技术领域technical field
本发明涉及M掺杂于Sex-Ru/C的一步溶剂热制备方法及应用，属于材料合成技术领域。The invention relates to a one-step solvothermal preparation method and application of M doped inSex -Ru/C, belonging to the technical field of material synthesis.
背景技术Background technique
在近几年里，雾霾发生频率之高、波及范围之广以及其污染程度的严重性均前所未有。PM2.5爆表、空气能见度降低、中小学停课、高速公路封闭等事实不断地警示我们，污染治理必须从源头抓起，即减少污染物的排放，其中减少化石能源的使用是行之有效的方法之一。同时由于化石能源的不可再生性，因此清洁可再生能源的研究受到了越来越多的重视，直接甲醇燃料电池(Directmethanolfuelcell,DMFC)是以甲醇为燃料，具有其它类型低温燃料电池不可比拟的优点，如燃料来源丰富、价格便宜、电化学活性高、易于携带存储等，特别适合作为小型化电源或可移动电源，具有广阔的应用前景。In recent years, the occurrence frequency of smog is high, the scope of influence is wide, and the severity of its pollution is unprecedented. Facts such as PM2.5 explosion, reduced air visibility, suspension of primary and secondary schools, and closed highways constantly warn us that pollution control must start from the source, that is, reduce pollutant emissions, among which reducing the use of fossil energy is effective One of the methods. At the same time, due to the non-renewability of fossil energy, the research on clean and renewable energy has received more and more attention. Direct methanol fuel cell (DMFC) uses methanol as fuel and has incomparable advantages over other types of low-temperature fuel cells. , such as rich sources of fuel, cheap price, high electrochemical activity, easy to carry and store, etc., are especially suitable as miniaturized power sources or mobile power sources, and have broad application prospects.
DMFC有着巨大的应用价值，然而较高的成本和较短的寿命严重制约了其商业化进程，这两大问题的核心都与催化剂密不可分。目前，DMFC的阴极催化剂仍以Pt系催化剂为主，尽管其负载量已可降至0.5mg/cm2以下，但由于Pt资源稀少、价格昂贵，导致电池成本居高不下，限制了DMFC的商品化和规模化生产。同时，阴极缓慢的氧还原(Oxygenreductionreaction,ORR)动力学、阳极甲醇渗透以及中间氧化产物使Pt系催化剂中毒等问题也制约着DMFC技术的大规模应用和发展。因此，探索低成本、高阴极催化活性以及抗甲醇渗透能力强的非Pt催化剂就显得尤为迫切，这也是突破燃料电池价格瓶颈的关键技术之一。DMFC has great application value, but its high cost and short life seriously restrict its commercialization process. The core of these two problems is inseparable from the catalyst. At present, the cathode catalyst of DMFC is still dominated by Pt-based catalysts. Although its loading capacity can be reduced to below 0.5mg/cm2 , the cost of batteries remains high due to the scarcity and high price of Pt resources, which limits the commercialization of DMFC. and large-scale production. At the same time, the slow oxygen reduction (Oxygenreduction reaction, ORR) kinetics of the cathode, the methanol permeation of the anode, and the poisoning of Pt-based catalysts by intermediate oxidation products also restrict the large-scale application and development of DMFC technology. Therefore, it is particularly urgent to explore non-Pt catalysts with low cost, high cathode catalytic activity and strong methanol permeation resistance, which is also one of the key technologies to break through the price bottleneck of fuel cells.
