CN110743571B - 一种利用H2液相还原制备碳载Pt壳核催化剂的方法 - Google Patents
一种利用H2液相还原制备碳载Pt壳核催化剂的方法 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 121
- 230000009467 reduction Effects 0.000 title claims abstract description 31
- 239000007791 liquid phase Substances 0.000 title claims abstract description 14
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 88
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 52
- 230000000694 effects Effects 0.000 claims abstract description 32
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 27
- 239000000956 alloy Substances 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 24
- 239000002243 precursor Substances 0.000 claims abstract description 24
- 239000011258 core-shell material Substances 0.000 claims abstract description 19
- 230000001603 reducing effect Effects 0.000 claims abstract description 18
- 239000013078 crystal Substances 0.000 claims abstract description 16
- 238000011068 loading method Methods 0.000 claims abstract description 16
- 229910001260 Pt alloy Inorganic materials 0.000 claims abstract description 13
- 230000032683 aging Effects 0.000 claims abstract description 8
- 239000011248 coating agent Substances 0.000 claims abstract description 8
- 238000000576 coating method Methods 0.000 claims abstract description 8
- 230000007704 transition Effects 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 22
- 229910052799 carbon Inorganic materials 0.000 claims description 17
- 239000003638 chemical reducing agent Substances 0.000 claims description 15
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 11
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 10
- 150000002500 ions Chemical class 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 239000004094 surface-active agent Substances 0.000 claims description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 6
- 230000009471 action Effects 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229910000069 nitrogen hydride Inorganic materials 0.000 claims description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 6
- 229910002621 H2PtCl6 Inorganic materials 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 230000005587 bubbling Effects 0.000 claims description 4
