CN107088415B - 一种铂合金纳米粉末催化剂的制备方法 - Google Patents
一种铂合金纳米粉末催化剂的制备方法 Download PDFInfo
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- 229910001260 Pt alloy Inorganic materials 0.000 title claims abstract description 26
- 239000003054 catalyst Substances 0.000 title claims abstract description 22
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- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- -1 transition metal salt Chemical class 0.000 claims abstract description 61
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 26
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 18
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 17
- 239000011259 mixed solution Substances 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 12
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- 229910045601 alloy Inorganic materials 0.000 claims abstract description 11
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- 238000000137 annealing Methods 0.000 claims abstract description 8
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- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 3
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- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 3
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- 239000001257 hydrogen Substances 0.000 claims description 24
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- 235000013024 sodium fluoride Nutrition 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 4
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- 229910021645 metal ion Inorganic materials 0.000 claims description 4
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- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- 150000001242 acetic acid derivatives Chemical class 0.000 claims description 2
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- 150000002823 nitrates Chemical class 0.000 claims description 2
- 150000003891 oxalate salts Chemical class 0.000 claims description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 2
- 235000011151 potassium sulphates Nutrition 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 abstract description 18
- 229910000510 noble metal Chemical class 0.000 abstract description 10
- 150000003839 salts Chemical class 0.000 abstract description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 abstract description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 abstract description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 abstract description 2
- 229910002651 NO3 Inorganic materials 0.000 abstract description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 abstract description 2
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 21
- 238000000034 method Methods 0.000 description 21
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 16
- 230000009467 reduction Effects 0.000 description 14
- 239000013078 crystal Substances 0.000 description 10
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- 229910002844 PtNi Inorganic materials 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
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- 238000006243 chemical reaction Methods 0.000 description 3
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
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- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- CMHKGULXIWIGBU-UHFFFAOYSA-N [Fe].[Pt] Chemical compound [Fe].[Pt] CMHKGULXIWIGBU-UHFFFAOYSA-N 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
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- 239000010419 fine particle Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- PCLURTMBFDTLSK-UHFFFAOYSA-N nickel platinum Chemical compound [Ni].[Pt] PCLURTMBFDTLSK-UHFFFAOYSA-N 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
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- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8906—Iron and noble metals
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Abstract
一种铂合金纳米粉末催化剂的制备方法,包括如下步骤:1)配制氯铂酸与至少一种过渡金属盐或贵金属盐以及至少一种碱金属盐或碱土金属盐的混合溶液;2)将步骤1)所获得的混合溶液通过喷雾干燥或冷冻干燥获得干燥粉末样品;3)、将步骤2)获得的粉末样品在还原气氛中低于碱金属盐或碱土金属盐熔点以下温度退火,使铂和过渡金属合金化得到铂合金;4)用水溶解步骤3获得产物中的碱金属盐或碱土金属盐,洗涤、干燥后得到铂合金纳米粉末催化剂;混合溶液包括过渡金属盐或贵金属盐、碱金属盐或碱土金属盐、溶剂;所述过渡金属盐包括铁、钴、镍、铜、钼以及钨的硝酸盐、氯化盐、碳酸盐、醋酸盐、草酸盐。
Description
技术领域
