CN103816894B - Doping type graphene-supported PtRu alloy nano eelctro-catalyst and preparation method thereof - Google Patents
Doping type graphene-supported PtRu alloy nano eelctro-catalyst and preparation method thereof Download PDFInfo
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- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 76
- 239000000956 alloy Substances 0.000 title claims abstract description 76
- 229910002849 PtRu Inorganic materials 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000003054 catalyst Substances 0.000 title description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 105
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 100
- 239000010411 electrocatalyst Substances 0.000 claims abstract description 53
- 239000000843 powder Substances 0.000 claims abstract description 27
- 239000002243 precursor Substances 0.000 claims abstract description 27
- 239000002245 particle Substances 0.000 claims abstract description 20
- 238000003756 stirring Methods 0.000 claims abstract description 20
- 239000011261 inert gas Substances 0.000 claims abstract description 19
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000004202 carbamide Substances 0.000 claims abstract description 15
- 239000007787 solid Substances 0.000 claims abstract description 15
- 239000004327 boric acid Substances 0.000 claims abstract description 11
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000000227 grinding Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- 239000002019 doping agent Substances 0.000 claims description 22
- 229910052757 nitrogen Inorganic materials 0.000 claims description 17
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- 239000000725 suspension Substances 0.000 claims description 12
- 229910052796 boron Inorganic materials 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 6
- 238000003746 solid phase reaction Methods 0.000 claims description 6
- 238000010671 solid-state reaction Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 239000002105 nanoparticle Substances 0.000 abstract description 16
- 238000000034 method Methods 0.000 abstract description 12
- 239000006185 dispersion Substances 0.000 abstract description 6
- 238000005265 energy consumption Methods 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 72
- 230000003647 oxidation Effects 0.000 description 15
- 238000007254 oxidation reaction Methods 0.000 description 15
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 15
- 230000000694 effects Effects 0.000 description 8
- 239000010970 precious metal Substances 0.000 description 8
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 6
- 238000006056 electrooxidation reaction Methods 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 239000000446 fuel Substances 0.000 description 5
- 231100000572 poisoning Toxicity 0.000 description 5
- 230000000607 poisoning effect Effects 0.000 description 5
- 125000005619 boric acid group Chemical group 0.000 description 4
- 238000002484 cyclic voltammetry Methods 0.000 description 4
- 238000010304 firing Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 229910001260 Pt alloy Inorganic materials 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000000970 chrono-amperometry Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 229910021397 glassy carbon Inorganic materials 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- -1 introducing B Chemical compound 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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Abstract
本发明涉及一种掺杂型石墨烯负载PtRu合金纳米电催化剂及其制备方法。其技术方案是：将石墨烯氧化物∶H2PtCl6·6H2O∶RuCl3·3H2O的质量比为70~90∶15~65∶5~40的原料搅拌均匀，向其中加入尿素或硼酸，在搅拌和20~60℃条件下恒温干燥，得到前驱体；将前驱体进行研磨，将研磨后得到的前驱体粉末在惰性气体保护和400~1000℃条件下固相反应5~120min，冷却，得到黑色固体粉末；将黑色固体粉末进行研磨，洗涤，干燥，制得掺杂型石墨烯负载PtRu合金纳米电催化剂；其中，PtRu合金为10~30wt%，掺杂型石墨烯为70~90wt%。本发明具有工艺简单和能耗低的特点，所制备的产品催化活性高、稳定性好、纳米粒子分散均匀和粒径可控。
The invention relates to a doped graphene supported PtRu alloy nano electrocatalyst and a preparation method thereof. The technical scheme is: stir evenly the raw materials whose mass ratio of graphene oxide: H 2 PtCl 6 6H 2 O : RuCl 3 3H 2 O is 70~90:15~65:5~40, and add urea or boric acid, stirring and drying at a constant temperature of 20-60°C to obtain the precursor; grind the precursor, and react the powder of the precursor obtained after grinding in the solid state for 5-120min under the protection of an inert gas and at 400-1000°C , cooled to obtain a black solid powder; the black solid powder is ground, washed, and dried to obtain a doped graphene-supported PtRu alloy nano-electrocatalyst; wherein, the PtRu alloy is 10~30wt%, and the doped graphene is 70 ~90wt%. The invention has the characteristics of simple process and low energy consumption, and the prepared product has high catalytic activity, good stability, uniform dispersion of nanoparticles and controllable particle size.
Description
技术领域 technical field
本发明属于燃料电池催化剂技术领域。具体涉及一种掺杂型石墨烯负载PtRu合金纳米电催化剂及其制备方法。 The invention belongs to the technical field of fuel cell catalysts. Specifically relates to a doped graphene supported PtRu alloy nano electrocatalyst and a preparation method thereof.
背景技术 Background technique
直接甲醇燃料电池具有结构简单、低温启动速度快、燃料廉价易得、清洁无污染、比能量高和能量转换效率高等特点，有望成为未来便携式电子产品以及电动汽车、飞机等的主流电源，并能缓解因煤、石油等化石能源的日益枯竭引起的能源危机以及因使用化石能源带来的环境污染等问题。 Direct methanol fuel cells have the characteristics of simple structure, fast start-up speed at low temperature, cheap and easy-to-obtain fuel, clean and pollution-free, high specific energy and high energy conversion efficiency. Alleviate the energy crisis caused by the depletion of fossil energy such as coal and oil and the environmental pollution caused by the use of fossil energy.
Pt是已知的对甲醇电氧化催化活性较好、使用较广泛的催化剂。然而，以金属铂为催化剂还存在成本过高和抵抗CO类似中间产物毒化能力较差等问题。研究发现，Ru原子在甲醇氧化过程中能吸附一些类似OH-的含氧物，这些含氧物能与吸附在Pt原子表面的CO类似中间产物发生反应，从而减轻Pt催化剂的中毒。因此，采用PtRu合金作为直接甲醇燃料电池阳极催化剂，能有效提高贵金属Pt催化剂的活性和利用率。 Pt is known as a catalyst with good catalytic activity for methanol electrooxidation and is widely used. However, the use of metal platinum as a catalyst still has problems such as high cost and poor resistance to poisoning by CO-like intermediates. It was found that Ru atoms can adsorb some OH-like oxygenates during methanol oxidation, and these oxygenates can react with CO-like intermediates adsorbed on the surface of Pt atoms, thereby reducing the poisoning of Pt catalysts. Therefore, using PtRu alloy as an anode catalyst for direct methanol fuel cells can effectively improve the activity and utilization of noble metal Pt catalysts.