- 239000011736 potassium bicarbonate Substances 0.000 claims description 4
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- 239000012279 sodium borohydride Substances 0.000 claims description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- KLFRPGNCEJNEKU-FDGPNNRMSA-L (z)-4-oxopent-2-en-2-olate;platinum(2+) Chemical compound [Pt+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O KLFRPGNCEJNEKU-FDGPNNRMSA-L 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- -1 F127 Polymers 0.000 claims description 3
- 229910020427 K2PtCl4 Inorganic materials 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 238000000921 elemental analysis Methods 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 2
- 229910010084 LiAlH4 Inorganic materials 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 2
- 239000006230 acetylene black Substances 0.000 claims description 2
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 claims description 2
- 150000001721 carbon Chemical group 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- 238000005253 cladding Methods 0.000 claims description 2
- 239000002526 disodium citrate Substances 0.000 claims description 2
- 235000019262 disodium citrate Nutrition 0.000 claims description 2
- CEYULKASIQJZGP-UHFFFAOYSA-L disodium;2-(carboxymethyl)-2-hydroxybutanedioate Chemical compound [Na+].[Na+].[O-]C(=O)CC(O)(C(=O)O)CC([O-])=O CEYULKASIQJZGP-UHFFFAOYSA-L 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- 239000003273 ketjen black Substances 0.000 claims description 2
- 239000012280 lithium aluminium hydride Substances 0.000 claims description 2
- 239000002923 metal particle Substances 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 229920002401 polyacrylamide Polymers 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 239000001509 sodium citrate Substances 0.000 claims description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 2
- 235000011083 sodium citrates Nutrition 0.000 claims description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- 125000004430 oxygen atom Chemical group O* 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 20