本发明涉及一种铂合金纳米粉末催化剂的制备方法,属于纳米材料合成和电化学领域。
背景技术
铂基纳米催化剂对反应物和产物具有合适的吸/脱附能力,在环境催化、燃料电池、精细化工等多相催化反应中扮演着极为重要的角色。例如,净化汽车尾气的3效催化剂的活性组分就是铂族元素,铂基纳米结构电极在燃料电池电催化反应中表现出优异的性能。由于铂金属储量稀少且价格昂贵,降低其使用量但同时保持甚至提高其催化性能及其循环利用率成为研究的焦点。制备铂基合金颗粒粒径更小、厚度更薄的纳米催化剂,可以增大其比表面积从而提高贵金属的质量活性与使用效率。
目前,有关铂合金催化剂的制备方法颇多,低温有机液相还原法、微乳液法、气相沉积法、电化学沉积法以及侵占-高温还原法。相比之下,有关高温还原法制备铂基合金催化剂有其独特的优势。由于能在高温退火,容易控制获得所需合金的晶体结构,该方法所需要的设备以及原材料比较普遍,且过程简单容易控制,有希望规模化生产降低生产成本。但目前高温还原法制备的铂合金催化剂颗粒尺寸大小以及1致性、晶体结构的可控性等方面的问题仍比较突出,很大程度上影响了铂合金催化剂的催化性能。
发明内容
针对现有技术的问题,本发明的目的在于,提供一种铂合金催化剂的制备方法。利用铂合金与碱金属或碱土金属盐界面不润湿、不反应的性质,通过混合溶液快速干燥析出的方法将铂合金粉末前躯体用碱金属盐或碱土金属盐粉末隔开,在高温退火中在获得所需晶体结构的同时,保持铂合金颗粒不长大的特点制备铂合金纳米颗粒粉末。
本发明是通过以下技术方案实现的:一种铂合金催化剂的制备方法,所述方法包括如下步骤:
步骤1、配制氯铂酸与至少1种过渡金属盐或贵金属盐以及至少1种碱金属盐或碱土金属盐的混合溶液;
步骤2、将步骤1所获得的混合溶液通过喷雾干燥或冷冻干燥获得干燥粉末样品;
步骤3、将步骤2获得的粉末样品在还原气氛中低于碱金属盐或碱土金属盐熔点以下温度退火,使铂和过渡金属合金化;
步骤4、用水溶解掉步骤3获得产物中的碱金属盐或碱土金属盐,洗涤、干燥后得到铂合金纳米粉末催化剂。
优选地,步骤1中所述过渡金属盐或贵金属盐以及碱金属盐或碱土金属盐的混合溶液包括过渡金属盐或贵金属盐、碱金属盐或碱土金属盐、溶剂;
优选地,所述过渡金属盐包括铁、钴、镍、铜、钼以及钨的硝酸盐、氯化盐、碳酸盐、醋酸盐、草酸盐;
优选地,所述贵金属盐包括铑、钯、铱、钌、金、银的硝酸盐、氯化盐、碳酸盐、醋酸盐、草酸盐;
优选地,所述碱金属盐或碱土金属盐包括:氯化钠、氯化钾、氯化钙、氯化钡、氟化钠、氟化钾、硫酸钠、硫酸钾;
优选地,所述溶剂为水、乙醇、异丙醇、甲醇、乙醚、丙酮、乙2醇中的1种或几种溶剂。
优选地,步骤1中所述氯铂酸中铂离子与过渡金属盐或贵金属盐中金属离子的摩尔比为1:(0.3~3);氯铂酸中铂离子加过渡金属盐或贵金属盐中金属离子之和与碱金属盐或碱土金属盐中碱金属离子或碱土金属离子的摩尔比为1:(1~300);溶质(氯铂酸加过渡金属盐或贵金属盐和碱金属盐或碱土金属盐)与溶剂的摩尔比为1:(1~100);
优选地,步骤2中所述干燥的方法包括喷雾干燥或冷冻干燥;
优选地,步骤3中所述合金化退火温度低于所用碱金属盐或碱土金属盐的熔点温度,最佳的温度为低于熔点以下50℃~100℃;
优选地,步骤3中所述还原气氛为H2、H2/N2混合气体、H2/Ar混合气体;
优选地,步骤四中所述溶解的溶剂采用去离子水或蒸馏水;洗涤的方式包括超声清洗和离心分离的方式、滤膜透析方式或过滤方式;干燥方式包括真空干燥、自然干燥。
有益效果:本发明利用铂合金与惰性的碱金属或碱土金属盐界面不润湿、不反应的性质,通过混合溶液快速干燥析出的方法将铂合金粉末前躯体用碱金属盐或碱土金属盐粉末隔开,在高温退火中在获得所需晶体结构的同时,保持铂合金颗粒不长大的特点制备铂合金纳米颗粒粉末。用该方法制备的铂合金纳米颗粒成分均匀、颗粒尺寸细小。该方法工艺简单,制造成本低,生产效率高,是一种简单易行、可规模化大量生产铂合金纳米粉末的制备方法。这类铂合金纳米粉末催化剂具有高的电催化性能。
附图说明
图1为800℃氢气还原5分钟PtFe纳米颗粒的TEM照片(图1中A、B、C是三个不同的尺度)和PtFe纳米颗粒在有机液体形成的胶体溶液(图1中D);
图2在不同温度和时间氢气还原后PtFe纳米颗粒的XRD结果;
图3不同条件制备的PtFe/导电炭黑以及商用Pt/导电炭黑电极在0.5M硫酸溶液中的析氢性能;
图4 800℃氢气还原5分钟的PtFe/导电炭黑电极以及商用Pt/导电炭黑电极在0.5M硫酸溶液中的析氢循环特性曲线。
具体实施方式
下面结合具体实例对本发明进行详细说明。
实施例1
PtFe纳米催化剂的制备方法,所述方法包括如下步骤:
步骤1,取2克氯铂酸、1.56克硝酸铁和30克氟化钠溶于1000ml的水中,通过超声得到均匀的混合溶液。铂与铁原子的摩尔比为1:1,铂与氟化钠的摩尔比为1:180。
步骤2,将混合好的混合溶液通过喷雾干燥方法获得干燥混合粉末样品;喷雾干燥所设空气温度为280℃,喷雾速度1升溶液/小时。
步骤3,将步骤2获得的干燥混合粉末样品在氢气中还原5分钟,还原温度为800℃。
