CN114759196B - 一种负载金属纳米颗粒的共轭微孔高分子电催化剂及其制备方法和应用 - Google Patents
一种负载金属纳米颗粒的共轭微孔高分子电催化剂及其制备方法和应用 Download PDFInfo
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- CN114759196B CN114759196B CN202210492104.3A CN202210492104A CN114759196B CN 114759196 B CN114759196 B CN 114759196B CN 202210492104 A CN202210492104 A CN 202210492104A CN 114759196 B CN114759196 B CN 114759196B
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- microporous polymer
- conjugated microporous
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- electrocatalyst
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- 239000013317 conjugated microporous polymer Substances 0.000 title claims abstract description 45
- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 22
- 239000002082 metal nanoparticle Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 43
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000000446 fuel Substances 0.000 claims abstract description 15
- 125000000623 heterocyclic group Chemical group 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 79
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 21
- 229910052763 palladium Inorganic materials 0.000 claims description 20
- 239000002994 raw material Substances 0.000 claims description 15
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical group [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 7
- 239000000725 suspension Substances 0.000 claims description 7
- 150000002148 esters Chemical class 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 239000000969 carrier Substances 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 230000001678 irradiating effect Effects 0.000 claims description 4
- 150000002736 metal compounds Chemical class 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- SWJPEBQEEAHIGZ-UHFFFAOYSA-N 1,4-dibromobenzene Chemical compound BrC1=CC=C(Br)C=C1 SWJPEBQEEAHIGZ-UHFFFAOYSA-N 0.000 claims description 3
- XIBIQFJKUZZLLX-UHFFFAOYSA-N 2,5-dibromo-1,3-thiazole Chemical compound BrC1=CN=C(Br)S1 XIBIQFJKUZZLLX-UHFFFAOYSA-N 0.000 claims description 3
