CN113275582A - 一种金属气凝胶电催化材料的制备方法 - Google Patents
一种金属气凝胶电催化材料的制备方法 Download PDFInfo
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- 239000000243 solution Substances 0.000 claims abstract description 35
- 239000000725 suspension Substances 0.000 claims abstract description 28
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 20
- 238000000352 supercritical drying Methods 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 13
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- 150000003839 salts Chemical class 0.000 claims abstract description 7
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- 238000006243 chemical reaction Methods 0.000 claims description 33
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 20
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- 239000001569 carbon dioxide Substances 0.000 claims description 10
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 229910021645 metal ion Inorganic materials 0.000 claims description 8
- MOOYVEVEDVVKGD-UHFFFAOYSA-N oxaldehydic acid;hydrate Chemical compound O.OC(=O)C=O MOOYVEVEDVVKGD-UHFFFAOYSA-N 0.000 claims description 7
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- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
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- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 5
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- 239000011591 potassium Substances 0.000 claims description 5
- 239000012279 sodium borohydride Substances 0.000 claims description 5
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 5
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 4
- ARPLKSKOWFTTTQ-UHFFFAOYSA-L cobalt(2+);dichloride;dihydrate Chemical compound O.O.Cl[Co]Cl ARPLKSKOWFTTTQ-UHFFFAOYSA-L 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 3
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 claims description 3
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 claims description 3
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 3
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 3
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 claims description 3
- FDFPDGIMPRFRJP-UHFFFAOYSA-K trichlorolanthanum;heptahydrate Chemical compound O.O.O.O.O.O.O.[Cl-].[Cl-].[Cl-].[La+3] FDFPDGIMPRFRJP-UHFFFAOYSA-K 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- RMIVHJQTAAVYAD-UHFFFAOYSA-K trichloroyttrium heptahydrate Chemical compound O.O.O.O.O.O.O.Cl[Y](Cl)Cl RMIVHJQTAAVYAD-UHFFFAOYSA-K 0.000 claims description 2