为了进一步提高贵金属催化剂的利用率、降低直接甲醇燃料电池的成本，采用炭黑、炭纤维、碳纳米管、石墨烯等材料负载Pt纳米粒子，能够调整Pt纳米粒子的尺寸、形貌和粒径分布，改善催化剂的性能。其中，石墨烯具有导电性高、比表面积大、化学稳定性好等特点，是一种新型、高效的催化剂载体材料。同时，对石墨烯进行掺杂，如在晶格中引入B、N等杂质原子，能够调控石墨烯的电子和能带结构，并进一步改善其物理、化学性能。目前，以掺杂型石墨烯为载体的Pt和Pt合金催化剂主要是通过多步反应合成（ZhangLS,LiangXQ等，PhysicalChemistryChemicalPhysics,2010,12,12055-12059；XiongB,ZhouYK等,Carbon,2013,52,181-192），即先对石墨烯进行掺杂，然后在掺杂型石墨烯表面负载Pt或Pt合金纳米粒子，这种制备方法工艺过程较复杂、生产周期较长、生产成本较高和不利于大量生产。 In order to further improve the utilization rate of noble metal catalysts and reduce the cost of direct methanol fuel cells, carbon black, carbon fiber, carbon nanotubes, graphene and other materials are used to support Pt nanoparticles, and the size, shape and particle size of Pt nanoparticles can be adjusted. distribution to improve catalyst performance. Among them, graphene has the characteristics of high electrical conductivity, large specific surface area, and good chemical stability, and is a new and efficient catalyst support material. At the same time, doping graphene, such as introducing B, N and other impurity atoms into the lattice, can regulate the electronic and energy band structure of graphene, and further improve its physical and chemical properties. At present, Pt and Pt alloy catalysts based on doped graphene are mainly synthesized by multi-step reactions (ZhangLS, LiangXQ, etc., PhysicalChemistryChemicalPhysics, 2010, 12, 12055-12059; XiongB, ZhouYK, etc., Carbon, 2013, 52, 181- 192), that is, doping graphene first, and then loading Pt or Pt alloy nanoparticles on the surface of doped graphene. This preparation method has complicated process, long production cycle, high production cost and is not conducive to mass production Production.
发明内容 Contents of the invention
本发明的目的是克服现有技术缺陷，提供一种工艺简单和能耗低的掺杂型石墨烯负载PtRu合金纳米电催化剂的制备方法；用该方法制备的掺杂型石墨烯负载PtRu合金纳米电催化剂的催化活性高、稳定性好、纳米粒子分散均匀和粒径可控。 The purpose of the present invention is to overcome the defects of the prior art, and provide a method for preparing a doped graphene-loaded PtRu alloy nano electrocatalyst with simple process and low energy consumption; the doped graphene-loaded PtRu alloy nano electrocatalyst prepared by this method The electrocatalyst has high catalytic activity, good stability, uniform dispersion of nanoparticles and controllable particle size.
为了实现上述目的，本发明采用的技术方案是：所述电催化剂中：PtRu合金为10~30wt%，掺杂型石墨烯为70~90wt%；PtRu合金的粒径为0.5~9.5nm。 In order to achieve the above object, the technical solution adopted in the present invention is: in the electrocatalyst: 10-30wt% of PtRu alloy, 70-90wt% of doped graphene; the particle size of PtRu alloy is 0.5-9.5nm.
所述掺杂型石墨烯中的掺杂元素为N和B中的一种；N或B的掺杂量为掺杂型石墨烯的1~10wt%。 The doping element in the doped graphene is one of N and B; the doping amount of N or B is 1-10wt% of the doped graphene.
所述PtRu合金中Pt与Ru的物质的量的比为1∶(0.5~2)。 The ratio of the amount of Pt to Ru in the PtRu alloy is 1: (0.5-2).
所述掺杂型石墨烯负载PtRu合金纳米电催化剂的制备方法，其具体步骤是： The preparation method of described doped graphene supported PtRu alloy nanometer electrocatalyst, its specific steps are:
(1)将石墨烯氧化物溶液、H2PtCl6·6H2O溶液和RuCl3·3H2O溶液搅拌均匀，得到均分散悬浮液； (1) Stir the graphene oxide solution, the H 2 PtCl 6 6H 2 O solution and the RuCl 3 3H 2 O solution evenly to obtain a homogeneously dispersed suspension;
其中，石墨烯氧化物∶H2PtCl6·6H2O∶RuCl3·3H2O的质量比为70~90∶15~65∶5~40；石墨烯氧化物溶液的浓度为2~10g/L，H2PtCl6·6H2O溶液的浓度为5~20g/L，RuCl3·3H2O溶液的浓度为5~20g/L。 Among them, the mass ratio of graphene oxide: H 2 PtCl 6 ·6H 2 O: RuCl 3 ·3H 2 O is 70~90:15~65:5~40; the concentration of graphene oxide solution is 2~10g/ L, the concentration of H 2 PtCl 6 ·6H 2 O solution is 5~20g/L, the concentration of RuCl 3 ·3H 2 O solution is 5~20g/L.
(2)向步骤(1)得到的均分散悬浮液中加入掺杂物，搅拌溶解后，在搅拌和20~60℃条件下恒温干燥，得到前驱体。 (2) Add dopant to the homogeneously dispersed suspension obtained in step (1), stir to dissolve, and then dry under stirring and constant temperature at 20-60° C. to obtain a precursor.
其中，掺杂物为尿素和硼酸中的一种，掺杂物与石墨烯氧化物的质量比为(1~3)︰1。 Wherein, the dopant is one of urea and boric acid, and the mass ratio of the dopant to graphene oxide is (1~3):1.