- LACYYWKMIJOHLU-UHFFFAOYSA-N 2,5-dibromofuran Chemical compound BrC1=CC=C(Br)O1 LACYYWKMIJOHLU-UHFFFAOYSA-N 0.000 claims description 3
- ZHXUWDPHUQHFOV-UHFFFAOYSA-N 2,5-dibromopyridine Chemical compound BrC1=CC=C(Br)N=C1 ZHXUWDPHUQHFOV-UHFFFAOYSA-N 0.000 claims description 3
- KBVDUUXRXJTAJC-UHFFFAOYSA-N 2,5-dibromothiophene Chemical compound BrC1=CC=C(Br)S1 KBVDUUXRXJTAJC-UHFFFAOYSA-N 0.000 claims description 3
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 3
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- 238000006069 Suzuki reaction reaction Methods 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 9
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 36
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 36
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- 238000001000 micrograph Methods 0.000 description 20
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- 230000005540 biological transmission Effects 0.000 description 15
- 238000002484 cyclic voltammetry Methods 0.000 description 13
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 11
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 239000012298 atmosphere Substances 0.000 description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 10
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- 229910052799 carbon Inorganic materials 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 7
- 239000012300 argon atmosphere Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 description 5
- 229910021642 ultra pure water Inorganic materials 0.000 description 5
- 239000012498 ultrapure water Substances 0.000 description 5
- 125000005842 heteroatom Chemical group 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 2
- NHCSMTQRYWPDDW-UHFFFAOYSA-N [C].[N].[S] Chemical compound [C].[N].[S] NHCSMTQRYWPDDW-UHFFFAOYSA-N 0.000 description 2
- OBOXTJCIIVUZEN-UHFFFAOYSA-N [C].[O] Chemical compound [C].[O] OBOXTJCIIVUZEN-UHFFFAOYSA-N 0.000 description 2
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000012876 carrier material Substances 0.000 description 2