- 239000002923 metal particle Substances 0.000 abstract description 3
- 238000001338 self-assembly Methods 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 2
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- 229940001593 sodium carbonate Drugs 0.000 description 11
- 229910052760 oxygen Inorganic materials 0.000 description 6
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 229910002668 Pd-Cu Inorganic materials 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
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- 238000010349 cathodic reaction Methods 0.000 description 2
- MQRJBSHKWOFOGF-UHFFFAOYSA-L disodium;carbonate;hydrate Chemical compound O.[Na+].[Na+].[O-]C([O-])=O MQRJBSHKWOFOGF-UHFFFAOYSA-L 0.000 description 2
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
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- 150000002431 hydrogen Chemical class 0.000 description 1
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- 239000002082 metal nanoparticle Substances 0.000 description 1
- 239000002707 nanocrystalline material Substances 0.000 description 1
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- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
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- 238000006276 transfer reaction Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
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- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
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- C25B1/00—Electrolytic production of inorganic compounds or non-metals
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Abstract
本发明涉及一种金属气凝胶电催化材料的制备方法。将金属盐前驱体溶于水中得到金属盐溶液A;将还原剂、碳酸钠混合均匀得到溶液B;将上述溶液B加入到溶液A中得到悬浮液;放入烘箱内静置待其凝胶,凝胶后加入老化液进行溶剂置换;再将湿凝胶进行超临界干燥处理,得到金属气凝胶材料。通过金属粒子自组装技术,经超临界干燥过程最终得到高比表面积、高活性位点和电催化性能优异的气凝胶材料。本发明具有能耗低、工艺简单等特点,容易实现规模生产。
Description
技术领域
本发明属于气凝胶材料的制备工艺领域,尤其涉及采用金属粒子自组装结合超临界干燥工艺的一种金属气凝胶电催化材料的制备方法。
背景技术
近年来随着世界人口的快速增长和经济的快速发展,人们对于能源的需求日益加大。作为不可再生资源的化石燃料即将面对枯竭的危险,更严重的隐患是若持续使用化石燃料将加剧温室效应,造成严重的环境问题。为了发展绿色化学,创造更美好的未来。人们需要寻求清洁能源、可再生能源,而其中电催化的方法就可以较好的解决上述问题。电催化目前在能源领域研究较热的就是电催化产氢 (HER)/产氧(OER)及用于燃料电池领域的氧还原(ORR)反应。所谓电催化HER和OER就是采用电催化的技术电解水,使水分解成氢气和氧气,其中阴极反应对应于HER反应,阳极反应对应于OER反应。在氢氧燃料电池中,阳极氢气氧化(HOR)反应速率极快,而阴极反应的ORR是一个多电子转移过程,包括四部基元步骤和反应中间体,因此这一过程成为反应的速控步,导致反应缓慢。
