CN103183313B - 储氢复合材料与其形成方法 - Google Patents
储氢复合材料与其形成方法 Download PDFInfo
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- CN103183313B CN103183313B CN201110449945.8A CN201110449945A CN103183313B CN 103183313 B CN103183313 B CN 103183313B CN 201110449945 A CN201110449945 A CN 201110449945A CN 103183313 B CN103183313 B CN 103183313B
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 151
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 151
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 146
- 239000002131 composite material Substances 0.000 title claims abstract description 86
- 238000000034 method Methods 0.000 title claims abstract description 33
- 239000003054 catalyst Substances 0.000 claims abstract description 85
- 239000002245 particle Substances 0.000 claims abstract description 38
- 239000011232 storage material Substances 0.000 claims abstract description 35
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 15
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 15
- 230000015572 biosynthetic process Effects 0.000 claims description 12
- 229910012375 magnesium hydride Inorganic materials 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- 229910052709 silver Inorganic materials 0.000 claims description 6
- 229910052804 chromium Inorganic materials 0.000 claims description 5
- 239000011651 chromium Substances 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 239000010931 gold Substances 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 3
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 3
- 238000007772 electroless plating Methods 0.000 claims description 3
- 238000000713 high-energy ball milling Methods 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 229910000484 niobium oxide Inorganic materials 0.000 claims description 3
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical class [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical group O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract description 2
- 239000000843 powder Substances 0.000 description 21
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- 206010070834 Sensitisation Diseases 0.000 description 11
- 230000008313 sensitization Effects 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 238000003795 desorption Methods 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 239000000956 alloy Substances 0.000 description 8
- 238000000227 grinding Methods 0.000 description 8