(3)将步骤(2)得到的前驱体进行研磨，得到前驱体粉末。 (3) Grinding the precursor obtained in step (2) to obtain precursor powder.
(4)将步骤(3)得到的前驱体粉末在惰性气体保护和400~1000℃条件下固相反应5~120min，然后进行冷却，得到黑色固体粉末。 (4) The precursor powder obtained in step (3) was subjected to a solid-state reaction at 400-1000° C. for 5-120 minutes under the protection of an inert gas, and then cooled to obtain a black solid powder.
其中，惰性气体为氮气和氩气中的一种。 Wherein, the inert gas is one of nitrogen and argon.
(5)将步骤(4)得到的黑色固体粉末进行研磨，依次用蒸馏水和无水乙醇洗涤，然后在10~80℃恒温干燥，制得掺杂型石墨烯负载PtRu合金纳米电催化剂。 (5) The black solid powder obtained in step (4) was ground, washed with distilled water and absolute ethanol in sequence, and then dried at a constant temperature of 10-80°C to prepare a doped graphene-supported PtRu alloy nano-electrocatalyst.
由于采用上述技术方案，本发明与现有技术相比具有如下突出特点： Due to the adoption of the above-mentioned technical scheme, the present invention has the following outstanding features compared with the prior art:
(1)本发明采用尿素为氮源对石墨烯进行氮掺杂、或采用硼酸为硼源对石墨烯进行硼掺杂，氮或硼的含量通过控制尿素或硼酸的加入量、反应温度和反应时间来进行调节；掺杂物直接溶于石墨烯氧化物溶液中，掺杂物与石墨烯氧化物充分接触，能快速高效地实现石墨烯的掺杂；掺杂型石墨烯作为载体，PtRu合金纳米粒子分散均匀，催化剂对甲醇的电催化活性明显提高。 (1) The present invention adopts urea as a nitrogen source to carry out nitrogen doping to graphene, or adopts boric acid as a boron source to carry out boron doping to graphene, and the content of nitrogen or boron is controlled by the addition of urea or boric acid, reaction temperature and reaction time to adjust; the dopant is directly dissolved in the graphene oxide solution, and the dopant is in full contact with the graphene oxide, which can quickly and efficiently realize the doping of graphene; the doped graphene is used as the carrier, and the PtRu alloy The nanoparticles are uniformly dispersed, and the electrocatalytic activity of the catalyst to methanol is obviously improved.
(2)本发明采用一步固相还原法制备掺杂型石墨烯负载PtRu合金纳米电催化剂，与现有技术相比，不需要先合成掺杂型石墨烯，也不需要很长的反应时间；而是将石墨烯的掺杂和PtRu合金纳米粒子的负载同时进行，反应温度为400~1000℃，反应时间为5~120min，故工艺简单，能耗低；采用惰性气体保护，能有效地防止石墨烯和贵金属的氧化；采用高温烧成和快速冷却的方法，可以通过控制烧成温度和保温时间来控制PtRu合金粒子的尺寸和粒径分布；催化剂中贵金属总含量在10~30wt%范围内可控，贵金属的利用率高。 (2) The present invention adopts a one-step solid-phase reduction method to prepare doped graphene-loaded PtRu alloy nano-electrocatalysts. Compared with the prior art, it is not necessary to first synthesize doped graphene, nor does it require a long reaction time; Instead, the doping of graphene and the loading of PtRu alloy nanoparticles are carried out at the same time, the reaction temperature is 400~1000°C, and the reaction time is 5~120min, so the process is simple and the energy consumption is low; the use of inert gas protection can effectively prevent Oxidation of graphene and precious metals; the size and particle size distribution of PtRu alloy particles can be controlled by controlling the firing temperature and holding time by high temperature firing and rapid cooling; the total content of precious metals in the catalyst is in the range of 10~30wt% Controllable, high utilization rate of precious metals.
本发明制备的掺杂型石墨烯负载PtRu合金纳米电催化剂，通过透射电镜观察：PtRu合金纳米粒子高度分散在掺杂型石墨烯表面，其粒径范围为0.5~9.5nm，XRD物相分析有很强的石墨烯（002）面衍射峰和PRu合金的（111）、（200）、（220）面衍射峰。其中掺杂型石墨烯比表面积大，PtRu合金纳米粒子分散度高，从而能有效提高贵金属的利用率。 The doped graphene-loaded PtRu alloy nano electrocatalyst prepared by the present invention is observed by transmission electron microscope: PtRu alloy nanoparticles are highly dispersed on the surface of doped graphene, and its particle size range is 0.5~9.5nm, XRD phase analysis has Strong graphene (002) plane diffraction peaks and PRu alloy (111), (200), (220) plane diffraction peaks. Among them, the doped graphene has a large specific surface area and a high dispersion of PtRu alloy nanoparticles, which can effectively improve the utilization rate of precious metals.
本发明采用三电极体系测试其甲醇氧化电催化性能，将催化剂、5wt%的Nation溶液和无水乙醇在超声波作用下混合均匀，将该均匀的浆料涂在玻碳电极上，在60℃下烘干，作为测量用的工作电极。测量用的对电极为碳棒，参比电极为Ag/AgCl电极（3.5MKCl），电解液为1MCH3OH+0.5MH2SO4。用循环伏安法评价本发明制备的PtRu合金纳米电催化剂对甲醇氧化的电催化活性，扫描速度为10mV/s，甲醇电氧化的峰电流密度为15.3~257.3A/g，正反向扫描对应的峰电流密度的比值为1.32~3.51，表现出很高的对甲醇氧化的电催化活性和抗CO中毒能力。用计时电流法评价本发明制备的掺杂型石墨烯负载PtRu合金纳米电催化剂的稳定性，初始电位为0.6V，经过500s，催化剂的甲醇氧化电流密度为5~108.5A/g，电流密度保持率为8.9~43.1%，对甲醇电氧化具有优异的稳定性。 The present invention uses a three-electrode system to test the electrocatalytic performance of methanol oxidation, mixes the catalyst, 5wt% Nation solution and absolute ethanol uniformly under the action of ultrasonic waves, coats the uniform slurry on the glassy carbon electrode, and heats the catalyst at 60°C Dry it and use it as a working electrode for measurement. The counter electrode used for measurement is carbon rod, the reference electrode is Ag/AgCl electrode (3.5MKCl), and the electrolyte is 1MCH 3 OH+0.5MH 2 SO 4 . Use cyclic voltammetry to evaluate the electrocatalytic activity of the PtRu alloy nano-electrocatalyst prepared by the present invention to methanol oxidation, the scan speed is 10mV/s, the peak current density of methanol electrooxidation is 15.3~257.3A/g, and the forward and reverse scans correspond to The ratio of peak current density is 1.32~3.51, showing high electrocatalytic activity for methanol oxidation and resistance to CO poisoning. Evaluate the stability of the doped graphene supported PtRu alloy nano electrocatalyst prepared by the present invention by chronoamperometry, the initial potential is 0.6V, after 500s, the methanol oxidation current density of the catalyst is 5～108.5A/g, and the current density maintains The ratio is 8.9~43.1%, and it has excellent stability to methanol electrooxidation.
