【作者】 马建丽；

【导师】 陈军；

【作者基本信息】 南开大学 ， 材料物理与化学， 2012， 博士

【摘要】 近年来，在高容量储氢材料的研究开发中，氨硼烷（AB）化合物的浸渍纳米填载技术已成为广大材料工作者的研究热点。与此同时，具有18电子结构的Mg基过渡金属氢化物也因其独特的结构备受人们的关注。本文综述了高容量储氢材料、介孔介质负载氨硼烷储氢材料以及具有18电子结构的Mg基过渡金属氢化物的研究进展。在此基础上，开展了介孔材料MCM-41及A-MCM-41负载AB的研究、介孔NiO制备及其负载AB的研究和镁基过渡金属氢化物储氢材料的制备及其表征研究。主要工作内容包括：（1）采用浸渍法，以四氢呋喃为溶剂，按照AB:MCM-41=1:2,1:1,2:1的比例制备负载材料AB/MCM-41，选用XRD、SAXRD、FTIR、氮气等温吸附、SEM、TEM等分析手段对负载材料进行表征。结果表明，AB:MCM-41=1:2的负载材料中的AB基本嵌入MCM-41中，呈现为了近程有序、远程无序的无定形相态；使AB:MCM-41=1:2负载材料在TG/DSC和TPD/MS的储氢性能测试中，免去了四方相向无定形态的转变，热解放氢温度降低了10°C，放氢过程中无氨气，但有硼嗪产生。（2）采用浸渍法，以含有4%Al₂O₃和96%SiO₂的A-MCM-41为主体，四氢呋喃为溶剂，按照AB:A-MCM-41=1:2,1:1,2:1的比例负载客体AB。XRD、SAXRD、FTIR、氮气等温吸附、SEM、TEM等分析手段用于表征负载材料AB/A-MCM-41。结果表明，AB:MCM-41=1:2的负载材料中的AB完全嵌入A-MCM-41中，呈现为了近程有序、远程无序的无定形相态；使AB:A-MCM-41=1:2负载材料在TG/DSC和TPD/MS储氢测试中，免去了四方相向无定形态的转变，热解放氢温度降低近10°C，放氢过程中无氨气和硼嗪产生。（3）以水热法合成NiO（1）：将蒸馏水:无水乙醇=1:1（体积比）的乙醇溶液75ml，六水氯化镍10mmol，尿素100mmol和十二烷基硫酸钠0.5g加入反应釜中，磁力搅拌混合后至110°C反应15h，再经抽滤、水洗、醇洗，80°C烘干12h，最后在电炉中以1°C/min的升温速率焙烧至300°C保温3h，制得黑色NiO（1）。产物与JCPDS No.65-6920相一致，为直径分布在50-70nm的实体近球形颗粒。将客体AB以AB:NiO（1）=1:1,1:2,1:4比例加载到NiO（1）中，以XRD、FTIR、SEM等表征负载材料AB/NiO（1），并以TG/DSC和TPD/MS对负载材料AB:NiO（1）=1:4的储氢性能进行测试。结果表明，AB:NiO（1）=1:4负载材料的热解放氢温度与原料AB相差仅3.6°C，但放氢过程中无氨气和硼嗪产生。（4）以均匀沉淀模板法合成NiO（2）：按照六水氯化镍:十二烷基硫酸钠:尿素:蒸馏水为20:40:600:1200的摩尔比混合，在40°C水域中搅拌0.5-1h，随后置入80°C烘箱均匀沉淀20h，再经抽滤、水洗、醇洗，60°C烘干12h，最后在电炉中以1°C/min的升温速率焙烧至300°C并保温3h，制得NiO（2）粉末与JCPDS No.65-2091相一致，为由薄片卷曲而成的球型颗粒。将客体AB以AB:NiO（2）=1:1,1:2,1:4比例加载到NiO（2）中，以XRD、FTIR、SEM等表征负载材料AB/NiO（2），并以TG/DSC和TPD/MS对负载材料AB:NiO（2）=1:4的储氢性能进行测试。结果表明，AB:NiO（2）=1:4负载材料的热解放氢温度与原料AB相差10.2°C，放氢过程中无氨气和硼嗪产生。（5）以回流非模板法合成NiO（3）:按照六水氯化镍：六次甲基四胺：蒸馏水为20:200:350000的摩尔比混合，在140°C加热回流2.5h，再经抽滤、水洗、醇洗，60-70°C烘干12h，最后在电炉中以1°C/min的升温速率焙烧至300°C并保温3h，得到NiO（3）粉末与JCPDS No.89-7130相一致，为由薄片交织而成的网状体。以AB:NiO（3）=1:1,1:2,1:4比例负载AB，以XRD、FTIR、SEM等表征负载材料AB/NiO（3），并以TG/DSC和TPD/MS对负载材料AB:NiO（3）=1:4的储氢性能进行测试。结果表明，AB:NiO（3）=1:4负载材料的热解放氢温度与原料AB相差2.2°C，放氢过程中无氨气和硼嗪产生。（6）采用反应球磨法制备镁基过渡金属氢化物。以纳米Fe:微米MgH₂=1:3摩尔比混合并球磨55h，制得与JCPDS No.38-843相一致的Mg₂FeH₆相，产物中含有未反应的Fe和MgH₂。相类似，以纳米Co:微米MgH₂=2:5摩尔比混合并球磨12h，完全反应制得与JCPDS No.78-215相一致的纳米晶Mg₂COH₅相，经HRTEM的FFT转换分析，Mg₂CoH₅的（101）晶面间距为0.366nm。更多还原