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- 230000002829 reductive effect Effects 0.000 description 8
- 229910045601 alloy Inorganic materials 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 150000002431 hydrogen Chemical class 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
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- 238000006722 reduction reaction Methods 0.000 description 4
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- 238000003917 TEM image Methods 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
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- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
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- 150000001875 compounds Chemical class 0.000 description 2
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- 239000000706 filtrate Substances 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- 150000004678 hydrides Chemical class 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
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- 150000003839 salts Chemical class 0.000 description 2
- 230000001235 sensitizing effect Effects 0.000 description 2
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- -1 oxonium ion Chemical class 0.000 description 1
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- NHDHVHZZCFYRSB-UHFFFAOYSA-N pyriproxyfen Chemical compound C=1C=CC=NC=1OC(C)COC(C=C1)=CC=C1OC1=CC=CC=C1 NHDHVHZZCFYRSB-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/348—Electrochemical processes, e.g. electrochemical deposition or anodisation
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
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- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
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- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
- C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
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- C—CHEMISTRY; METALLURGY
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- C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
- C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
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- B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
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- B01J23/626—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead with tin
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/32—Hydrogen storage
Abstract
本发明提供一种储氢复合材料，包括：复合催化剂，包括催化剂粒子均匀披覆于载体的表面上；以及储氢材料；其中复合催化剂镶嵌于储氢材料的表面上。本发明还提供的一种储氢复合材料的形成方法，包括：将催化剂粒子均匀披覆于载体的表面上，以形成复合催化剂；以及将复合催化剂镶嵌至储氢材料的表面上，以形成储氢复合材料。
Description
技术领域
本发明是涉及储氢复合材料，及其形成方法。
背景技术
氢能为洁净的能源选择，其关键技术之一就是安全且低成本地储存与输送氢气。由于钢瓶高压氢气储运以及液态氢储运的方式存在着储氢密度低、安全性差、耗能、及成本高的问题，因此最具潜力的储氢方式乃是以金属或合金材料储存氢。储氢合金的原理是利用外界环境的温度、及/或压力改变，使合金吸收氢气而形成合金氢化物。当需要利用氢气时，再由合金氢化物释放氢气。储放氢气的过程如扩散、相变、及化合等阶段，均受到热效应与速度的限制而不易爆炸。
利用金属氢化物作为储氢媒介的优点为贮氢密度高、安全程度高、以及氢气释放纯度高。然而目前储氢合金的缺点在于高储氢量的合金如镁基合金，其吸放氢动力差，放氢操作温度仍过高(镁基合金一般需要300℃以上才能放氢)，大幅降低其实用性。综上所述，目前亟需可在较低的温度下吸放氢的储氢复合材料，以利未来氢能源的运用。
发明内容
本发明的目的在于提供一种可在较低的温度下吸放氢的储氢复合材料。
本发明一实施例提供一种储氢复合材料，包括：复合催化剂，包括催化剂粒子均匀披覆于载体的表面上；以及储氢材料；其中复合催化剂镶嵌于储氢材料的表面上。
本发明一实施例提供一种储氢复合材料的形成方法，包括：将催化剂粒子均匀披覆于载体的表面上，以形成复合催化剂；以及，将复合催化剂镶嵌至储氢材料的表面上，以形成储氢复合材料。
本发明的优点在于：本发明提供的储氢复合材料可在较低的温度下进行吸放氢，有利于氢能源的运用。
附图说明
图1是本发明一实施例中的复合催化剂的示意图；
图2是本发明一实施例中的储氢复合材料的示意图；
图3A是本发明实施例1中的复合催化剂α-Al2O3/Ag的X光衍射图谱；
图3B是本发明实施例1中的复合催化剂α-Al2O3/Ag的TEM影像；
图4是本发明的实施例1与比较例1的催化剂的吸氢/放氢量对时间的曲线图；
图5A是本发明实施例2中的复合催化剂α-Al2O3/Pd的X光衍射图谱；
图5B是本发明实施例2中的复合催化剂α-Al2O3/Pd的TEM影像；以及
图6是本发明的实施例2与比较例1的催化剂的吸氢/放氢量对时间的曲线图；
其中，主要元件符号说明：
11～催化剂粒子； 13～载体；
15～复合催化剂； 17～储氢材料；
19～储氢复合材料； 51～虚线框。
具体实施方式
本发明提供的储氢复合材料的形成方法如下。首先，将催化剂粒子11均匀披覆于载体13表面上，以形成复合催化剂15，如图1所示。在本发明一实施例中，催化剂粒子11可为银、钯、镍、铬、金、铂或铜组成的粒子，且催化剂粒子的尺寸介于10nm至100nm之间。若催化剂粒子11的尺寸过大，则催化活性较低。若催化剂粒子11的尺寸过小，则无法于合成的过程中稳定形成。在本发明一实施例中，载体13可为氧化铝、氧化钛、氧化铌、氧化钴或多孔碳材，且载体13的尺寸介于100nm至1μm之间。若载体13的尺寸过大，则披覆上去的金属催化剂粒子较粗而降低催化活性。若载体13的尺寸过小，则不容易将金属催化剂粒子披覆于载体表面。在本发明一实施例中，催化剂粒子11与载体13的重量比介于1∶100至1∶10之间。若催化剂粒子的比例过高，则催化剂颗粒不易均匀分散于载体表面而形成团聚、粗化。若催化剂粒子的比例过低，则催化活性较差。
将催化剂粒子11均匀披覆于载体13表面上，以形成复合催化剂15的方法可为无电镀法。举例来说，可先调配催化剂的盐类溶液作为化学镀液，接着将表面已进行敏化处理后的载体含浸于化学镀液中。之后加入还原剂使催化剂的盐类还原成金属催化剂并披覆于载体表面上。通过调整还原剂浓度、反应酸碱值、反应时间、以及反应温度，可控制披覆于载体表面的催化剂粒子的数量与尺寸，进而得到复合催化剂。敏化载体表面的敏化剂可为SnCl2。催化剂的盐类可为银、钯、镍、铬、金、铂或铜的化合物(可能为卤化物或络合物)。还原剂可为葡萄糖、次磷酸钠、或联氨。还原剂浓度介于0.05M至0.5M之间。若还原剂的浓度过高，则会造成金属催化剂粒子生成过快而导致其粒径粗化或颗粒团聚。若还原剂的浓度过低，则还原能力不足，会造成金属催化剂粒子的生成量过低。上述无电镀的反应时间介于5分钟至30分钟之间。若无电镀的反应时间过长，则生成的金属催化剂数量太多而容易造成颗粒团聚或粗化。若无电镀的反应时间过短，则生成的金属催化剂数量过少，而造成催化活性不佳。上述无电镀的反应温度介于15℃至75℃之间。若无电镀的反应温度过高，则导致金属催化剂生成速率过于剧烈而使生成量过高。若无电镀的反应温度过低，则造成反应速率过慢而不易生成催化剂粒子。在本发明一实施例中，可采用SnCl2的酸性溶液敏化氧化铝载体，使Sn2+离子吸附至载体表面。接着将敏化后的氧化铝载体加入由NaOH、NH4OH和AgNO3所形成的银氨水溶液中，使Sn2+氧化成Sn4+而Ag+还原成Ag。接着可再加入还原剂葡萄糖，则使更多的Ag+还原并披覆于氧化铝载体的表面上。以无电镀法使离子还原为纳米等级的金属粒子于载体表面上，可避免纳米催化剂于高温热处理下产生凝聚的问题。通过均匀分散于载体表面的方式可维持催化剂的高比表面积，进而增加其反应活性。