- 239000001301 oxygen Substances 0.000 abstract description 20
- 229910052760 oxygen Inorganic materials 0.000 abstract description 20
- 239000000446 fuel Substances 0.000 abstract description 17
- 230000010757 Reduction Activity Effects 0.000 abstract description 9
- 230000008569 process Effects 0.000 abstract description 9
- 238000006555 catalytic reaction Methods 0.000 abstract description 8
- 239000002105 nanoparticle Substances 0.000 abstract description 6
- 229910052697 platinum Inorganic materials 0.000 abstract description 6
- 238000006722 reduction reaction Methods 0.000 description 30
- 239000000243 solution Substances 0.000 description 15
- 239000010410 layer Substances 0.000 description 11
- 230000003197 catalytic effect Effects 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 5
- 229910052723 transition metal Inorganic materials 0.000 description 5
- 150000003624 transition metals Chemical class 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000000840 electrochemical analysis Methods 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910002845 Pt–Ni Inorganic materials 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
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- 238000005087 graphitization Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
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- 239000012085 test solution Substances 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
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Abstract
本发明涉及一种利用H2液相体系还原制备低铂合金核壳结构催化剂的方法，特别是一种Pt合金壳层表面包覆非贵金属核的纳米合金催化剂，包括如下步骤：1)非贵金属前驱体的分散和负载；2)非贵金属核的还原和担载；3)过渡贵金属壳层的置换包覆；4)在H2还原作用下，贵金属合金壳层的还原包覆；5)晶体陈化生长；6)离心、干燥获得低铂壳核合金催化剂。获得的Pt及其合金壳层表面包覆的非贵金属核纳米核壳合金催化剂是一种超细纳米颗粒，具有高效的氧还原活性，催化剂载量低，活性和稳定性好，在燃料电池和电化学氧还原催化过程中具有重要应用价值。
Description
技术领域
本发明属于燃料电池和电化学催化技术领域，具体涉及一种高性能低Pt壳核催化剂的制备方法，该催化剂具有优异的氧还原活性，在氢燃料电池和和氧还原催化过程中具有重要价值和应用。
背景技术
作为一种高效的将化学能转化成电能的能量转化装置，质子交换膜燃料电池在动力交通、固定电站、便携式电源、热电联产等领域有重要的应用，它具有能量转换效率高，室温下快速启动，清洁环保无噪声的优点(Zhao Zipeng et al., Advanced materials,2019)。近年燃料电池性能有突破性进展，但是目前国内燃料电池电堆比功率与国际水平相比有较大差距。提高燃料电池电堆比功率的重要途径之一在于制备高活性氧还原催化剂，降低燃料电池的活化极化。燃料电池的活化极化与催化剂活性密切相关，由于燃料电池氧还原反应的交换电流密度远低于氢氧化反应，其极化损失主要来自于阴极侧，因此，提高阴极侧催化剂的活性具有决定性的影响。