传统HER和ORR催化剂主要是铂、钯等贵金属及其氧化物材料,而OER 常用的催化剂主要是一些过渡金属氧化物及其复合材料。例如,Yu等采用一步法制备了氮掺杂石墨烯负载钴氧化物纳米晶材料,该材料氧还原途径为典型四电子转移反应,半波电位甚至比商用的Pt/C电极大30mV(Journal of Electroanalytical Chemistry,2017.787:46-54.)。Wu等制备了三维氮掺杂石墨烯气凝胶负载Fe3O4纳米粒子作为ORR催化剂,该催化剂在碱性介质中有较高的起始电位和电流密度,氧还原反应为四电子途径,且显示出比铂碳催化剂更好的耐久性(Journal of the American Chemical Society,2012.134(22):9082-9085.)。但是金属及其氧化物普遍比表面积低,活性位点少,导致电催化效率较低,并且这些贵金属材料普遍造价昂贵、资源稀缺,进一步限制了其应用。
发明内容
本发明的目的是为了改进现有技术存在的不足而提供一种金属气凝胶电催化材料的制备方法。本发明制备的金属气凝胶不仅保留了金属的高催化活性,同时金属用量相对金属纳米颗粒减小,成本降低,同时该材料还保留了气凝胶材料的高比表面积,从而大大提高了催化的效率。该方法工艺简单,结构可控,制备出的气凝胶材料具备高比表、活性位点多和催化性能优异等特性,对实现气凝胶材料在工业化工领域的应用具备积极的生产意义。
本发明的技术方案为:一种金属气凝胶电催化材料的制备方法,其具体步骤如下:
(1)将金属盐前驱体溶于水中,在20~70℃下均匀搅拌,得到金属离子浓度为0.2mM~2mM金属盐溶液A;
(2)将还原剂、碳酸钠按照摩尔比1:(1~10)进行混合均匀,在20~70℃下均匀搅拌,得到溶液B;
(3)将上述溶液B加入到溶液A中,在20~70℃下均匀搅拌,得到悬浮液;其中溶液B中还原剂与溶液A中的金属盐按照摩尔比(5~20):1进行混合;
(4)将步骤(3)中得到的悬浮液,放入烘箱内静置待其凝胶,凝胶后加入老化液进行溶剂置换;
(5)将步骤(4)中得到的湿凝胶进行超临界干燥处理,得到金属气凝胶材料。
优选步骤(1)、步骤(2)和步骤(3)中的搅拌速度均为300~500rmp;步骤(1)中的搅拌时间为5~20min;步骤(2)中的搅拌时间为5~20min;步骤(3) 中搅拌时间为10~30min。
优选步骤(1)中所述的金属盐前驱体为氯化铜、二水合氯化钴、六水合氯化镍、氯铂酸、四氯合钯酸、氯化铑、氯金酸、硝酸银、氯化钌、氯化铱、七水合氯化钇、七水合氯化镧中的一种或两种;双金属合金体系中两种金属的摩尔比为1:(0.3~3)。
优选步骤(2)中所述的还原剂为一水乙醛酸、水合肼、硼氢化钠、硼氢化钾或过氧化氢中的一种或几种。
优选步骤(4)中所述的老化液为乙醇、丙酮、二甲醚、甲醇、异丙醇或乙腈中的一种或几种。
优选步骤(4)中烘箱温度40~70℃,溶剂置换3~9次,每次间隔时间8~24h。
优选步骤(5)中所述的干燥方法为乙醇或二氧化碳超临界干燥法:乙醇超临界干燥时,反应温度为250~270℃,高压反应釜内压强为5~20MPa,干燥时间为2~10h。二氧化碳超临界干燥时,以二氧化碳作为干燥介质,反应温度为 40~75℃,高压反应釜内压强为5~15MPa,干燥速率为3~8L/min,干燥时间为 9~18h。
有益效果:
本发明方法以及由该方法制备的一种用于电催化的金属气凝胶材料具有如下特点:
(1)工艺简单,能耗低。采用金属粒子自组装技术,并通过后续的超临界干燥工艺即可制备高比表面积、多活性位点、电催化性能优异的气凝胶材料。
(2)材料具备稳定性高和颗粒均匀等特点。
(3)本项目制备的金属气凝胶可以为完整块体材料,这对于实现气凝胶材料在电化学领域应用具备重要意义。
附图说明
图1是实例1中制得的Pd-Cu金属气凝胶材料的实物照片;
图2是实例1中所制得的Pd-Cu金属气凝胶材料在不同转速下的ORR过程LSV 曲线;
图3是实例2中La金属气凝胶材料SEM图。
具体实施方式
实例1
将0.65mg四氯合钯酸(0.2mM)和0.27mg氯化铜(0.2mM)溶于10ml水中,在60℃300rmp转速下搅拌5min得到金属盐溶液A;同时将0.0073g一水乙醛酸与0.0594g碳酸钠溶于20ml水中(一水乙醛酸按照与金属离子20:1的摩尔比加入,碳酸钠按照与一水乙醛酸摩尔比7:1加入),在60℃下300rmp转速下搅拌10min得到溶液B;将B溶液缓慢加入到A中,在60℃下300rmp转速下搅拌15min得到悬浮液C;将悬浮液放入50℃烘箱静置待其凝胶,凝胶后采用乙醇进行溶剂置换9次,每次间隔时间8h;然后将该湿凝胶进行二氧化碳超临界干燥,其中反应温度为40℃,高压反应釜内压强为8MPa,干燥速率为 5L/min,干燥时间为10h。从而得到Pd-Cu金属气凝胶材料。如图1所示,该材料外表为黑色块体。从图2中可以看出该材料在1600rpm下ORR反应的半波电位为0.86V,极限电流为6.35mA/cm2。
实例2
将6.31mg七水合氯化镧(1.7mM)溶于10ml水中,在50℃450rmp转速下搅拌12min得到金属盐溶液A;同时将0.0263g一水乙醛酸和1.531g碳酸钠溶于 20ml水中,(一水乙醛酸按照与金属离子17:1的摩尔比加入,碳酸钠按照与一水乙醛酸摩尔比5:1加入)在50℃下450rmp转速下搅拌12min得到溶液B;将B 溶液缓慢加入到A中,在50℃下450rmp转速下搅拌20min得到悬浮液C,将悬浮液放入55℃烘箱静置待其凝胶,凝胶后采用乙醇进行溶剂置换6次,每次间隔时间12h。然后进行乙醇超临界干燥时,反应温度为265℃,高压反应釜内压强为15MPa,干燥时间为8h。从而得到La金属气凝胶材料。如图3所示,该材料有着典型的气凝胶多孔结构,孔洞大小在几十纳米至几百纳米之间,颗粒与颗粒之间通过点接触方式相连,粒径大小在几十纳米左右。测得该材料在 1600rmp下OER反应10mA/cm2对应电位1.61v。
实例3