接着将复合催化剂15镶嵌至储氢材料17的表面上，以形成储氢复合材料19，如图2所示。储氢材料17可为镁、氢化镁、或镁基合金，如Mg1-xAx，A是Li、Ca、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Al、Y、Zr、Nb、Mo、In、Sn、Si、B、C、或Be，且0＜x≤0.3。在本发明一实施例中，复合催化剂15与储氢材料17的重量比介于1∶100至1∶10。若复合催化剂15的比例过高，则会占据整体材料系统中太多的重量而损失一些储氢量。若复合催化剂15的比例过低，则对于储放氢反应的催化活性不足。
将复合催化剂15镶嵌至储氢材料17的表面上，以形成储氢复合材料19的方法可为高能球磨法。举例来说，可将复合催化剂15与储氢材料17置于球磨罐中，于氩气下进行球磨制程以形成储氢复合材料19。球磨珠可为碳化钨或不锈钢，其直径介于1mm至5mm之间。若球磨珠的直径过小，则研磨能量较低而机械嵌合的效率较差。若球磨珠的直径过大，则容易在研磨珠与研磨罐之间的空隙产生死角，而使部分粉体无法充分被磨珠撞击而嵌合。球磨珠与复合催化剂15及储氢材料17的重量比介于10∶1至50∶1之间。若复合催化剂15及储氢材料17的比例过高，则研磨、嵌合的效率较差。若复合催化剂15及储氢材料17的比例过低，则容易造成研磨珠的磨耗。球磨方式可为行星式旋转、搅拌或振荡，且球磨制程历时0.25至1.5小时。若球磨制程历时过短，则机械嵌合的效果较差。若球磨制程历时过长，则可能造成催化剂金属从载体表面脱落，并与储氢材料产生合金化。利用机械力研磨的撞击方式，可将复合催化剂15直接镶嵌于储氢材料17的表面上，使催化剂可以发挥催化活性，让储氢材料17在较低的温度下有效地进行放氢。由于已先行将催化剂粒子11披覆于载体13表面，除了有助于均匀分散催化剂粒子11外，更可形成保护界面，降低催化剂粒子11在高能球磨中与储氢材料17合金化的可能性。此外，可进一步选用坚硬的纳米陶瓷粉体作为载体13，在球磨制程中可以充当助磨剂来撞击储氢合金，使储氢复合材料19产生晶界与缺陷而有利氢原子扩散。当复合催化剂15通过机械力的方式与储氢材料17的表面达成固相接合时，即可于两相的交界处提供氢原子扩散的路径，而有助于降低吸放氢的活化能能障。另一方面，镶嵌于储氢材料17表面的载体13的氧离子也有机会在表面形成微弱的氢键吸引力，来帮助储氢材料17储存的氢由内部释放出来。
为了让本发明的上述和其它目的、特征、和优点能更明显易懂，下文特举数实施例配合所附附图，作详细说明如下：
【实施例】
实施例1
首先将α-Al2O3粉体进行敏化处理(Sensitization Processing)。敏化剂的溶液的调配是取0.4g的SnCl2溶解于34ml的去离子水中，此时SnCl2会水解产生Sn(OH2)Cl白色沉淀，再滴入3ml的1N的HCl水溶液直至整体溶液澄清即可使用。而后将2g的α-Al2O3粉体(大明株式会社，TM-DAR)浸入上述调配好的敏化剂溶液中，于室温下搅拌5分钟，使Sn2+离子吸附在α-Al2O3粉体表面上，再利用离心方式去除滤液以得敏化的α-Al2O3粉体。将敏化后的α-Al2O3粉体浸入由30mL的0.9N的NaOH(l)、35mL的2N的NH4OH(l)以及30mL的0.3N的AgNO3(l)所形成的银氨水溶液中，并加入含有C6H12O6的还原剂溶液。这时粉体表面上的Sn2+离子会将银离子还原而吸附在α-Al2O3粉体表面，而含C6H12O6的溶液则强化银的还原反应，待反应5分钟的时间后，将粉体以离心方式收集，则得到复合催化剂α-Al2O3/Ag，其X光衍射图谱如图3A所示，且其TEM影像如图3B所示。
将上述复合催化剂α-Al2O3/Ag以机械力的方式，将其镶嵌于氢化镁的储氢材料上。首先将氢化镁与复合催化剂α-Al2O3/Ag以重量比92∶8的比例混合后，再将混合后的粉体与碳化钨磨球以球粉重量比32∶1的方式填入碳化钨研磨罐体中，并充填氩气。将研磨罐置入震荡球磨机(SPEXInc.，8000M)中以30分钟的时间进行球磨撞击，进而将复合催化剂α-Al2O3/Ag镶嵌于氢化镁的表面上，形成储氢复合材料。上述储氢复合材料于140℃下的吸氢/放氢量对时间的曲线如图4所示。上述吸放氢测试采用Sievert系统，在密闭且固定的容积内放入储氢材料，通过测量充放氢过程中气体压力的变化量来推知储放氢量。吸氢测试所采用的氢气压力为20atm，放氢测试所采用的氢气压力低于1atm。由于本实验的Sievert系统仅能量得吸氢曲线，故放氢的测量则是由材料于第一次吸氢后，让材料于＜1atm的压力环境下充分放氢一天，而后测量其第二次吸氢曲线来判断该材料的放氢量。
实施例2
首先将α-Al2O3粉体进行敏化处理。敏化剂溶液的调配是取5g的SnCl2溶解于7.5mL的37％的HCl(l)中，再将整体溶液以去离子水稀释至50mL后即可使用。而后将2g的α-Al2O3粉体(大明株式会社，TM-DAR)浸入上述调配好的敏化剂溶液中，于室温下搅拌5分钟，使Sn2+离子吸附在α-Al2O3粉体表面上，再利用离心方式去除滤液以得敏化的α-Al2O3粉体。将敏化后的α-Al2O3粉体浸入45mL的氯化钯水溶液中，该溶液的调配乃是取1g的PdCl2溶解于30ml的37％的HCl(l)中，再将整体溶液以去离子水稀释至100mL后即可使用。这时粉体表面上的Sn2+离子会将钯离子还原而吸附在α-Al2O3粉体表面，待反应5分钟的时间后，将粉体以离心方式收集，则得到复合催化剂α-Al2O3/Pd，其X光衍射图谱如图5A所示；其TEM分析影像则如图5B所示。在图5B中，虚线框51标示的深色部份为还原后的钯金属，而其余浅色的部份为α-Al2O3粉体。