目前质子交换膜燃料电池中常用的商用催化剂是Pt/C，由Pt纳米颗粒分散到碳粉XC-72等载体上，制备的担载型催化剂，实际使用和测试发现当前的商用催化剂在活性、稳定性、载量、成本等方面存在一定不足。当前氧还原催化剂的研究主要集中在通过控制Pt晶面提高Pt/C催化剂的性能；通过制备Pt单原子层催化剂，制备高活性氧还原催化剂；通过Pt的表面修饰增加催化活性；通过制备Pt-M合金和Pt-M核壳催化剂降低贵金属用量，提高催化剂活性和稳定性 (Kwon Hyukbu et al,Nano Letters,2018)。Pt-M催化剂是Pt与过渡金属形成的合金催化剂，通过过渡金属对Pt的电子与几何效应，提高催化剂的稳定性的同时，质量比活性也有所提升，制备Pt-M合金及壳核结构催化剂可以明显降低贵金属的用量，大幅度降低催化剂的成本(Zhang Weiyu et al,Advanced Materials,2019)。其中Pt-Co/C(Ren Weina et al,Carbon,2019)、Pt-Fe/C(Mani Prasanna et al,Journal of PowerSources,2011)、Pt-Ni/C(Reyes-Rodriguez, J.L.et al,Catalysis Science&Technology,2019)等合金催化剂都显示出较好的活性和稳定性(Xu Yanchao et al,NanoResearch，2019)。通过调节晶面和形貌，利用催化剂的尺寸效应、几何效应、电子效应，调节催化剂金属间的晶格应力和电子对Pt表面进行改性，降低催化剂中Pt的用量，提高Pt的利用率，降低催化剂成本，同时提高催化剂活性和寿命(Saedy S.et al.,Journal ofMaterials Chemistry A,2017)。Pt基核壳结构催化剂M@Pt(M＝Co，Ni,Cu 等过渡金属)核壳结构电催化剂在降低Pt载量、提高催化剂活性等方面表现出的良好性能(Wu Zhifu etal,Acs Applied Materials&Interfaces,2019；Wu Meixia et al,Electrochimica Acta，2019；Lai Wei-Hong et al,Advanced Functional Materials,2019),已经成为燃料电池领域的研究热点
发明内容
氧还原反应是燃料电池实现能量转换的最重要过程之一,由于氧还原反应动力学过程缓慢需大量使用Pt贵金属催化剂，导致燃料电池成本较高，阻碍了其商业化进程。近年来，高活性、高稳定性、低Pt载量的Pt基核壳催化剂的研究引起人们广泛关注。本发明利用H2液相体系还原的方法制备低铂合金核壳结构催化剂。制备Pt及其合金壳层表面包覆非贵金属核的纳米核壳超细纳米颗粒，具有高效的氧还原活性，催化剂载量低，活性和稳定性好，在燃料电池和电化学氧还原催化过程中具有重要应用价值。
本发明的具体技术方案如下:
一种利用H2液相体系还原制备高活性低铂合金核壳结构催化剂的方法，其特征在于：所述低铂核壳催化剂的制备，首先通过强还原剂快速还原的办法制备非贵金属晶核，然后通过金属置换的方法制备Pt壳过渡包覆层，再在辅助还原剂的作用下，通过H2鼓泡还原溶液中的Pt前驱体制备完整包覆的壳核催化剂。 H2液相体系还原制备低铂核壳结构催化剂过程，具体制备步骤如下：
1)非贵金属分散与负载：在惰性气体保护作用下，加入表面活性剂，通过超声、搅拌的方法将非贵金属前驱体分散，并负载在碳载体上；超声时间为20～ 50min，搅拌处理的反应温度为40～100℃，反应时间为20～50min；所述的非贵金属离子浓度为0.01～0.5mol/L，加入量0.1～10mL；碳载体加入量25～150mg；表面活性剂加入量0.01～0.8g，分散溶剂体积60～160mL。
2)非贵金属还原：通过加入强还原剂进行非贵金属前驱体的快速还原和分散，制备稳定的超细非贵金属核结构；非贵金属前驱体还原和分散所需的反应温度为40～100℃，反应时间为40min～2h；
3)贵金属过渡壳层置换：通过金属置换反应，制备过渡贵金属壳层，进行非贵金属核的置换包覆；金属置换过程的反应温度为40～100℃，反应时间为 40min～3h；Pt前驱体溶液的浓度为0.1mM～1M，加入量为0.1～50mL。
4)贵金属合金壳层的H2还原与包覆：在辅助还原剂的作用下，通过H2鼓泡还原溶液中的Pt前驱体，制备完整包覆的壳核催化剂，进行贵金属及其合金壳层的还原包覆；所述的液相H2还原过程的反应温度为40～100℃，反应时间为2～6h；前驱体溶液的浓度为0.1mM～1M，加入量为0.1～50mL，非贵金属离子浓度为0.01～0.5mol/L，加入量0.1～10mL。
5)晶体陈化生长：调节pH值，在恒温搅拌作用下，进行晶体的陈化生长；所述的晶体的陈化生长温度为50～100℃，反应时间为6～16h；
6)离心、干燥获得壳核合金催化剂。
本发明的意义在于获得Pt及其合金壳层表面包覆非贵金属核的纳米核壳合金催化剂，该催化剂为超细纳米颗粒，具有高效的氧还原活性，催化剂载量低，活性和稳定性好，在燃料电池和电化学氧还原催化过程中具有重要应用价值。