- 229910021397 glassy carbon Inorganic materials 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- TZHYBRCGYCPGBQ-UHFFFAOYSA-N [B].[N] Chemical compound [B].[N] TZHYBRCGYCPGBQ-UHFFFAOYSA-N 0.000 description 1
- GJEAMHAFPYZYDE-UHFFFAOYSA-N [C].[S] Chemical compound [C].[S] GJEAMHAFPYZYDE-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
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- 125000003545 alkoxy group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000000861 blow drying Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
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- 238000011161 development Methods 0.000 description 1
- SYHPANJAVIEQQL-UHFFFAOYSA-N dicarboxy carbonate Chemical compound OC(=O)OC(=O)OC(O)=O SYHPANJAVIEQQL-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000003709 fluoroalkyl group Chemical group 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
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- 230000003993 interaction Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000002055 nanoplate Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000009790 rate-determining step (RDS) Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
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- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
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- 238000005556 structure-activity relationship Methods 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
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- 238000001308 synthesis method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- -1 thio carbon Chemical compound 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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Abstract
本发明公开了一种负载金属纳米颗粒的共轭微孔高分子电催化剂及其制备方法和应用,属于燃料电池技术领域。将有机分子结构单元通过交叉偶联反应制备得到具有多样化杂环结构的共轭微孔高分子载体,然后负载金属纳米颗粒,得到负载金属纳米颗粒的共轭微孔高分子电催化剂。利用共轭微孔高分子中的单元结构可调,活性位点可控的特点,可有效调控载体与金属纳米颗粒之间的界面效应,进一步作为阳极催化剂直接应用在直接醇类燃料电池。本发明的电催化剂在电化学性能测试中表现出优秀的电催化活性,良好的反应动力学特性和长期的稳定性,将其作为直接醇类燃料电池的阳极催化材料获得了优异的器件性能。