将上述复合催化剂α-Al2O3/Pd以机械力的方式，将其镶嵌于氢化镁的储氢材料上。首先将氢化镁与复合催化剂α-Al2O3/Pd以重量百分比92∶8的比例混合后，再将混合后的粉体与碳化钨磨球以球粉重量比32∶1的方式填入碳化钨研磨罐体中，并充填氩气。将研磨罐置入震荡球磨机(SPEXInc.，8000M)中以30分钟的时间进行球磨撞击，进而将复合催化剂α-Al2O3/Pd镶嵌于氢化镁的表面上，形成储氢复合材料。上述储氢复合材料于140℃下的吸氢/放氢量对时间的曲线如图6所示。上述吸放氢测试采用Sievert系统，在密闭且固定的容积内放入储氢材料，通过测量充放氢过程中气体压力的变化量来推知储放氢量。吸氢测试所采用的氢气压力为20atm，放氢测试所采用的氢气压力低于1atm。放氢的测量是让材料于第一次吸氢后，使材料于＜1atm的压力环境下充分放氢一天，而后测量其第二次吸氢曲线来判断该材料的放氢量。
比较例1
取100重量份的氢化镁置于140℃下，其吸氢/放氢量对时间的曲线如图4及图6所示。由图4及图6可知，未添加催化剂的氢化镁在140℃下几乎无法放氢，而表面镶嵌有复合催化剂的氢化镁则维持稳定的放氢量。上述吸放氢测试采用Sievert系统，在密闭且固定的容积内放入储氢材料，通过测量充放氢过程中气体压力的变化量来推知储放氢量。吸氢测试所采用的氢气压力为20atm，放氢测试所采用的氢气压力低于1atm。放氢的测量是让材料于第一次吸氢后，使材料于＜1atm的压力环境下充分放氢一天，而后测量其第二次吸氢曲线来判断该材料的放氢量。
虽然本发明已以数个较佳实施例揭露如上，然其并非用以限定本发明，任何熟习此技艺者，在不脱离本发明的精神和范围内，当可作任意的更动与润饰，因此本发明的保护范围当视后附的权利要求书所界定的范围为准。
Claims (14)
1.一种储氢复合材料，包括：
一复合催化剂，包括一催化剂粒子均匀披覆于一载体的表面上；以及
一储氢材料；
其中所述复合催化剂镶嵌于所述储氢材料的表面上。
2.如权利要求1所述的储氢复合材料，其中所述催化剂粒子为银、钯、镍、铬、金、铂、或铜的粒子，且所述催化剂粒子的尺寸介于10nm至100nm之间。
3.如权利要求1所述的储氢复合材料，其中所述载体为氧化铝、氧化钛、氧化铌、氧化钴、或多孔碳材，且所述载体的尺寸介于100nm至1μm之间。
4.如权利要求1所述的储氢复合材料，其中所述复合催化剂中，所述催化剂粒子与所述载体的重量比介于1∶100至1∶10之间。
5.如权利要求1所述的储氢复合材料，其中所述储氢材料为镁、氢化镁、或镁基合金。
6.如权利要求1所述的储氢复合材料，其中所述复合催化剂与所述储氢材料的重量比介于1∶100至1∶10之间。
7.一种储氢复合材料的形成方法，包括：
将一催化剂粒子均匀披覆于一载体的表面上，以形成一复合催化剂；以及
将所述复合催化剂镶嵌至一储氢材料的表面上，以形成一储氢复合材料。
8.如权利要求7所述的储氢复合材料的形成方法，其中所述催化剂粒子为银、钯、镍、铬、金、铂、或铜的粒子，且该催化剂粒子的尺寸介于10nm至100nm之间。
9.如权利要求7所述的储氢复合材料的形成方法，其中所述复合催化剂中，所述催化剂粒子与所述载体的重量比介于1∶100至1∶10之间。
10.如权利要求7所述的储氢复合材料的形成方法，其中所述载体为氧化铝、氧化钛、氧化铌、或氧化钴，且所述载体的尺寸介于100nm至1μm之间。
11.如权利要求7所述的储氢复合材料的形成方法，其中所述复合催化剂与所述储氢材料的重量比介于1∶100至1∶10之间。
12.如权利要求7所述的储氢复合材料的形成方法，其中所述储氢材料为镁、氢化镁、或镁基合金。
13.如权利要求7所述的储氢复合材料的形成方法，其中所述将催化剂粒子均匀披覆于载体的表面上，以形成复合催化剂的步骤是无电镀法。
14.如权利要求7所述的储氢复合材料的形成方法，其中将所述复合催化剂镶嵌至储氢材料的表面上，以形成储氢复合材料的步骤是高能球磨法。
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1565958A (zh) * | 2003-06-10 | 2005-01-19 | 中国科学院大连化学物理研究所 | 含氢无机化合物水溶液制氢催化剂及制氢方法 |
| CN101289161A (zh) * | 2007-04-20 | 2008-10-22 | 中国科学院大连化学物理研究所 | 一种储氢材料的制备方法 |
| CN101671788A (zh) * | 2008-09-12 | 2010-03-17 | 财团法人工业技术研究院 | 镁基储氢材料纳米化方法 |
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| CN101289161A (zh) * | 2007-04-20 | 2008-10-22 | 中国科学院大连化学物理研究所 | 一种储氢材料的制备方法 |
| CN101671788A (zh) * | 2008-09-12 | 2010-03-17 | 财团法人工业技术研究院 | 镁基储氢材料纳米化方法 |
| CN101862686A (zh) * | 2009-04-17 | 2010-10-20 | 财团法人工业技术研究院 | 用于催化放氢反应的催化剂的制造方法 |
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| US20130161559A1 (en) | 2013-06-27 |
| TWI450764B (zh) | 2014-09-01 |
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