进一步，所述的非贵金属包括Co2+、Ni2+、Fe3+、Fe2+、Cu2+、Mn2+、Mo5+、Zr4+、 Ag+等3d、4d过渡金属中的一种或两种以上；
所述负载的碳载体包括Vulcan XC-72、Ketjenblack、BP2000、EC300、EC300J、乙炔黑、碳纳米管、石墨烯等高导电性高比表面积的碳导电碳材料；
所述的非贵金属离子分散的表面活性剂主要是易于溶解的高分子表面活性剂，分子量范围4300-100000，表面活性剂优选为P123、F127、聚丙烯酰胺、PVP、CTAB、聚乙二醇或聚氧化乙烯中的一种或两种以上；
所述的分散溶剂形式包括H2O、CH3CH2OH、乙二醇、正丙醇、异丙醇等中的一种或几种的混合溶液；
所述的保护性气体为N2、Ar、He、CO2等非活性保护气体中的一种或以上。
所述的非贵金属离子浓度为0.01～0.5mol/L，加入量0.1～10mL；碳载体加入量25～150mg；表面活性剂加入量0.01～0.8g，分散溶剂体积60～160mL。
进一步，所述的非贵金属前驱体快速还原的强还原剂包括NaBH4、KBH4、 LiAlH4、肼等高活性快速还原还原剂中的一种或一种以上；
所述的快速还原制备稳定的超细非贵金属核结构的pH调节剂种类包括氨水、NaOH、KOH、K2CO3、KHCO3、Na2CO3、NaHCO3等无机碱中的一种或一种以上， pH调节范围为5～8。
进一步，所述的进行非贵金属核的置换包覆的Pt前驱体包括H2PtCl6、 K2PtCl4、氯铂酸铵、乙酰丙酮铂、Pt(NH3)6Cl2、Pt(NH3)4Cl2、Pt(NO2)2(NH3)2等中的一种或几种的混合物；所述的Pt前驱体溶液的浓度为0.1mM～1M，加入量为 0.1～50mL。
进一步，所述的辅助还原剂包括草酸、草酸铵、柠檬酸、柠檬酸钠、柠檬酸二钠、Na2SO3、FeSO4、SnCl2等中的一种或以上，用于辅助促进壳层金属的还原。
所述的还原气氛主要是通过H2或H2与Ar、He、N2等的混合气进行鼓泡，还原溶液中的Pt及其Pt-M混合离子的前驱体，制备完整包覆的壳核催化剂，形成贵金属或其合金壳层的还原包覆催化剂。
所述的壳层合金前驱体中，Pt前驱体包括H2PtCl6、K2PtCl4、氯铂酸铵、乙酰丙酮铂、Pt(NH3)6Cl2、Pt(NH3)4Cl2、Pt(NO2)2(NH3)2等中的一种或几种的混合物；前驱体溶液的浓度为0.1mM～1M，加入量为0.1～50mL。合金离子包括Co2+、 Ni2+、Fe3+、Fe2+、Cu2+、Mn2+、Mo5+、Zr4+、Ag+等3d、4d过渡金属中的一种或两种以上，非贵金属离子浓度为0.01～0.5mol/L，加入量0.1～10mL。
所述的晶体陈化过程调节体系的pH值范围控制在8～14，其中pH调节剂种类包括氨水、NaOH、KOH、K2CO3、KHCO3、Na2CO3、NaHCO3等无机碱中的一种或一种以上，在恒温搅拌作用下促进晶体的陈化生长。
总之，由上述方法通过H2液相体系还原的方法制备低铂合金核壳结构催化剂是Pt及其合金壳层包覆非贵金属核的纳米核壳合金超细纳米颗粒，具有高效的氧还原活性，催化剂载量低，活性和稳定性好，在燃料电池和电化学氧还原催化过程中具有重要应用价值。所述的负载型碳载壳核结构合金催化剂金属组分担载量范围为5～35％，碳载体质量分数65～95％。
所述催化剂表面元素分析：碳原子百分比90～98％，O元素元素原子百分比 2～10％；表面Pt富集，载量5～40％，金属粒径尺寸2～10nm。催化剂Pt用量低，但氧还原活性优于商用Pt/C催化剂，对降低催化剂成本，减少Pt等贵金属的使用有重要意义。H2液相还原条件下制备的Pt合金壳核催化剂，形成尖锐的Pt峰，催化剂组分较纯净；Pt的利用率提高是催化剂性能提高的重要原因。
本发明的特点及有益效果：
(1)本发明是一种H2液相体系还原制备高活性低铂合金核壳结构催化剂的方法，首先通过强还原剂快速还原的办法制备非贵金属晶核，然后通过金属置换的方法制备Pt壳过渡层包覆层，再在辅助还原剂的作用下，通过H2鼓泡还原溶液中的Pt及非贵金属前驱体，制备完整包覆的壳核催化剂。
(2)该Pt及其合金壳层包覆非贵金属核的纳米核壳合金催化剂是一种超细纳米颗粒，具有高效的氧还原活性，催化剂载量低，活性和稳定性好，在燃料电池和电化学氧还原催化过程中具有重要应用价值。
(3)通过线性电压扫描、循环伏安等电化学测试，证明该催化剂具有高ORR 催化活性，优于商用Pt/C催化剂，催化剂活性提高，提高了Pt的利用率，对降低催化剂成本，减少Pt等贵金属的使用有重要意义。
附图说明
图1是本发明实施例1所制备的催化剂的TEM形貌图。
图2是本发明实施例1制备的催化剂的XRD图。
图3是本发明实施例1制备的催化剂的XPS元素分析图。其中3a是C1s的 XPS分峰图，3b是O1s的XPS分峰图，3c是Pt4f的XPS分峰图，3d是Cu2p的 XPS分峰图。
图4是本发明实施例1制备的催化剂的电化学性能表征图。其中4a是制备 Cu@PtMo/C催化剂与商业化40％Pt/C(JM)催化剂活性CV对比图；4b是制备 Cu@PtMo/C催化剂与商业化40％Pt/C(JM)催化剂ORR对比图。
