碳纸负载纳米结构钴、镍及其合金薄膜催化剂的研制及其催化硼氢化钠水解制氢研究
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摘要
采用溶剂热还原法,在外磁场的作用下,用碳纸作为基体材料,以不同物质的量配比的六水合氯化钴和六水合氯化镍为前驱物合成出负载于碳纸上的钴、镍及钴镍合金薄膜催化剂,并考察了所制备的催化剂对硼氢化钠水解制氢的催化性能.重点研究了改变合成条件对纳米薄膜催化性能的影响,同时研究了催化反应条件对水解制氢的影响.研究表明在EDTA做络合剂,钴做前驱物的条件下合成的催化剂的活性最高,在35℃条件下反应1 h,放氢量可达176 m L.较高的反应温度、较高的反应物浓度和较多的催化剂用量有助于提高催化性能.
In this paper,a magnetic-field assisted solvothermal approach was adopted to fabricate Co,Ni,and Co Ni alloy supported on carbon papers. Their catalytic performance in the hydrolysis of sodium borohydride was investigated. It was found that the Co film exhibited the highest catalytic activity when EDTA was used as complexing agent. The volume of H2 generated by hydrolysis of sodium borohydride could reach ca. 176 m Lat reaction time of 1 h and reaction temperature of 35 ℃. This study also found that higher reaction temperature,higher concentration of sodium borohydride and larger dosage of catalysts would promotethecatalyticperformance.
In this paper,a magnetic-field assisted solvothermal approach was adopted to fabricate Co,Ni,and Co Ni alloy supported on carbon papers. Their catalytic performance in the hydrolysis of sodium borohydride was investigated. It was found that the Co film exhibited the highest catalytic activity when EDTA was used as complexing agent. The volume of H2 generated by hydrolysis of sodium borohydride could reach ca. 176 m Lat reaction time of 1 h and reaction temperature of 35 ℃. This study also found that higher reaction temperature,higher concentration of sodium borohydride and larger dosage of catalysts would promotethecatalyticperformance.
引文
[1]PANWAR N L,KAUSHIK S C,KOTHARI S.Role of renewable energy sources in environmental protection:A revierw[J].Renew Sust Energ Rev,2011,15(3):1513-1524.
[2]ZHANG X,WEI Z H,GUO Q J,et al.Kinetics of sodium borohydride hydrolysis catalyzed via carbon nanosheets supported Co/Zr[J].J Power Source,2013,231(1):190-196.
[3]DUBEY P K,SINHA A S K,TALAPATRA S,et al.Hydrogen generation by water electrolysis using carbon nanotube anode[J].Int J Hydrogen Energy,2010,35(9):3945-3950.
[4]JIANG H L,XU Q.Catalytic hydrolysis of ammonia borane for chemical hydrogen storage[J].Catal Today,2011,170(1):56-63.
[5]杨兰,罗威,程功臻.氨硼烷水解制氢的研究进展[J].大学化学,2014,29(6):1-10.
[6]GHOSH T K,PRELAS M A.Energy Resources and Systems:Renewable Resources(Volume 2)[M].Columbia:Springer,2011:495-629.
[7]LU J,ZAHEDI A,YANG C S,et al.Building the hydrogen economy in China:Drivers,resources and technologies[J].Renew Sust Energ Rev,2013(23):543-556.
[8]王书明,蒋利军,刘晓鹏,等.硼氢化钠水解供氢的研究[J].电源设计与研究设计,2006,10(35):810-812.
[9]METIN?,?ZKAR S.Water soluble nickel(0)and cobalt(0)nanoclusters stabilized by poly(4-styrenesulfonic acid-co-maleic acid):Highly active,durable and cost effective catalysts in hydrogen generation from the hydrolysis of ammonia borane[J].Int J Hydrogen Energy,2011,36(2):1424-1432.
[10]JAMES JR C W,BRINKMAN K S,GRAY J R,et al.Fundamental environmental reactivity testing and analysis of the hydrogen storage material 2Li BH·Mg H4 2[J].Int J Hydrogen Energy,2014,39(3):1371-1381.
[11]ATTIA N F,LEE S M,KIM H J,et al.Nanoporous polypyrrole:preparation and hydrogen storage properties[J].Int J Energ Res,2014,38(4):466-476.
[12]OUMELLAL Y,COURTY M,ROUGIER A,et al.Electrochemical reactivity of magnesium hydride toward lithium:New synthesis route of nano-particles suitable for hydrogen storage[J].Int J Hydrogen Energy,2014,39(11):5852-5857.
[13]王凤娥.化学氢化物催化分解供氢技术[J].电源技术,2006,30(1):79-82.
[14]叶威,张华民,董民全.硼氢化钠水解给PEMFC供氢的研究[J].电源技术,2009,133(6):466-469.
[15]SIMAGINA V I,STOROZHENKO P A,NETSKINA O V,et al.Development of catalysts for hydrogen generation from hydride compounds[J].Catal Today,2008,138(3-4):253-259.
[16]HSUEH C L,CHEN C Y,KU J R,et al.Simple and fast fabrication of polymer template Ru composite as a catalyst for hydrogen generation from alkaline Na BH4 solution[J].J Power Source,2008,177(2):485-492.
[17]KRISHNAN P,YANG T H,LEE W Y,et al.Pt Ru-Li Co O2 an efficient catalyst for hydrogen generation from sodium borohydride solutions[J].J Power Source,2005,143(1-2):17-23.