【Abstract】 Recently, hydrogen storage materials of ammonia borane compound with highgravimetric hydrogen capacity have become the research focus by nano-loadingtechnology. In the meantime, Mg-based transition metal hydrides with18electronicstructure have also attracted much attention because of their uniquestructure. Thisarticle reviews the research progress of high-capacity hydrogen storage materials, themesoporous medium loading of ammonia borane hydrogen storage materials, as wellas Mg-based transition metal hydrides with18electronic structure. On this basis, thepaper expands the research of the loading of AB in mesoporous material MCM-41and A-MCM-41, the preparation of mesoporous NiO and its loading of AB, and thepreparation and characterization of magnesium-based transition metal hydrides. Themain contents include:（1）AB/MCM-41samples were synthesized by an impregnation method intetrahydrofuran （THF） at room temperature. The ratios of AB: MCM-41are fixed at1:2,1:1, and2:1. The as-prepared samples have been characterized by XRD,SAXRD, FTIR, BET, SEM, and TEM. The results show that most AB was loadedinto the MCM-41with short-range ordered and long-range disorderd phase. TheTG/DSC and TPD/MS investigations show that the AB: MCM-41=1:2sampledecreased the dehydrogenation temperature of AB for10°C without NH3releasingbut with borazine.（2）AB: A-MCM-41samples were synthesized by an impregnation method intetrahydrofuran （THF） at room temperature. The ratios of AB: A-MCM-41are fixedat1:2,1:1, and2:1. The as-prepared samples have been characterized by XRD,SAXRD, FTIR, BET, SEM, and TEM. The results show that AB was loaded into theA-MCM-41with short-range ordered and long-range disorderd phase. The TG/DSCand TPD/MS investigations show that the AB: A-MCM-41=1:2sample decreasedthe dehydrogenation temperature of AB for10°C without any borazine or NH3releasing. （3）NiO（1） was synthesized by a hydrothermal method at the conditions andprocesses of distilled water: ethanol=1:1（volume ratio） with ethanol solution75ml,six nickel chloride10mmol, urea100mmol, and sodium dodecyl sulfate0.5g addedto the reactionkettle, stirred the mixture and heated to110°C for15h, then filtered,washed with water and alcohol, drying at80°C for12h, and finally calcined in thefurnace to300°C with a heating rate of1°C/min for3h. The as-prepared blackNiO（1） is nearly spherical particles with the diameter of50-70nm. AB was loadedinto NiO（1） with the AB:NiO（1） ratio of1:1,1:2, and1:4. The as-prepared sampleshave been characterized by XRD, FTIR, SEM, TG/DSC and TPD/MS. The resultsshow that the sample with the ratio of AB:NiO（1）=1:4suppressed the releasing ofborazine and NH3, and decreased the dehydrogenation temperature for3.6°C.（4）NiO（2） was synthesized by a homogeneous precipitation-template methodin the following conditions: the molar ratio of nickel chloride: sodium dodecylsulfate: urea: distilled water is20:40:600:1200, the mixture stirred in water bath for40°C for0.5-1h, placed in an oven for drying at80°C for20h, filtered, washed withwater and alcohol, dried at80°C for12h, and finally calcined in the furnace to300°C with a heating rate of1°C/min for3h. The obtained NiO（2） powder is consistentwith the JCPDS No.65-2091. NiO（2） is flasks which are consisting of sphericalparticles. AB was loaded into NiO（2） with the AB:NiO（2） ratios of1:1,1:2, and1:4.The as-prepared samples have been characterized by XRD, FTIR, SEM, TG/DSCand TPD/MS. The results show that the AB:NiO（2）=1:4sample suppressed thereleasing of borazine and NH3, and decreased the dehydrogenation temperature for10.2°C.（5）NiO（3） was synthesized by a reflux method in the conditions of the molarratio of nickel chloride: hexamethylenetetramine: distilled water is20:200:350000.The mixture was refluxed at140°C for2.5h, filtered, washed with water and alcohol,dried at80°C for20h, and finally calcined in the furnace to300°C with a heatingrate of1°C/min for3h. The obtained NiO（3） powder powder is consistent with theJCPDS No.89-7130. NiO（3） is consisting of flasks. AB was loaded into NiO（3） withthe AB:NiO（3） ratio of1:1,1:2, and1:4. The as-prepared samples have beencharacterized by XRD, FTIR, SEM, TG/DSC and TPD/MS. The results indicate that the sample with the ratio of AB:NiO（3）=1:4suppressed the releasing of borazine andNH3, and decreased the dehydrogenation temperature for3.2°C.（6）Mg-based transition metal hydrides were synthesized by ball-millingmethod. The molar ratio of nano-Fe: micro-MgH₂is1:3. The mixture was milled for55h. The obtained Mg₂FeH₆phase is consistent with the JCPDS No.38-843. Theproduct contains unreacted Fe and MgH₂. Similarly, the molar ratio of nano-Co:micro-MgH₂is2:5. The obtained Mg₂CoH₅phase is consistent with the JCPDS No.78-215. The conversion analysis by HRTEM and FFT shows that the crystal planespacing of Mg₂CoH₅（101） is0.366nm.更多还原