因此，本发明具有工艺简单和能耗低的特点，所制备的掺杂型石墨烯负载PtRu合金纳米电催化剂催化活性高、稳定性好、纳米粒子分散均匀和粒径可控。 Therefore, the present invention has the characteristics of simple process and low energy consumption, and the prepared doped graphene-supported PtRu alloy nano electrocatalyst has high catalytic activity, good stability, uniform dispersion of nanoparticles and controllable particle size.
附图说明 Description of drawings
图1为本发明制备的一种掺杂型石墨烯负载PtRu合金纳米电催化剂的TEM图； Fig. 1 is the TEM figure of a kind of doped type graphene supported PtRu alloy nano-electrocatalyst prepared by the present invention;
图2为图1所述电催化剂的粒径分布直方图； Fig. 2 is the particle size distribution histogram of electrocatalyst described in Fig. 1;
图3为图1所述电催化剂的XRD图； Fig. 3 is the XRD figure of electrocatalyst described in Fig. 1;
图4为图1所述电催化剂在10mV/s扫描速度下的甲醇电催化氧化循环伏安曲线图； Fig. 4 is the cyclic voltammetry curve of methanol electrocatalytic oxidation of the electrocatalyst described in Fig. 1 at a scanning speed of 10mV/s;
图5为图1所述电催化剂的电流-时间曲线图。 FIG. 5 is a current-time graph of the electrocatalyst shown in FIG. 1 .
具体实施方式 detailed description
下面结合附图和具体实施方式对本发明的制备过程、表征及性能测试结果作进一步的描述，但本发明提供的催化剂并不仅仅限于下列的实施案例。 The preparation process, characterization and performance test results of the present invention will be further described below in conjunction with the accompanying drawings and specific embodiments, but the catalyst provided by the present invention is not limited to the following examples.
实施例1Example 1
一种掺杂型石墨烯负载PtRu合金纳米电催化剂及其制备方法。所述电催化剂中：PtRu合金为25~30wt%，掺杂型石墨烯为70~75wt%；PtRu合金的粒径为0.5~9.5nm。 A doped graphene-supported PtRu alloy nano electrocatalyst and a preparation method thereof. In the electrocatalyst: the PtRu alloy is 25-30wt%, and the doped graphene is 70-75wt%; the particle size of the PtRu alloy is 0.5-9.5nm.
所述掺杂型石墨烯中的掺杂元素为N；N的掺杂量为掺杂型石墨烯的7~10wt%。 The doping element in the doped graphene is N; the doping amount of N is 7-10wt% of the doped graphene.
所述PtRu合金中Pt与Ru的物质的量的比为1∶(1.6~2)。 The ratio of the amount of Pt to Ru in the PtRu alloy is 1:(1.6~2).
所述掺杂型石墨烯负载PtRu合金纳米电催化剂的制备方法，其具体步骤是： The preparation method of described doped graphene supported PtRu alloy nanometer electrocatalyst, its specific steps are:
(1)将石墨烯氧化物溶液、H2PtCl6·6H2O溶液和RuCl3·3H2O溶液搅拌均匀，得到均分散悬浮液； (1) Stir the graphene oxide solution, the H 2 PtCl 6 6H 2 O solution and the RuCl 3 3H 2 O solution evenly to obtain a homogeneously dispersed suspension;
其中，石墨烯氧化物∶H2PtCl6·6H2O∶RuCl3·3H2O的质量比为70~75∶50~65∶30~40；石墨烯氧化物溶液的浓度为2~10g/L，H2PtCl6·6H2O溶液的浓度为5~20g/L，RuCl3·3H2O溶液的浓度为5~20g/L。 Among them, the mass ratio of graphene oxide: H 2 PtCl 6 ·6H 2 O: RuCl 3 ·3H 2 O is 70~75:50~65:30~40; the concentration of graphene oxide solution is 2~10g/ L, the concentration of H 2 PtCl 6 ·6H 2 O solution is 5~20g/L, the concentration of RuCl 3 ·3H 2 O solution is 5~20g/L.
(2)向步骤(1)得到的均分散悬浮液中加入掺杂物，搅拌溶解后，在搅拌和20~60℃条件下恒温干燥，得到前驱体。 (2) Add dopant to the homogeneously dispersed suspension obtained in step (1), stir to dissolve, and then dry under stirring and constant temperature at 20-60° C. to obtain a precursor.
其中，掺杂物为尿素，尿素与石墨烯氧化物的质量比为(2.5~3)︰1。 Wherein, the dopant is urea, and the mass ratio of urea to graphene oxide is (2.5~3)︰1.
(3)将步骤(2)得到的前驱体进行研磨，得到前驱体粉末。 (3) Grinding the precursor obtained in step (2) to obtain precursor powder.