[18]KOJIMA Y,SUZUKI K I,FUKUMOTO K,et al.Hydrogen generation using sodium borohydride solution and metal catalyst coated on metal oxide[J].Int J Hydrogen Energy,2002,27(10):1029-1034.
[19]王志远,周晶,高洪涛.硼氢化钠水解制氢研究进展[J].化工技术与开发,2009,38(4):15-19.
[20]JEONG S U,KIM R K,CHO E A,et al.A study on hydrogen generation from Na BH4 solution using the high-performance Co-B catalyst[J].J Power Source,2005(144):129-134.
[21]XU D Y,DAI P,LIU X M,etal.Carbon-supported cobalt catalyst for hydrogen generation from alkaline sodium borohydride solution[J].J Power Source,2008,182(2):616-620.
[22]KREEVOY M M,JACOBSON R W.The rate of decomposition of Na BH4 in basic aqueous solutions[J].Ventron Alembic,1979(15):2-3.
[23]李浩,张喜斌.络合剂/表面活性剂对溶剂热法制备钴纳米化的影响[J].无机盐工业,2010,42(6):30-35.
[2]ZHANG X,WEI Z H,GUO Q J,et al.Kinetics of sodium borohydride hydrolysis catalyzed via carbon nanosheets supported Co/Zr[J].J Power Source,2013,231(1):190-196.
[3]DUBEY P K,SINHA A S K,TALAPATRA S,et al.Hydrogen generation by water electrolysis using carbon nanotube anode[J].Int J Hydrogen Energy,2010,35(9):3945-3950.
[4]JIANG H L,XU Q.Catalytic hydrolysis of ammonia borane for chemical hydrogen storage[J].Catal Today,2011,170(1):56-63.
[5]杨兰,罗威,程功臻.氨硼烷水解制氢的研究进展[J].大学化学,2014,29(6):1-10.
[6]GHOSH T K,PRELAS M A.Energy Resources and Systems:Renewable Resources(Volume 2)[M].Columbia:Springer,2011:495-629.
[7]LU J,ZAHEDI A,YANG C S,et al.Building the hydrogen economy in China:Drivers,resources and technologies[J].Renew Sust Energ Rev,2013(23):543-556.
[8]王书明,蒋利军,刘晓鹏,等.硼氢化钠水解供氢的研究[J].电源设计与研究设计,2006,10(35):810-812.
[9]METIN?,?ZKAR S.Water soluble nickel(0)and cobalt(0)nanoclusters stabilized by poly(4-styrenesulfonic acid-co-maleic acid):Highly active,durable and cost effective catalysts in hydrogen generation from the hydrolysis of ammonia borane[J].Int J Hydrogen Energy,2011,36(2):1424-1432.
[10]JAMES JR C W,BRINKMAN K S,GRAY J R,et al.Fundamental environmental reactivity testing and analysis of the hydrogen storage material 2Li BH·Mg H4 2[J].Int J Hydrogen Energy,2014,39(3):1371-1381.
[11]ATTIA N F,LEE S M,KIM H J,et al.Nanoporous polypyrrole:preparation and hydrogen storage properties[J].Int J Energ Res,2014,38(4):466-476.
[12]OUMELLAL Y,COURTY M,ROUGIER A,et al.Electrochemical reactivity of magnesium hydride toward lithium:New synthesis route of nano-particles suitable for hydrogen storage[J].Int J Hydrogen Energy,2014,39(11):5852-5857.
[13]王凤娥.化学氢化物催化分解供氢技术[J].电源技术,2006,30(1):79-82.
[14]叶威,张华民,董民全.硼氢化钠水解给PEMFC供氢的研究[J].电源技术,2009,133(6):466-469.
[15]SIMAGINA V I,STOROZHENKO P A,NETSKINA O V,et al.Development of catalysts for hydrogen generation from hydride compounds[J].Catal Today,2008,138(3-4):253-259.
[16]HSUEH C L,CHEN C Y,KU J R,et al.Simple and fast fabrication of polymer template Ru composite as a catalyst for hydrogen generation from alkaline Na BH4 solution[J].J Power Source,2008,177(2):485-492.
[17]KRISHNAN P,YANG T H,LEE W Y,et al.Pt Ru-Li Co O2 an efficient catalyst for hydrogen generation from sodium borohydride solutions[J].J Power Source,2005,143(1-2):17-23.
[18]KOJIMA Y,SUZUKI K I,FUKUMOTO K,et al.Hydrogen generation using sodium borohydride solution and metal catalyst coated on metal oxide[J].Int J Hydrogen Energy,2002,27(10):1029-1034.
[19]王志远,周晶,高洪涛.硼氢化钠水解制氢研究进展[J].化工技术与开发,2009,38(4):15-19.
[20]JEONG S U,KIM R K,CHO E A,et al.A study on hydrogen generation from Na BH4 solution using the high-performance Co-B catalyst[J].J Power Source,2005(144):129-134.
[21]XU D Y,DAI P,LIU X M,etal.Carbon-supported cobalt catalyst for hydrogen generation from alkaline sodium borohydride solution[J].J Power Source,2008,182(2):616-620.
[22]KREEVOY M M,JACOBSON R W.The rate of decomposition of Na BH4 in basic aqueous solutions[J].Ventron Alembic,1979(15):2-3.
[23]李浩,张喜斌.络合剂/表面活性剂对溶剂热法制备钴纳米化的影响[J].无机盐工业,2010,42(6):30-35.
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