Description
技术领域
本发明属于燃料电池技术领域,具体涉及一种负载金属纳米颗粒的共轭微孔高分子电催化剂及其制备方法和在直接醇类燃料电池中的应用。
背景技术
由于不可再生能源的广泛消费和日益严重的环境污染问题,对清洁可再生能源的需求也日趋增加。直接醇类燃料电池以其醇类燃料的广泛可用性、比氢燃料电池更方便的储存和运输以及环境友好而备受关注。而大量研究证实,钯(Pd)基电催化剂以其来源丰富、耐久性好等优势,已被证明是直接醇类燃料电池阳极电催化剂最有希望的替代品之一。但是,Pd基电催化剂仍存在许多缺陷,如电极表面中毒、化学活性低、Pd纳米粒子易团聚等。为了克服上述障碍,调控界面效应来调控负载型Pd催化剂被认为是一种有效的策略。界面效应不仅通过金属与载体之间形成良好的共价键来控制金属纳米粒子的分散和稳定,而且通过电子转移可引起电荷的重新分布。电荷再分布可调节负载金属的d带结构,降低了能垒,还能促进速率限制步骤,提高电催化活性。
近年来,科研人员研究了杂原子在载体中对界面效应的影响,如氮掺杂碳纳米管、硼氮掺杂多孔碳、氮硫掺杂石墨烯、氮硫共掺杂碳纳米片,掺杂氮、硫、硼等杂原子是一种由于碳材料电子结构变化而暴露其表面活性位点从而提高其电化学性能的有效方法。然而,传统的Pd基类杂原子掺杂碳基催化剂的载体是通过高温热解、水热合成、溶剂热合成等方法制备获得,很难在碳基催化剂载体中生成单一类型活性位点,这限制了对活性位点的深入了解。
发明内容
本发明的目的是:提出采用杂原子界面工程策略可控性调节催化活性位点,设计合成一类无碳化、结构可调、活性位点可控的共轭微孔高分子催化载体材料,通过负载金属来开发高效的直接醇类燃料电池催化材料体系。
为了实现上述目的,本发明的技术方案如下:
一种负载金属纳米颗粒的共轭微孔高分子电催化剂,所述共轭微孔高分子电催化剂以杂环单元构建的共轭微孔高分子为载体,载体表面负载有金属纳米颗粒;
所述共轭微孔高分子的结构通式M如下:
其中,选自如下结构中的一种:
其中,X为O、S、Se、Te中的任一种;R为H或C1~C40的或支链或烷氧链或氟代烷基链。
进一步的,所述为/>
进一步的,所述金属为钯、银、镍、锌或钴。
本发明还提供了上述的负载金属纳米颗粒的共轭微孔高分子电催化剂的制备方法,具体步骤如下:
步骤1:通过化学方法合成结构式M所示的共轭微孔高分子
合成路线:
上述产物M的制备方法具体步骤如下:
在氩气环境下,分别加入原料1和原料2以及有机溶剂,加入催化剂和碱溶液,在100-180℃条件下回流24-72小时进行suzuki交叉偶联反应,得到共轭微孔高分子;
所述原料1为1,3,5-苯三硼酸三频哪醇酯,所述原料2的结构式为其中如上所述;
步骤2:负载金属纳米颗粒的共轭微孔高分子电催化剂的制备
(1)将步骤1得到的共轭微孔高分子分散在溶剂(优选为乙醇)中形成悬浊液(优选为用超声搅拌0.5-2小时将其均匀分散在溶液中后形成悬浊液);
(2)将金属化合物的溶液加入到步骤(1)中的悬浊液中,在室温下搅拌至均匀,过滤、洗涤、干燥后,在紫外灯下照射1-5小时(优选为在功率为8瓦,主谱线为254nm的紫外灯下照射2小时)得到负载金属纳米颗粒的共轭微孔高分子电催化剂;
所述金属化合物为氯化钯、氯化银、氯化镍、硝酸锌或硝酸钴。
进一步的,所述原料2为2,5-二溴噻唑、2,5-二溴呋喃、2,5-二溴噻吩、2,5-二溴吡啶或1,4-二溴苯。
进一步的,所述有机溶剂为N,N-二甲基甲酰胺;所述碱溶液为碳酸钾溶液。
进一步的,所述原料1和原料2的摩尔量比为1:(0.75~2)。
进一步的,所述催化剂为原料1物质的量的2%-10%的四(三苯基膦)钯。
进一步的,所述干燥条件为在40-100℃下真空干燥6-12小时。
本发明还提供了负载金属纳米颗粒的共轭微孔高分子电催化剂在直接醇类燃料电池催化中的应用。
上述负载金属纳米颗粒的共轭微孔高分子电催化剂可以作为阳极催化剂直接应用在直接醇类燃料电池中。
本发明的技术方案与现有技术相比,具有以下优势:
(1)利用共轭微孔高分子作为金属基催化剂载体,避免了传统方法中高温热解、水热合成等费时费力的合成方法,本发明合成方法环保绿色,安全性好,可重复性高。
(2)以共轭微孔高分子为载体的金属基催化剂在醇氧化性能测试中表现出较高的催化活性,可广泛利用在直接醇类燃料电池中。
(3)通过在共轭微孔高分子中引入不同的杂环结构单元,通过调节载体与金属的界面相互作用,开发出高活性的直接醇类燃料电池催化材料体系,这对促进研发高活性的金属基催化剂具有重要的意义。
附图说明
图1中a,b,c分别为Pd/SNC催化剂的扫描电镜图,透射电镜图,高分辨率透射电镜图。
图2中a,b,c分别为Pd/OC催化剂的扫描电镜图,透射电镜图,高分辨率透射电镜图。
图3中a,b,c分别为Pd/SC催化剂的扫描电镜图,透射电镜图,高分辨率透射电镜图。