图5是本发明实施例2制备的催化剂的电化学性能表征图。其中5a是制备的Cu@PtMo/C催化剂与商业化40％Pt/C(JM)催化剂CV活性对比图；5b是制备的 Cu@PtMo/C催化剂与商业化40％Pt/C(JM)催化剂ORR对比图。
具体实施方式：
下面结合附图和实施例对本发明做进一步说明。
图1是实施例1所制备催化剂TEM形貌图，可见H2液相还原条件下制备的 Pt合金包覆催化剂为超细分散纳米颗粒。
图2是实施例1所制备催化剂的XRD图，催化剂形成尖锐晶体衍射峰，但是与典型的Pt晶面(111)、(200)、(220)、(311)、(222)晶面衍射峰相比，催化剂衍射峰都向高衍射角方向移动，衍射角增大,说明晶面间距变小，可见Pt晶格间距由于合金化的作用实现调节，晶格减速缩小有利于催化剂表面O2吸附，提高Pt的催化活性。同时谱图证明，催化剂中无明显Cu单质衍射峰，催化剂组分比较纯净，Cu、Mo的存在对催化剂实现合金化掺杂；该催化剂制备了较好的贵金属合金包覆层，还原制备过程有利于Pt在催化剂表面的富集，提高Pt的利用率，是催化剂性能提高的重要原因。
图3是实施例1所制备的催化剂的XPS元素分析图。表面碳原子百分比为 92.6％，O原子百分比为6.06％，Pt原子百分比0.69％，Cu原子百分比0.34％。其中，3a是C1s的XPS分峰图，C占92.6％(atomic)，可见碳载体主要以高石墨化程度碳形式存在，有利于提高催化剂的导电性。3b是O1s的XPS分峰图可见催化剂表面形成丰富的C-O结构，一定程度增加催化剂表面的亲水性，有利于催化过程的进行；3c是Pt4f的XPS分峰图，表面Pt占0.69％，主要以Pt0的形式存在，有未被彻底还原的Pt2+；3d是Cu2p的XPS分峰图，结合XRD谱图分析，可知催化剂表面Cu以Cu+形式存在，催化剂表面无游离的单质。
图4是本发明实施例1制备催化剂的电化学性能表征图。其中，4a是 Cu@PtMo/C(pH>7)与40％Pt/C电化学活性面积对比，催化剂还原峰电位显著优于商业Pt/C，有良好催化活性。4b是Cu@PtMo/C(pH>7)与40％Pt/C氧还原活性对比，Cu@PtMo/C(pH>7)的氧还原活性显著优于40％Pt/C。
图5是本发明实施例2制备催化剂的电化学性能表征图。其中，5a是 Cu@PtMo/C(pH<7)与40％Pt/C电化学活性面积对比，还原峰电位较高，有良好催化活性。5b是Cu@PtMo/C(pH<7)与40％Pt/C氧还原活性对比，Cu@PtMo/C(pH<7) 的氧还原活性虽然弱于碱性条件催化剂，但仍然显著优于40％Pt/C。
实施例1
取PVP(聚乙烯吡咯烷酮)0.057g溶解在50mL乙醇与30mL水的混合溶液中，加入0.1M的CuCl2溶液2mL,加入碳载体XC-72 50mg,超声分散30min。在N2保护作用下，80℃油浴，加入碱性还原剂NaBH4 0.03g，其中NaOH 0.015g,水30mL， N2保护80℃搅拌1h。加入0.015mol/L H2PtCl6溶液3mL,N2保护下，置换2h。加入草酸鳌合的MoCl5(0.02g)和H2PtCl6(0.015mol/L,3mL)的混合溶液,调节 pH＝11,在H2还原条件下，80℃反应4h制备合金壳层结构。加入NaBH4 0.2g,NaOH 0.06g,在N2保护作用下晶体陈化过夜。离心，60℃干燥，从而获得高活性低铂 Pt合金壳核结构催化剂。
实施例2
取PVP(聚乙烯吡咯烷酮)0.057g溶解在50mL乙醇与30mL水的混合溶液中，加入0.1M的CuCl2溶液2mL,加入碳载体XC-72 50mg,超声分散30min。在N2保护作用下，80℃油浴，加入碱性还原剂NaBH4 0.03g，其中NaOH 0.015g,水30mL， N2保护80℃搅拌1h。加入0.015mol/L H2PtCl6溶液3mL,N2保护下，置换2h。加入草酸鳌合的MoCl5(0.02g)和H2PtCl6(0.015mol/L,3mL)的混合溶液,调节pH＝5, 在H2还原条件下，80℃反应4h制备合金壳层结构。加入NaBH4 0.2g,NaOH 0.06g, 在N2保护作用下晶体陈化过夜。离心，60℃干燥，从而获得高活性低铂Pt合金壳核结构催化剂。
实施例3
电化学测试在三电极体系中进行，用于表征催化剂的氧还原活性。该体系电解质溶液为0.1mol L-1的HClO4，对电极为Pt片电极，参比电极为饱和甘汞电极，循环伏安测试电解质溶液被N2饱和，测试系统为Gamry3000；ORR测试溶液被O2饱和。旋转圆盘电极膜催化层的制备：40％Pt/C催化剂：5mg催化剂，2.5 mL异丙醇，超声；加5wt％Nafion溶液50μL，超声，取3.2μL上述分散好的浆料涂覆在旋转圆盘电极表面，作为工作电极。由于Cu@PtMo/C催化剂载量低，膜催化层制备：5mg催化剂，2.5mL异丙醇，超声；加5wt％Nafion溶液50μL，超声，取8μL上述分散好的浆料涂覆在旋转圆盘电极表面，作为工作电极。电极催化剂载量20μgcm-2.