(4)将步骤(3)得到的前驱体粉末在惰性气体保护和700~1000℃条件下固相反应90~120min，然后进行冷却，得到黑色固体粉末。 (4) The precursor powder obtained in step (3) was subjected to a solid-state reaction at 700-1000° C. for 90-120 minutes under the protection of an inert gas, and then cooled to obtain a black solid powder.
其中，惰性气体为氮气。 Wherein, the inert gas is nitrogen.
(5)将步骤(4)得到的黑色固体粉末进行研磨，依次用蒸馏水和无水乙醇洗涤，然后在10~80℃恒温干燥，制得掺杂型石墨烯负载PtRu合金纳米电催化剂。 (5) The black solid powder obtained in step (4) was ground, washed with distilled water and absolute ethanol in sequence, and then dried at a constant temperature of 10-80°C to prepare a doped graphene-supported PtRu alloy nano-electrocatalyst.
实施例2Example 2
一种掺杂型石墨烯负载PtRu合金纳米电催化剂及其制备方法。所述电催化剂中：PtRu合金为20~25wt%，掺杂型石墨烯为75~80wt%；PtRu合金的粒径为0.5~9.5nm。 A doped graphene-supported PtRu alloy nano electrocatalyst and a preparation method thereof. In the electrocatalyst: the PtRu alloy is 20-25wt%, and the doped graphene is 75-80wt%; the particle size of the PtRu alloy is 0.5-9.5nm.
所述掺杂型石墨烯中的掺杂元素为N；N的掺杂量为掺杂型石墨烯的5~8wt%。 The doping element in the doped graphene is N; the doping amount of N is 5-8wt% of the doped graphene.
所述PtRu合金中Pt与Ru的物质的量的比为1∶(1.2~1.6)。 The ratio of the amount of Pt to Ru in the PtRu alloy is 1: (1.2-1.6).
所述掺杂型石墨烯负载PtRu合金纳米电催化剂的制备方法，其具体步骤是： The preparation method of described doped graphene supported PtRu alloy nanometer electrocatalyst, its specific steps are:
(1)将石墨烯氧化物溶液、H2PtCl6·6H2O溶液和RuCl3·3H2O溶液搅拌均匀，得到均分散悬浮液； (1) Stir the graphene oxide solution, the H 2 PtCl 6 6H 2 O solution and the RuCl 3 3H 2 O solution evenly to obtain a homogeneously dispersed suspension;
其中，石墨烯氧化物∶H2PtCl6·6H2O∶RuCl3·3H2O的质量比为75~80∶40~55∶20~30；石墨烯氧化物溶液的浓度为2~10g/L，H2PtCl6·6H2O溶液的浓度为5~20g/L，RuCl3·3H2O溶液的浓度为5~20g/L。 Among them, the mass ratio of graphene oxide: H 2 PtCl 6 ·6H 2 O: RuCl 3 ·3H 2 O is 75~80:40~55:20~30; the concentration of graphene oxide solution is 2~10g/ L, the concentration of H 2 PtCl 6 ·6H 2 O solution is 5~20g/L, the concentration of RuCl 3 ·3H 2 O solution is 5~20g/L.
(2)向步骤(1)得到的均分散悬浮液中加入掺杂物，搅拌溶解后，在搅拌和20~60℃条件下恒温干燥，得到前驱体。 (2) Add dopant to the homogeneously dispersed suspension obtained in step (1), stir to dissolve, and then dry under stirring and constant temperature at 20-60° C. to obtain a precursor.
其中，掺杂物为尿素，尿素与石墨烯氧化物的质量比为(2~2.5)︰1。 Wherein, the dopant is urea, and the mass ratio of urea to graphene oxide is (2~2.5)︰1.
(3)将步骤(2)得到的前驱体进行研磨，得到前驱体粉末。 (3) Grinding the precursor obtained in step (2) to obtain precursor powder.
(4)将步骤(3)得到的前驱体粉末在惰性气体保护和600~900℃条件下固相反应60~90min，然后进行冷却，得到黑色固体粉末。 (4) The precursor powder obtained in step (3) was subjected to a solid-state reaction at 600-900° C. for 60-90 minutes under the protection of an inert gas, and then cooled to obtain a black solid powder.
其中，惰性气体为氩气。 Wherein, the inert gas is argon.
(5)将步骤(4)得到的黑色固体粉末进行研磨，依次用蒸馏水和无水乙醇洗涤，然后在10~80℃恒温干燥，制得掺杂型石墨烯负载PtRu合金纳米电催化剂。 (5) The black solid powder obtained in step (4) was ground, washed with distilled water and absolute ethanol in sequence, and then dried at a constant temperature of 10-80°C to prepare a doped graphene-supported PtRu alloy nano-electrocatalyst.
实施例3Example 3
一种掺杂型石墨烯负载PtRu合金纳米电催化剂及其制备方法。所述电催化剂中：PtRu合金为15~20wt%，掺杂型石墨烯为80~85wt%；PtRu合金的粒径为0.5~9.5nm。 A doped graphene-supported PtRu alloy nano electrocatalyst and a preparation method thereof. In the electrocatalyst: the PtRu alloy is 15-20wt%, and the doped graphene is 80-85wt%; the particle size of the PtRu alloy is 0.5-9.5nm.
所述掺杂型石墨烯中的掺杂元素为N；N的掺杂量为掺杂型石墨烯的3~6wt%。 The doping element in the doped graphene is N; the doping amount of N is 3~6wt% of the doped graphene.
所述PtRu合金中Pt与Ru的物质的量的比为1∶(0.8~1.2)。 The ratio of the amount of Pt to Ru in the PtRu alloy is 1: (0.8-1.2).