图4中a,b,c分别为Pd/NC催化剂的扫描电镜图,透射电镜图,高分辨率透射电镜图。
图5中a,b,c分别为Pd/Ph催化剂的扫描电镜图,透射电镜图,高分辨率透射电镜图。
图6为实施例1-5所得催化剂的傅立叶变换红外光谱图。
图7为实施例1-5所得催化剂的X射线光电子能谱图。
图8为Pd/SNC催化剂的循环伏安曲线;电解液为1摩尔每升甲醇和1摩尔每升氢氧化钾的共混体系,电解液中的气氛为氮气。
图9为Pd/OC催化剂的循环伏安曲线;电解液为1摩尔每升甲醇和1摩尔每升氢氧化钾的共混体系,电解液中的气氛为氮气。
图10为Pd/SC催化剂的循环伏安曲线;电解液为1摩尔每升甲醇和1摩尔每升氢氧化钾的共混体系,电解液中的气氛为氮气。
图11为Pd/NC催化剂的循环伏安曲线;电解液为1摩尔每升甲醇和1摩尔每升氢氧化钾的共混体系,电解液中的气氛为氮气。
图12为Pd/Ph催化剂的循环伏安曲线;电解液为1摩尔每升甲醇和1摩尔每升氢氧化钾的共混体系,电解液中的气氛为氮气。
图13为Pd/SNC催化剂的循环伏安曲线;电解液为1摩尔每升乙醇和1摩尔每升氢氧化钾的共混体系,电解液中的气氛为氮气。
图14为Pd/OC催化剂的循环伏安曲线;电解液为1摩尔每升乙醇和1摩尔每升氢氧化钾的共混体系,电解液中的气氛为氮气。
图15为Pd/SC催化剂的循环伏安曲线;电解液为1摩尔每升乙醇和1摩尔每升氢氧化钾的共混体系,电解液中的气氛为氮气。
图16为Pd/NC催化剂的循环伏安曲线;电解液为1摩尔每升乙醇和1摩尔每升氢氧化钾的共混体系,电解液中的气氛为氮气。
图17为Pd/Ph催化剂的循环伏安曲线;电解液为1摩尔每升乙醇和1摩尔每升氢氧化钾的共混体系,电解液中的气氛为氮气。
具体实施方式
实施例1:硫氮碳基共轭微孔高分子(SNC)的制备:
1,3,5-苯三硼酸三频哪醇酯(200毫克,0.44毫摩尔)、2,5-二溴噻唑(160.3毫克,0.66毫摩尔)和四(三苯基膦)钯(6毫克,0.00528毫摩尔)与10毫升N,N-二甲基甲酰胺和碳酸钾水溶液(2摩尔每升,2毫升)混合。在氩气气氛下,在150℃下搅拌48小时,接着冷却至室温后,将所得混合物取出,依次用超纯水、甲醇和二氯甲烷洗涤两次,去除Pd残留物和低聚物,经过滤、真空120℃干燥8小时后得到硫氮碳基共轭微孔高分子(SNC)(18毫克),收率约为21%。
实施例2:氧碳基共轭微孔高分子(OC)的制备:
1,3,5-苯三硼酸三频哪醇酯(200毫克,0.44毫摩尔)、2,5-二溴呋喃(149.1毫克,0.66毫摩尔)和四(三苯基膦)钯(6毫克,0.00528毫摩尔)与10毫升N,N-二甲基甲酰胺和碳酸钾水溶液(2摩尔每升,2毫升)混合。在氩气气氛下,在150℃下搅拌48小时,接着冷却至室温后,将混合物取出,依次用超纯水、甲醇和二氯甲烷洗涤两次,去除Pd残留物和低聚物。产品经过滤、真空120℃干燥8小时后,得到氧碳基共轭微孔高分子(OC)(65毫克),得率约为85%。
实施例3:硫碳基共轭微孔高分子(SC)的制备:
1,3,5-苯三硼酸三频哪醇酯(200毫克,0.44毫摩尔)、2,5-二溴噻吩(159.7毫克,0.66毫摩尔)和四(三苯基膦)钯(6毫克,0.00528毫摩尔)与10毫升N,N-二甲基甲酰胺和碳酸钾水溶液(2摩尔每升,2毫升)混合。在氩气气氛下,在150℃下搅拌48小时。冷却至室温后,将混合物取出,依次用超纯水、甲醇和二氯甲烷洗涤两次,去除Pd残留物和低聚物。产品经过滤、真空120℃干燥8小时后,得到硫碳基共轭微孔高分子(SC)(76毫克),得率约为88%。
实施例4:氮碳基共轭微孔高分子(NC)的制备:
1,3,5-苯三硼酸三频哪醇酯(200毫克,0.44毫摩尔)、2,5-二溴吡啶(156.3毫克,0.66毫摩尔)和四(三苯基膦)钯(6毫克,0.00528毫摩尔)与10毫升N,N-二甲基甲酰胺和碳酸钾水溶液(2摩尔每升,2毫升)混合。在氩气气氛下,在150℃下搅拌48小时。冷却至室温后,将混合物取出,依次用超纯水、甲醇和二氯甲烷洗涤两次,去除Pd残留物和低聚物。产品经过滤、干燥真空120℃干燥8小时后,得到氮碳基共轭微孔高分子(NC)(77毫克),得率约为92%。
实施例5:纯碳基共轭微孔高分子(Ph)的制备:
1,3,5-苯三硼酸三频哪醇酯(200毫克,0.44毫摩尔)、1,4-二溴苯(155.7毫克,0.66毫摩尔)和四(三苯基膦)钯(6毫克,0.00528毫摩尔)与10毫升N,N-二甲基甲酰胺和碳酸钾水溶液(2摩尔每升,2毫升)混合。在氩气气氛下,在150℃下搅拌48小时。冷却至室温后,将混合物取出,用超纯水、甲醇和二氯甲烷洗涤两次,去除Pd残留物和低聚物。经过滤、真空120℃干燥8小时后,得到纯碳基共轭微孔高分子(Ph)(73毫克),得率约为88%。
实施例6:负载金属纳米颗粒的共轭微孔高分子电催化剂(Pd/SNC,Pd/OC,Pd/SC,Pd/NC,Pd/Ph)的制备:
1、分别取上述实施例1-5的高分子产物分散在30毫升的乙醇溶液中,超声搅拌0.5小时将其均匀分散在溶液中形成悬浊液;
2、再将2毫升的氯化钯乙醇溶液(1毫克每毫升)加入到步骤1中的悬浊液中,在室温下搅拌过夜后过滤,并将所得固体用乙醇和水多次洗涤至无钯离子残留,过滤后在60℃真空下干燥12小时,然后在功率为8瓦,主谱线为254纳米的紫外灯下照射2小时,分别得到混合催化剂备用,混合催化剂分别标记为Pd/SNC,Pd/OC,Pd/SC,Pd/NC,Pd/Ph,上述混合催化剂的扫描电镜图,透射电镜图,高分辨率透射电镜依次见图1-图5;
3、分别将得到的混合催化剂与一定比例的乙炔黑(催化剂与乙炔黑质量比为1:1)在玛瑙研钵中碾磨半小时。
4、取1毫克步骤3研磨后的混合物,向其中加入200微升异丙醇、25微升的5%全氟磺酸树脂溶液,超声至均匀后,取5微升均匀滴涂到玻碳电极上,涂抹厚度0.3微米,吹干后进行醇氧化性能测试。
本申请实施例的电化学测试使用三电极体系的半电池进行,以涂有催化剂的玻碳电极为工作电极,其中催化剂分别为Pd/SNC,Pd/OC,Pd/SC,Pd/NC,Pd/Ph,辅助电极和参比电极分别为铂电极和银/氯化银/氯化钾饱和溶液参比电极,电化学工作站参数设置:工作模式CV,扫描速度50mV/s,扫描电压0.3V~1V,扫描循环5,电解液分别为1摩尔每升甲醇加上1摩尔每升氢氧化钾的水溶液以及1摩尔每升乙醇加上1摩尔每升氢氧化钾的水溶液,结果见图8-17。
对数据测试图的分析:
本发明所制得的钯基催化剂具有良好的醇氧化催化活性,从图6,7中可以看出我们将钯基催化剂载体成功合成,并将钯金属颗粒锚定在载体上。在图1-5的扫描电镜图,透射电镜图和高分辨率透射电镜图中可以看到催化剂载体呈现由亚微米颗粒相互连接形成的多孔网络,可以提供电荷传输通道,同时钯纳米颗粒均匀分布在载体表面,暴露出更多的活性位点。图8-17为钯基催化剂在醇溶液中的循环伏安曲线图,电流密度越大说明催化活性越好。在甲醇氧化反应中,循环伏安曲线电流密度排序为:Pd/SNC(1575.0毫安每毫克钯)>Pd/OC(1108.8毫安每毫克钯)>Pd/SC(252.0毫安每毫克钯)>Pd/NC(214.2毫安每毫克钯)>Pd/Ph(126.0毫安每毫克钯)。在乙醇氧化反应中,循环伏安曲线电流密度排序为:Pd/SNC(1071.0毫安每毫克钯)>Pd/OC(667.8毫安每毫克钯)>Pd/SC(88.2毫安每毫克钯)>Pd/NC(63.0毫安每毫克钯)>Pd/Ph:25.2毫安每毫克钯)。通过含有不同杂环单元的共轭微孔高分子构建的钯基催化剂在醇氧化中的性能比较,结果证明了本发明创造性制备出了性能优异的负载金属纳米颗粒的共轭微孔高分子电催化剂。其中Pd/SNC和Pd/OC在醇溶液中的催化活性较为突出,这有助于我们研究钯基催化剂在醇氧化反应中的构效关系,为设计优良的金属基催化剂载体材料提供了一种新的研究思路。
Claims (5)
1.一种负载金属纳米颗粒的共轭微孔高分子电催化剂的制备方法,所述共轭微孔高分子电催化剂以杂环单元构建的共轭微孔高分子为载体,所述载体表面负载有金属纳米颗粒;
所述共轭微孔高分子的结构通式M如下:
所述为/>
所述制备方法的具体步骤如下:
步骤1:通过化学方法合成结构式M所示的共轭微孔高分子:
在氩气环境下,在反应容器中分别加入原料1和原料2以及有机溶剂,然后加入催化剂和碱溶液,在100-180℃条件下回流24-72小时进行suzuki交叉偶联反应,得到共轭微孔高分子;
所述原料1为1,3,5-苯三硼酸三频哪醇酯,所述原料2为2,5-二溴噻唑、2,5-二溴呋喃、2,5-二溴噻吩、2,5-二溴吡啶或1,4-二溴苯;
步骤2:负载金属纳米颗粒的共轭微孔高分子电催化剂的制备:
(1)将步骤1得到的共轭微孔高分子分散在溶剂中形成悬浊液;
(2)将金属化合物的溶液加入到步骤(1)中的悬浊液中,在室温下搅拌至均匀,过滤、洗涤、干燥后,在紫外灯下照射1-5小时得到负载金属纳米颗粒的共轭微孔高分子电催化剂;
所述金属化合物为氯化钯、氯化银、氯化镍、硝酸锌或硝酸钴。
2.根据权利要求1所述的制备方法,其特征在于,所述金属为钯、银、镍、锌或钴。
3.根据权利要求1所述的制备方法,其特征在于,所述有机溶剂为N,N-二甲基甲酰胺;所述碱溶液为碳酸钾溶液;所述催化剂为原料1物质的量2%-10%的四(三苯基膦)钯。
4.根据权利要求1所述的制备方法,其特征在于,所述原料1和原料2的摩尔量比为1:(0.75~2);所述干燥条件为在40-100℃下真空干燥6-12小时。
5.权利要求1-4任意一项所述制备方法得到的共轭微孔高分子电催化剂在直接醇类燃料电池催化中的应用。
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