将4.19mg氯化铑(2mM)和1.66mg二水合氯化钴(1mM)溶于10ml水中,在20℃400rmp转速下搅拌15min得到金属盐溶液A;同时将0.0150g水合肼与 0.3180g碳酸钠溶于20ml水中(水合肼按照与金属离子10:1的摩尔比加入,碳酸钠按照与水合肼摩尔比10:1加入),在20℃下400rmp转速下搅拌15min得到溶液B;将B溶液缓慢加入到A中,在20℃下400rmp转速下搅拌10min得到悬浮液C;将悬浮液放入40℃烘箱静置待其凝胶,凝胶后采用甲醇进行溶剂置换5次,每次间隔时间16h;然后将该湿凝胶进行二氧化碳超临界干燥,其中反应温度为50℃,高压反应釜内压强为6MPa,干燥速率为3L/min,干燥时间为 14h,从而得到Rh2-Co金属气凝胶材料。测得该材料在1600rpm下ORR反应的半波电位为0.83V,极限电流为6.08mA/cm2。
实例4
将0.51mg硝酸银(0.3mM)和1.87mg氯化钌(0.9mM)溶于10ml水中,在70℃350rmp转速下搅拌20min得到金属盐溶液A;同时将0.0164g过氧化氢与0.0382g碳酸钠溶于20ml水中(过氧化氢按照与金属离子15:1的摩尔比加入,碳酸钠按照与过氧化氢摩尔比2:1加入),在70℃下350rmp转速下搅拌20min 得到溶液B;将B溶液缓慢加入到A中,在70℃下350rmp转速下搅拌20min 得到悬浮液C;将悬浮液放入70℃烘箱静置待其凝胶,凝胶后采用异丙醇进行溶剂置换3次,每次间隔时间24h;然后将该湿凝胶进行二氧化碳超临界干燥,其中反应温度为75℃,高压反应釜内压强为6MPa,干燥速率为3L/min,干燥时间为12h,从而得到Ag-Ru3金属气凝胶材料。测得该材料在1600rmp下OER反应10mA/cm2对应电位1.55v。
实例5
将1.65mg氯金酸(0.4mM)和3.80mg氯化铱(1.2mM)溶于10ml水中,在30℃500rmp转速下搅拌18min得到金属盐溶液A;同时将0.0061g硼氢化钾与0.0712g碳酸钠溶于20ml水中(硼氢化钾按照与金属离子7:1的摩尔比加入,碳酸钠按照与硼氢化钾摩尔比6:1加入),在30℃下500rmp转速下搅拌12min 得到溶液B;将B溶液缓慢加入到A中,在30℃下500rmp转速下搅拌25min 得到悬浮液C;将悬浮液放入65℃烘箱静置待其凝胶,凝胶后采用乙醇进行溶剂置换9次,每次间隔时间8h;然后将该湿凝胶进行乙醇超临界干燥时,反应温度为255℃,高压反应釜内压强为10MPa,干燥时间为4h。从而得到Au-Ir3金属气凝胶材料。测得该材料在1600rpm下ORR反应的半波电位为0.81V,极限电流为5.72mA/cm2。
实例6
将氯铂酸6.15mg(1.5mM)和六水合氯化镍1.19mg(0.5mM)溶于10ml水中,在40℃380rmp转速下搅拌10min得到金属盐溶液A;同时将0.0091硼氢化钠与0.0424g碳酸钠溶于20ml水中(硼氢化钠按照与金属离子5:1的摩尔比加入,碳酸钠按照与硼氢化钠摩尔比4:1加入),在40℃下380rmp转速下搅拌5min得到溶液B;将B溶液缓慢加入到A中,在40℃下380rmp转速下搅拌30min得到悬浮液C;将悬浮液放入60℃烘箱静置待其凝胶,凝胶后采用丙酮进行溶剂置换6次,每次间隔时间16h;然后将该湿凝胶进行二氧化碳超临界干燥,其中反应温度为65℃,高压反应釜内压强为13MPa,干燥速率为8L/min,干燥时间为17h,从而得到Pt3-Ni金属气凝胶材料。测得该材料在1600rpm下ORR反应的半波电位为0.89V,极限电流为6.93mA/cm2。
Claims (7)
1.一种金属气凝胶电催化材料的制备方法,其具体步骤如下:
(1)将金属盐前驱体溶于水中,在20~70℃下均匀搅拌,得到金属离子浓度为0.2mM~2mM金属盐溶液A;
(2)将还原剂、碳酸钠按照摩尔比1:(1~10)进行混合均匀,在20~70℃下均匀搅拌,得到溶液B;
(3)将上述溶液B加入到溶液A中,在20~70℃下均匀搅拌,得到悬浮液;其中溶液B中还原剂与溶液A中的金属盐按照摩尔比(5~20):1进行混合;
(4)将步骤(3)中得到的悬浮液,放入烘箱内静置待其凝胶,凝胶后加入老化液进行溶剂置换;
(5)将步骤(4)中得到的湿凝胶进行超临界干燥处理,得到金属气凝胶材料。
2.根据权利要求1所述的制备方法,其特征在于步骤(1)、步骤(2)和步骤(3)中的搅拌速度均为300~500rmp;步骤(1)中的搅拌时间为5~20min;步骤(2)中的搅拌时间为5~20min;步骤(3)中搅拌时间为10~30min。
3.根据权利要求1所述的制备方法,其特征在于步骤(1)中所述的金属盐前驱体为氯化铜、二水合氯化钴、六水合氯化镍、氯铂酸、四氯合钯酸、氯化铑、氯金酸、硝酸银、氯化钌、氯化铱、七水合氯化钇、七水合氯化镧中的一种或两种;双金属合金体系中两种金属的摩尔比为1:(0.3~3)。
4.根据权利要求1所述的制备方法,其特征在于步骤(2)中所述的还原剂为一水乙醛酸、水合肼、硼氢化钠、硼氢化钾或过氧化氢中的一种或几种。
5.根据权利要求1所述的制备方法,其特征在于步骤(4)中所述的老化液为乙醇、丙酮、二甲醚、甲醇、异丙醇或乙腈中的一种或几种。
6.根据权利要求1所述的制备方法,其特征在于步骤(4)中烘箱温度40~70℃,溶剂置换3~9次,每次间隔时间8~24h。
7.根据权利要求1所述的制备方法,其特征在于步骤(5)中所述的干燥方法为乙醇或二氧化碳超临界干燥法:乙醇超临界干燥时,反应温度为250~270℃,高压反应釜内压强为5~20MPa,干燥时间为2~10h。二氧化碳超临界干燥时,以二氧化碳作为干燥介质,反应温度为40~75℃,高压反应釜内压强为5~15MPa,干燥速率为3~8L/min,干燥时间为9~18h。
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