步骤4,采用超声方法溶解步骤3获得产物中的氟化钠,洗涤、离心、干燥后得到铂铁合金纳米粉末。
效果:实施例1制备的PtFe纳米颗粒的TEM照片如图1所示,PtFe合金纳米颗粒尺寸分布在3nm-8nm范围。在800℃温度氢气还原后的XRD结果如图2所示,PtFe纳米颗粒的晶体结构为四方相L10有序结构。为了测试PtFe纳米颗粒的析氢催化活性,将制备获得PtFe纳米颗粒与购置的导电炭黑按重量比1:2配比制得PtFe/导电炭黑混合体,在0.5M硫酸溶液中测试析氢性能,其结果如图3所示,PtFe/导电炭黑析氢催化活性能高于商用的Pt/导电炭黑催化剂。PtFe/导电炭黑的析氢催化活性在0.5M硫酸溶液中的耐久性测试结果如图4所示,在1万次循环后变化很小,循环耐久性高于商用Pt/导电炭黑催化剂。
实施例2
本实例为实施例1的变化例。其他实施条件同实施例1,变化之处在于:步骤3中的氢气还原温度为800℃,还原时间为200分钟。
效果:PtFe合金纳米颗粒尺寸3nm—10nm。PtFe纳米颗粒的晶体结构为四方相L10有序结构(见图2)。PtFe/导电炭黑混合体在0.1M硫酸溶液中测试析氢性能略低于商用的Pt/导电炭黑催化剂(见图3)。
实施例3
本实例为实施例1的变化例。其他实施条件同实施例1,变化之处在于:步骤3中的氢气还原温度为900℃。
效果:PtFe合金纳米颗粒尺寸6nm—10nm。PtFe纳米颗粒的晶体结构为四方相L10有序结构(见图2)。PtFe/导电炭黑混合体在0.1M硫酸溶液中测试析氢性能接近商用的Pt/导电炭黑催化剂(见图3)。
实施例4
本实例为实施例1的变化例。其他实施条件同实施例1,变化之处在于:步骤1中取10克氟化钠,铂与氟化钠的摩尔比为1:60。
效果:PtFe合金纳米颗粒尺寸在15-25nm范围。在800℃温度氢气还原后PtFe纳米颗粒的晶体结构为L10有序结构。
以上实施例中采用氟化钾能够得到同样的结果。
实施例5
本实例为实施例1的变化例。其他实施条件同实施例1,变化之处在于:步骤1中取4.68克硝酸铁,铂与铁原子的摩尔比为3:1。
效果:Pt3Fe合金纳米颗粒尺寸类似于实施例1。Pt3Fe纳米颗粒的晶体结构为Pt3Fe有序结构。Pt3Fe/导电炭黑混合体,在0.5M硫酸溶液中测试析氢性能,Pt3Fe/导电炭黑析氢催化活性能接近商用的Pt/导电炭黑催化剂。
实施例6
PtNi纳米催化剂的制备方法,所述方法包括如下步骤:
步骤1,取2克氯铂酸、1.12克硝酸镍和32克氯化钠溶于200ml的水中,通过超生或机械搅拌得到均匀的混合溶液。铂与镍原子的摩尔比为1:1,铂与氯化钠的摩尔比为1:140。
步骤2,将混合好的混合溶液通过喷雾干燥方法获得干燥混合粉末样品;喷雾干燥所设空气温度为260℃,喷雾速度1升溶液/小时。
步骤3,将步骤2获得的干燥混合粉末样品在氢气中还原20分钟,还原温度为750℃。
步骤4,采用超生方法溶解步骤3获得产物中的氯化钠,洗涤、离心、干燥后得到铂镍合金纳米粉末。
采用氯化钾能够得到同样的结果。
效果:实施例4制备的PtNi纳米颗粒的尺寸分布在5nm-10nm范围。在750℃温度氢气还原后的晶体结构为L10有序结构。为了测试PtNi纳米颗粒的析氢催化活性,将制备获得PtNi纳米颗粒与购置的导电炭黑按重量比1:2配比制得PtNi/导电炭黑混合体,在0.5M硫酸溶液中测试析氢性能,其结果表明PtNi/导电炭黑析氢催化活性能高于商用的Pt/导电炭黑催化剂。
以上所述仅为本发明的优选实施例,并不用于限制本发明,对于本领域的技术人员来说,凡在本发明的精神和原则之内,所作的任何修改、改进等,均应包括在本发明的保护范围之内。
Claims (1)
1.一种铂合金纳米粉末析氢催化剂的制备方法,其特征在于,包括如下步骤:
步骤1、配制氯铂酸与至少一种过渡金属盐以及至少一种碱金属盐的混合溶液;
步骤2、将步骤1所获得的混合溶液通过喷雾干燥或冷冻干燥获得干燥粉末样品;
步骤3、将步骤2获得的粉末样品在还原气氛中低于碱金属盐熔点以下温度退火,使铂和过渡金属合金化得到铂合金;
步骤4、用水溶解步骤3获得产物中的碱金属盐,洗涤、离心、干燥后得到铂合金纳米粉末催化剂;
所述过渡金属盐包括铁、钴、镍的硝酸盐、氯化盐、碳酸盐、醋酸盐、草酸盐;
所述碱金属盐包括:氯化钠、氯化钾、氟化钠、氟化钾、硫酸钠、硫酸钾;
构成溶液的溶剂为水、乙醇、异丙醇、甲醇、乙醚、丙酮、乙二醇中的一种或几种溶剂;
步骤1中所述氯铂酸中铂离子与过渡金属盐中金属离子的摩尔比为1:0.3-3;氯铂酸中铂离子加过渡金属盐中金属离子之和与碱金属盐中碱金属离子摩尔比为1:1-300;溶质即氯铂酸加过渡金属盐和碱金属盐之和与溶剂的摩尔比为1:1-100;
步骤3中所述合金化退火温度为低于所用碱金属盐熔点温度,温度为低于碱金属盐熔点以下50oC-100oC;步骤3中所述还原气氛为H2、H2/N2混合气体、H2/Ar混合气体;
步骤4中所述溶解的溶剂采用去离子水或蒸馏水;洗涤的方式包括超声清洗;干燥方式包括真空干燥、自然干燥。
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