions[J].Carbon,2016,106:74-83.
[33]CHEN Ping,WANG Li-kun,WANG Gan,GAO Min-gui,GE Jin,YUAN Wen-jin.Nitrogen-doped nanoporous carbon nanosheets derived from plant biomass:An efficient catalyst for oxygen reduction reaction[J].Energy Environ Sci,2014,7:4095-4103.
[34]QIAN Ying-dan,DU Pan,WU Ping,CAI Chen-xin,GERVASIO D F.Chemical nature of catalytic active sites for the oxygen reduction reaction on nitrogen-doped carbonsupported non-noble metal catalysts[J].J Phys Chem C,2016,120:9884-9896.
[35]YANG Xiao-ling,ZOU Wen-jian,SU Yun-he,ZHU Yi-hua,JIANG Hong-liang,SHEN Jian-hua.Activated nitrogendoped carbon nanofibers with hierarchical pore as efficient oxygen reduction reaction catalyst for microbial fuel cells[J].J Power Sources,2014,266:36-42.
[36]ZHANG Jun-li,CHEN Gao-li,ZHANG Qian,KANG Fei,YOU Bo.Self-assembly synthesis of N-doped carbon aerogels for supercapacitor and electrocatalytic oxygen reduction[J].ACS Appl Mater Interfaces,2015,7:12760-12786.
[37]LIANG Ji,DU Xin,GIBSON C,DU Xi-wen,QIAOShi-zhang.N-doped graphene natively grown on hierarchical ordered porous carbon for enhanced oxygen reduction[J].Adv Mater,2013,25:6226-6231.
[38]SUN Yi-qing,LI Chun,SHI Gao-quan.Nanoporous nitrogen-doped carbon modified graphene as electrocatalyst for oxygen reduction reaction[J].J Mater Chem,2012,22(25):12810-12816.
[39]LAI Lin-fei,POTTS J R,ZHAN Da,WANG Liang,POH CK,TANG Chun-hua,GONG Hao,SHEN Ze-xiang,LINJian-yi,RUOFF R S.Exploration of the active center structure of nitrogen-doped graphene-based catalysts for oxygen reduction reaction[J].Energy Environ Sci,2012,5:7936-7942.
[40]LIU Rui-li,WU Dong-qing,FENG Xin-liang,MLLEN K.Nitrogen-doped ordered mesoporous graphitic arrays with high electrocatalytic activity for oxygen reduction[J].Angew Chem Int Ed,2010,122:2619-2623.
[41]WIGGINS-CAMACHO J D,STEVENSON K J.Mechanistic discussion of the oxygen reduction reaction at nitrogen-doped carbon nanotubes[J].J Phys Chem C,2011,115(40):20002-20010.
[42]YANG Wen,FELLINGER T P,Antonietti M.Efficient metal-free oxygen reduction in alkaline medium on high-surface-area mesoporous nitrogen-doped carbons made from ionic liquids and nucleobases[J].J Am Chem Soc,2011,133:206-209.
[43]LI Jing-sha,FU Liang,LUAN Jing-yi,XIE Hua-lin,CHENGFang-yi,TANG You-gen,WANG Hai-yan.A strategy to achieve well-dispersed hollow nitrogen-doped carbon microspheres with trace iron for highly efficient oxygen reduction reaction in Al-air batteries[J].J Electrochem Soc,2018,165:A3766-A3772.
[44]LIU De-pei,FU Liang,HUANG Xiao-bing,LIU Kun,LIJing-sha,XIE Hua-lin,TIAN Jing,WANG Hai-yan,Tang You-gen.Influence of iron source type on the electrocatalytic activity towards oxygen reduction reaction in Fe-N/C for Al-air batteries[J].J Electrochem Soc,2018,165(9):F662-F670.
[45]SONG Jing-ya,REN Yu-rong,LI Jing-sha,HUANGXiao-bing,CHENG Fang-yi,TANG You-gen,Wang Hai-yan.Core-shell Co/CoNx@C nanoparticles enfolded by Co-Ndoped carbon nanosheets as a highly efficient electrocatalyst for oxygen reduction reaction[J].Carbon,2018,138:300-308.
[46]WANG Li-ping,FU Liang,LI Jing-sha,ZENG Xian-guang,XIE Hua-lin,HUANG Xiao-bing,WANG Hai-yan,TANGYou-gen.On an easy way to prepare highly efficient Fe/N-co-doped carbon nanotube/nanoparticle composite for oxygen reduction reaction in Al-air batteries[J].J Mater Sci,2018,53:10280-10291.
[47]LI Jing-sha,ZHOU Nan,SONG Jing-ya,FU Liang,YANJun,TANG You-gen,WANG Hai-yan.Cu-MOF derived Cu/Cu2O nanoparticles and CuNxCy species to boost oxygen reduction activity of ketjenblack carbon in Al-air battery[J].ACS Sus Chem Engin,2018,6:413-421.
[48]LI Fu-zhi,LI Jing-sha,FENG Qiu-ju,YAN Jun,TANGYou-gen,WANG Hai-yan.Significantly enhanced oxygen reduction activity of Cu/CuNxCy co-decorated ketjenblack catalyst for Al-air batteries[J].J Energy Chem,2018,27:419-425.