所述掺杂型石墨烯负载PtRu合金纳米电催化剂的制备方法，其具体步骤是： The preparation method of described doped graphene supported PtRu alloy nanometer electrocatalyst, its specific steps are:
(1)将石墨烯氧化物溶液、H2PtCl6·6H2O溶液和RuCl3·3H2O溶液搅拌均匀，得到均分散悬浮液； (1) Stir the graphene oxide solution, the H 2 PtCl 6 6H 2 O solution and the RuCl 3 3H 2 O solution evenly to obtain a homogeneously dispersed suspension;
其中，石墨烯氧化物∶H2PtCl6·6H2O∶RuCl3·3H2O的质量比为80~85∶30~45∶10~20；石墨烯氧化物溶液的浓度为2~10g/L，H2PtCl6·6H2O溶液的浓度为5~20g/L，RuCl3·3H2O溶液的浓度为5~20g/L。 Among them, the mass ratio of graphene oxide: H 2 PtCl 6 ·6H 2 O: RuCl 3 ·3H 2 O is 80~85:30~45:10~20; the concentration of graphene oxide solution is 2~10g/ L, the concentration of H 2 PtCl 6 ·6H 2 O solution is 5~20g/L, the concentration of RuCl 3 ·3H 2 O solution is 5~20g/L.
(2)向步骤(1)得到的均分散悬浮液中加入掺杂物，搅拌溶解后，在搅拌和20~60℃条件下恒温干燥，得到前驱体。 (2) Add dopant to the homogeneously dispersed suspension obtained in step (1), stir to dissolve, and then dry under stirring and constant temperature at 20-60° C. to obtain a precursor.
其中，掺杂物为尿素，尿素与石墨烯氧化物的质量比为(1.5~2)︰1。 Wherein, the dopant is urea, and the mass ratio of urea to graphene oxide is (1.5~2)︰1.
(3)将步骤(2)得到的前驱体进行研磨，得到前驱体粉末。 (3) Grinding the precursor obtained in step (2) to obtain precursor powder.
(4)将步骤(3)得到的前驱体粉末在惰性气体保护和500~800℃条件下固相反应30~60min，然后进行冷却，得到黑色固体粉末。 (4) The precursor powder obtained in step (3) was subjected to a solid-state reaction at 500-800° C. for 30-60 minutes under the protection of an inert gas, and then cooled to obtain a black solid powder.
其中，惰性气体为氮气。 Wherein, the inert gas is nitrogen.
(5)将步骤(4)得到的黑色固体粉末进行研磨，依次用蒸馏水和无水乙醇洗涤，然后在10~80℃恒温干燥，制得掺杂型石墨烯负载PtRu合金纳米电催化剂。 (5) The black solid powder obtained in step (4) was ground, washed with distilled water and absolute ethanol in sequence, and then dried at a constant temperature of 10-80°C to prepare a doped graphene-supported PtRu alloy nano-electrocatalyst.
实施例4Example 4
一种掺杂型石墨烯负载PtRu合金纳米电催化剂及其制备方法。所述电催化剂中：PtRu合金为10~15wt%，掺杂型石墨烯为85~90wt%；PtRu合金的粒径为0.5~9.5nm。 A doped graphene-supported PtRu alloy nano electrocatalyst and a preparation method thereof. In the electrocatalyst: the PtRu alloy is 10-15wt%, the doped graphene is 85-90wt%, and the particle size of the PtRu alloy is 0.5-9.5nm.
所述掺杂型石墨烯中的掺杂元素为N；N的掺杂量为掺杂型石墨烯的1~4wt%。 The doping element in the doped graphene is N; the doping amount of N is 1-4wt% of the doped graphene.
所述PtRu合金中Pt与Ru的物质的量的比为1∶(0.5~0.8)。 The substance amount ratio of Pt and Ru in the PtRu alloy is 1: (0.5-0.8).
所述掺杂型石墨烯负载PtRu合金纳米电催化剂的制备方法，其具体步骤是： The preparation method of described doped graphene supported PtRu alloy nanometer electrocatalyst, its specific steps are:
(1)将石墨烯氧化物溶液、H2PtCl6·6H2O溶液和RuCl3·3H2O溶液搅拌均匀，得到均分散悬浮液； (1) Stir the graphene oxide solution, the H 2 PtCl 6 6H 2 O solution and the RuCl 3 3H 2 O solution evenly to obtain a homogeneously dispersed suspension;
其中，石墨烯氧化物∶H2PtCl6·6H2O∶RuCl3·3H2O的质量比为85~90∶15~35∶5~15；石墨烯氧化物溶液的浓度为2~10g/L，H2PtCl6·6H2O溶液的浓度为5~20g/L，RuCl3·3H2O溶液的浓度为5~20g/L。 Among them, the mass ratio of graphene oxide: H 2 PtCl 6 ·6H 2 O: RuCl 3 ·3H 2 O is 85~90:15~35:5~15; the concentration of graphene oxide solution is 2~10g/ L, the concentration of H 2 PtCl 6 ·6H 2 O solution is 5~20g/L, the concentration of RuCl 3 ·3H 2 O solution is 5~20g/L.
(2)向步骤(1)得到的均分散悬浮液中加入掺杂物，搅拌溶解后，在搅拌和20~60℃条件下恒温干燥，得到前驱体。 (2) Add dopant to the homogeneously dispersed suspension obtained in step (1), stir to dissolve, and then dry under stirring and constant temperature at 20-60° C. to obtain a precursor.
其中，掺杂物为尿素，尿素与石墨烯氧化物的质量比为(1~1.5)︰1。 Wherein, the dopant is urea, and the mass ratio of urea to graphene oxide is (1~1.5)︰1.
(3)将步骤(2)得到的前驱体进行研磨，得到前驱体粉末。 (3) Grinding the precursor obtained in step (2) to obtain precursor powder.
(4)将步骤(3)得到的前驱体粉末在惰性气体保护和400~700℃条件下固相反应5~30min，然后进行冷却，得到黑色固体粉末。 (4) The precursor powder obtained in step (3) was subjected to a solid-state reaction at 400-700° C. for 5-30 minutes under the protection of an inert gas, and then cooled to obtain a black solid powder.
其中，惰性气体为氩气。 Wherein, the inert gas is argon.
(5)将步骤(4)得到的黑色固体粉末进行研磨，依次用蒸馏水和无水乙醇洗涤，然后在10~80℃恒温干燥，制得掺杂型石墨烯负载PtRu合金纳米电催化剂。 (5) The black solid powder obtained in step (4) was ground, washed with distilled water and absolute ethanol in sequence, and then dried at a constant temperature of 10-80°C to prepare a doped graphene-supported PtRu alloy nano-electrocatalyst.