上述实施例对本发明的技术方案进行了详细说明。显然，本发明并不局限于所描述的实施例。基于本发明中的实施例，熟悉本技术领域的人员还可据此做出多种变化，但任何与本发明等同或相类似的变化都属于本发明保护的范围。
Claims (7)
1.一种利用H2液相体系还原制备高活性低铂合金核壳结构催化剂的方法，其特征在于，包括以下步骤：
1)在惰性气体保护作用下，加入表面活性剂，通过超声、搅拌将非贵金属前驱体分散，并负载在碳载体上；所述表面活性剂分子量范围4300-100000，为P123、F127、聚丙烯酰胺、PVP、CTAB、聚乙二醇或聚氧化乙烯中的一种或两种以上；加入量0.01～0.8g；所述非贵金属离子包括Co2+、Ni2+、Fe3+、Fe2+、Cu2+、Mn2+、Mo5+、Zr4+、Ag+中的一种；
2)通过加入强还原剂进行非贵金属前驱体的快速还原和分散，制备稳定的超细非贵金属核结构；
3)通过金属置换反应，制备过渡贵金属壳层，进行非贵金属核的置换包覆；
4)在辅助还原剂的作用下，通过液相H2鼓泡还原溶液中的Pt前驱体，制备完整包覆的壳核催化剂，进行贵金属及其合金壳层的还原包覆；所述辅助还原剂包括草酸、草酸铵、柠檬酸、柠檬酸钠、柠檬酸二钠、Na2SO3、FeSO4、SnCl2中的一种；所述Pt前驱体包括H2PtCl6、K2PtCl4、氯铂酸铵、乙酰丙酮铂、Pt(NH3)6Cl2、Pt(NH3)4Cl2、Pt(NO2)2(NH3)2中的一种或几种的混合物；所述H2液相鼓泡是通过H2或H2与Ar、He、N2混合气进行鼓泡；所述还原包覆的反应温度为40～100℃，反应时间为2～6h；
5)调节pH值，在恒温搅拌作用下，进行晶体的陈化生长；
6)通过离心、干燥，获得低铂合金壳核结构催化剂。
2.根据权利要求1所述的方法，其特征在于，步骤1)中所述惰性气体为N2、Ar、He、CO2中的一种；所述超声时间为20～50min，所述搅拌的温度为40～100℃，反应时间为20～50min；所述非贵金属的离子浓度为0.01～0.5mol/L，加入量0.1～10mL；所述分散，使用的溶剂包括H2O、CH3CH2OH、乙二醇、正丙醇、异丙醇中的一种或几种的混合溶液；所述溶剂体积60～160mL；所述负载的碳载体包括Vulcan XC-72、Ketjenblack、BP2000、EC300、EC300J、乙炔黑、碳纳米管、石墨烯；加入量25～150mg。
3.根据权利要求1所述的方法，其特征在于，步骤2)中所述强还原剂包括NaBH4、KBH4、LiAlH4、肼中的一种；反应温度为40～100℃，反应时间为40min～2h；使用pH调节剂，将pH调节为5～8；所述pH调节剂包括氨水、NaOH、KOH、K2CO3、KHCO3、Na2CO3、NaHCO3中的一种。
4.根据权利要求1所述的方法，其特征在于，步骤3)所述金属置换反应的温度为40～100℃，反应时间为40min～3h；所述贵金属为Pt前驱体溶液，所述Pt前驱体溶液的浓度为0.1mM～1M，加入量为0.1～50mL。
5.根据权利要求1所述的方法，其特征在于，步骤5)中所述调节pH值的pH范围8～14，其中调节pH值使用的pH调节剂包括氨水、NaOH、KOH、K2CO3、KHCO3、Na2CO3、NaHCO3中的一种；所述陈化生长的温度为50～100℃，反应时间为6～16h。
6.权利要求1-5任一项所述方法制备的高活性低铂合金核壳结构催化剂，其特征在于，所述催化剂金属组分含量范围为5～35％，碳载体质量分数65～95％。
7.根据权利要求6所述的催化剂，其特征在于，所述催化剂表面元素分析：碳原子百分比90～98％，O原子百分比2～10％；表面Pt富集，含量5～40％，金属粒径尺寸2～10nm。
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