实施例5Example 5
一种掺杂型石墨烯负载PtRu合金纳米电催化剂及其制备方法。除下述技术参数外，其余同实施例1： A doped graphene-supported PtRu alloy nano electrocatalyst and a preparation method thereof. Except following technical parameter, all the other are with embodiment 1:
所述掺杂型石墨烯中的掺杂元素为B；所述掺杂物为硼酸；所述惰性气体为氩气。 The doping element in the doped graphene is B; the dopant is boric acid; and the inert gas is argon.
实施例6Example 6
一种掺杂型石墨烯负载PtRu合金纳米电催化剂及其制备方法。除下述技术参数外，其余同实施例2： A doped graphene-supported PtRu alloy nano electrocatalyst and a preparation method thereof. Except following technical parameter, all the other are with embodiment 2:
所述掺杂型石墨烯中的掺杂元素为B；所述掺杂物为硼酸；所述惰性气体为氮气。 The doping element in the doped graphene is B; the dopant is boric acid; and the inert gas is nitrogen.
实施例7Example 7
一种掺杂型石墨烯负载PtRu合金纳米电催化剂及其制备方法。除下述技术参数外，其余同实施例3： A doped graphene-supported PtRu alloy nano electrocatalyst and a preparation method thereof. Except following technical parameter, all the other are with embodiment 3:
所述掺杂型石墨烯中的掺杂元素为B；所述掺杂物为硼酸；所述惰性气体为氩气。 The doping element in the doped graphene is B; the dopant is boric acid; and the inert gas is argon.
实施例8Example 8
一种掺杂型石墨烯负载PtRu合金纳米电催化剂及其制备方法。除下述技术参数外，其余同实施例4： A doped graphene-supported PtRu alloy nano electrocatalyst and a preparation method thereof. Except following technical parameter, all the other are with embodiment 4:
所述掺杂型石墨烯中的掺杂元素为B；所述掺杂物为硼酸；所述惰性气体为氮气。 The doping element in the doped graphene is B; the dopant is boric acid; and the inert gas is nitrogen.
本具体实施方式与现有技术相比具有如下突出特点： Compared with the prior art, this specific embodiment has the following prominent features:
(1)本具体实施方式采用尿素为氮源对石墨烯进行氮掺杂、或采用硼酸为硼源对石墨烯进行硼掺杂，氮或硼的含量通过控制尿素或硼酸的加入量、反应温度和反应时间来进行调节；掺杂物直接溶于石墨烯氧化物溶液中，掺杂物与石墨烯氧化物充分接触，能快速高效地实现石墨烯的掺杂；掺杂型石墨烯作为载体，PtRu合金纳米粒子分散均匀，催化剂对甲醇的电催化活性明显提高。 (1) This specific embodiment adopts urea as a nitrogen source to carry out nitrogen doping to graphene, or adopts boric acid as a boron source to carry out boron doping to graphene, and the content of nitrogen or boron is controlled by the addition of urea or boric acid, the reaction temperature and the reaction time to adjust; the dopant is directly dissolved in the graphene oxide solution, and the dopant is in full contact with the graphene oxide, which can quickly and efficiently realize the doping of graphene; doped graphene is used as a carrier, The PtRu alloy nanoparticles are uniformly dispersed, and the electrocatalytic activity of the catalyst to methanol is obviously improved.
(2)本具体实施方式采用一步固相还原法制备掺杂型石墨烯负载PtRu合金纳米电催化剂，与现有技术相比，不需要先合成掺杂型石墨烯，也不需要很长的反应时间；而是将石墨烯的掺杂和PtRu合金纳米粒子的负载同时进行，反应温度为400~1000℃，反应时间为5~120min，故工艺简单，能耗低；采用惰性气体保护，能有效地防止石墨烯和贵金属的氧化；采用高温烧成和快速冷却的方法，可以通过控制烧成温度和保温时间来控制PtRu合金粒子的尺寸和粒径分布；催化剂中贵金属总含量在10~30wt%范围内可控，贵金属的利用率高。 (2) This specific embodiment adopts one-step solid phase reduction method to prepare doped graphene supported PtRu alloy nano-electrocatalyst, compared with the prior art, it is not necessary to first synthesize doped graphene, and it does not need a very long reaction Time; instead, the doping of graphene and the loading of PtRu alloy nanoparticles are carried out at the same time, the reaction temperature is 400~1000°C, and the reaction time is 5~120min, so the process is simple and the energy consumption is low; the use of inert gas protection can effectively It can effectively prevent the oxidation of graphene and precious metals; by using high-temperature firing and rapid cooling, the size and particle size distribution of PtRu alloy particles can be controlled by controlling the firing temperature and holding time; the total content of precious metals in the catalyst is 10~30wt% It is controllable within a certain range, and the utilization rate of precious metals is high.
本具体实施方式制备的掺杂型石墨烯负载PtRu合金纳米电催化剂，PtRu合金纳米粒子高度分散在掺杂型石墨烯表面，其粒径范围为0.5~9.5nm，有很强的石墨烯和PRu合金的面衍射峰。其中掺杂型石墨烯比表面积大，PtRu合金纳米粒子分散度高，从而能有效提高贵金属的利用率。如说明书附图所示：图1~图3为关于实施例1制备的一种掺杂型石墨烯负载PtRu合金纳米电催化剂TEM图、粒径分布直方图和XRD图；从图1可以看出，PtRu合金纳米粒子高度分散在掺杂型石墨烯表面；从图2可以看出，其粒径范围为0.5~9.5nm；从图3可以看出，XRD物相分析有很强的石墨烯（002）面衍射峰和PtRu合金的（111）、（200）、（220）面衍射峰。 The doped graphene-supported PtRu alloy nano electrocatalyst prepared in this specific embodiment, the PtRu alloy nanoparticles are highly dispersed on the surface of doped graphene, and its particle size range is 0.5 ~ 9.5nm, which has strong graphene and PRu Surface diffraction peaks of the alloy. Among them, the doped graphene has a large specific surface area and a high dispersion of PtRu alloy nanoparticles, which can effectively improve the utilization rate of precious metals. As shown in the accompanying drawings of the description: Fig. 1 ~ Fig. 3 is a kind of doped graphene supported PtRu alloy nano-electrocatalyst TEM figure, particle size distribution histogram and XRD figure prepared about embodiment 1; As can be seen from Fig. 1 , PtRu alloy nanoparticles are highly dispersed on the surface of doped graphene; as can be seen from Figure 2, the particle size range is 0.5~9.5nm; as can be seen from Figure 3, XRD phase analysis has a strong graphene ( 002) plane diffraction peaks and (111), (200), (220) plane diffraction peaks of PtRu alloy.
本具体实施方式采用三电极体系测试其甲醇氧化电催化性能，将催化剂、5wt%的Nation溶液和无水乙醇在超声波作用下混合均匀，将该均匀的浆料涂在玻碳电极上，在60℃下烘干，作为测量用的工作电极。测量用的对电极为碳棒，参比电极为Ag/AgCl电极（3.5MKCl），电解液为1MCH3OH+0.5MH2SO4。用循环伏安法评价本具体实施方式制备的PtRu合金纳米电催化剂对甲醇氧化的电催化活性，扫描速度为10mV/s，甲醇电氧化的峰电流密度为15.3~257.3A/g，正反向扫描对应的峰电流密度的比值为1.32~3.51，表现出很高的对甲醇氧化的电催化活性和抗CO中毒能力。用计时电流法评价本具体实施方式制备的掺杂型石墨烯负载PtRu合金纳米电催化剂的稳定性，初始电位为0.6V，经过500s，催化剂的甲醇氧化电流密度为5~108.5A/g，电流密度保持率为8.9~43.1%，故本具体实施方式所制备的掺杂型石墨烯负载PtRu合金纳米电催化剂对甲醇电氧化具有优异的稳定性。图4~图5为关于实施例1制备的一种掺杂型石墨烯负载PtRu合金纳米电催化剂在10mV/s扫描速度下的甲醇电催化氧化循环伏安曲线和电流-时间曲线，从图4可以看出，甲醇电氧化的峰电流密度为229.2A/g，正反向扫描对应的峰电流密度的比值为2.13，表现出很高的对甲醇氧化的电催化活性和抗CO中毒能力；从图5可以看出，经过500s，催化剂的甲醇氧化电流密度为95.3A/g，电流密度保持率为33.7%，表明催化剂具有很好的稳定性。 This specific embodiment uses a three-electrode system to test its methanol oxidation electrocatalytic performance. The catalyst, 5wt% Nation solution and absolute ethanol are mixed evenly under the action of ultrasonic waves, and the uniform slurry is coated on the glassy carbon electrode. It was dried at ℃ and used as the working electrode for measurement. The counter electrode used for measurement is carbon rod, the reference electrode is Ag/AgCl electrode (3.5MKCl), and the electrolyte is 1MCH 3 OH+0.5MH 2 SO 4 . Use cyclic voltammetry to evaluate the electrocatalytic activity of the PtRu alloy nano electrocatalyst prepared in this specific embodiment to the oxidation of methanol. The scan speed is 10mV/s, and the peak current density of methanol electrooxidation is 15.3~257.3A/g, forward and reverse The ratio of peak current densities corresponding to the scans is 1.32–3.51, showing high electrocatalytic activity for methanol oxidation and resistance to CO poisoning. Evaluate the stability of the doped graphene-loaded PtRu alloy nano-electrocatalyst prepared in this specific embodiment by chronoamperometry, the initial potential is 0.6V, after 500s, the methanol oxidation current density of the catalyst is 5 ~ 108.5A/g, the current The density retention rate is 8.9-43.1%, so the doped graphene-supported PtRu alloy nano electrocatalyst prepared in this specific embodiment has excellent stability for methanol electrooxidation. Fig. 4 ~ Fig. 5 is about the methanol electrocatalytic oxidation cyclic voltammetry curve and current-time curve of a kind of doped type graphene supported PtRu alloy nanometer electrocatalyst prepared in embodiment 1 under the scanning speed of 10mV/s, from Fig. 4 It can be seen that the peak current density of methanol electrooxidation is 229.2A/g, and the ratio of the peak current density corresponding to the forward and reverse scanning is 2.13, showing high electrocatalytic activity and anti-CO poisoning ability for methanol oxidation; from It can be seen from Figure 5 that after 500 s, the methanol oxidation current density of the catalyst is 95.3 A/g, and the current density retention rate is 33.7%, indicating that the catalyst has good stability.
因此，本具体实施方式具有工艺简单和能耗低的特点，所制备的掺杂型石墨烯负载PtRu合金纳米电催化剂催化活性高、稳定性好、纳米粒子分散均匀和粒径可控。 Therefore, this specific embodiment has the characteristics of simple process and low energy consumption, and the prepared doped graphene-supported PtRu alloy nano electrocatalyst has high catalytic activity, good stability, uniform dispersion of nanoparticles and controllable particle size.
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| CN107732260A (en) * | 2017-09-26 | 2018-02-23 | 天津工业大学 | A kind of preparation method of the N doping platinum nickel bimetal ethanol oxidation catalyst of cubic structure |
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| CN109482214A (en) * | 2018-10-23 | 2019-03-19 | 深圳市本征方程石墨烯技术股份有限公司 | The catalyst and preparation method of a kind of graphene-supported ruthenium metal and application |
| CN109596686B (en) * | 2018-12-06 | 2020-08-04 | 山西大学 | Electrochemical sensor for simultaneously detecting guanine and adenine and preparation method thereof |
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| CN114497583B (en) * | 2022-01-12 | 2024-05-07 | 青岛创启新能催化科技有限公司 | Preparation method of PtRu/CN catalyst for fuel cell |
| CN118800922A (en) * | 2024-09-13 | 2024-10-18 | 中汽研汽车检验中心（天津）有限公司 | Lamellar graphite carbon-based ruthenium cobalt electrocatalyst and preparation method thereof, and battery |
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