目前，非Pt催化剂主要有过渡金属硫族化合物、过渡金属大环化合物以及过渡金属含氮载体复合物、过渡金属氧化物等。其中过渡金属硫族化合物在酸性介质中ORR活性高、选择性强、稳定性好，是一类很有前途的DMFC用阴极催化剂材料。在此类催化剂的研究中，Alonso-Vante教授领导的课题组做出了重要的贡献。1986年，他们首先报道了具有Chevrel相结构的Mo4.2Ru1.8Se8的合成方法，并证明其在酸性介质中对ORR具有可以与Pt相比的催化活性(见Alonso-VanteN.,TributschH.Energyconversioncatalysisusingsemiconductingtransitionmetalclustercompounds.Nature,1986,333:431-432)。2000年，他们又成功制备了Ru1.92Mo0.08SeO4，并发现其具有很好电催化活性的同时对甲醇呈现出完全的惰性(见SchmidtT.J.,PaulusU.A.,GasteigerH.A.,Alonso-VanteN.,BehmR.J.OxygenreductiononRu1.92Mo0.08SeO4,Ru/carbon,andPt/carboninpureandmethanolcontainingelectrolytes.J.Electrochem.Soc.,2000,147:2620-2624)。之后过渡金属硫族化合物得到了广泛的研究，然而Ru作为另外一种贵金属，减少其用量，同时增强催化剂的稳定性和抗甲醇性能对推动直接甲醇燃料电池的商业化有非常重要的意义。At present, non-Pt catalysts mainly include transition metal chalcogenides, transition metal macrocycles, transition metal nitrogen-containing support complexes, and transition metal oxides. Among them, transition metal chalcogenides have high ORR activity, strong selectivity, and good stability in acidic media, and are a promising class of cathode catalyst materials for DMFC. In the research of such catalysts, the research group led by Professor Alonso-Vante has made important contributions. In 1986, they first reported the synthesis method of Mo4.2 Ru1.8 Se8 with Chevrel phase structure, and proved that it has catalytic activity comparable to that of Pt for ORR in acidic medium (see Alonso-VanteN., TributschH.Energyconversioncatalysisusingsemiconductingtransitionmetalclustercompounds . Nature, 1986, 333:431-432). In 2000, they successfully prepared Ru1.92 Mo0.08 SeO4 , and found that it has good electrocatalytic activity and is completely inert to methanol (see SchmidtT.J., PaulusU.A., GasteigerH.A., Alonso-Vante N., Behm R.J. Oxygen reduction on Ru1.92Mo0.08SeO4, Ru/carbon, and Pt/carboninpureandmethanolcontainingelectrolytes. J. Electrochem. Soc., 2000, 147:2620-2624). Afterwards, transition metal chalcogenides have been extensively studied. However, as another noble metal, reducing the amount of Ru, while enhancing the stability and methanol resistance of the catalyst is of great significance to promote the commercialization of direct methanol fuel cells.
发明内容Contents of the invention
为解决现有技术的不足，本发明的目的在于提供一种制备工艺简单、周期短、氧还原活性高且具有良好抗甲醇性能的M掺杂于Sex-Ru/C的一步溶剂热制备方法及应用，即RuxMySez复合催化剂的溶剂热原位制备方法及应用。In order to solve the deficiencies of the prior art, the object of the present inventionis to provide a one-step solvothermal preparation method of M doped in Sex-Ru/C with simple preparation process, short cycle, high oxygen reduction activity and good methanol resistance And application, that is, the solvothermal in-situ preparation method and application of RuxMySez composite catalyst.
为了实现上述目标，本发明采用如下的技术方案：In order to achieve the above object, the present invention adopts the following technical solutions:
M掺杂于Sex-Ru/C的一步溶剂热制备方法，包括如下步骤：A one-step solvothermal preparation method for doping M on Sex -Ru/C, comprising the following steps:
S1、取0.6mmol钌盐、0.2～0.6mmol亚硒酸、95.6mg活性炭及M源加入到异丙醇溶剂中，超声搅拌得到混合均匀的反应前驱液，所述M源为0.009mmol钼盐或0.06mmol铂源或0.06mmol铁盐；S1. Take 0.6mmol of ruthenium salt, 0.2-0.6mmol of selenous acid, 95.6mg of activated carbon and M source into the isopropanol solvent, and ultrasonically stir to obtain a uniformly mixed reaction precursor solution. The M source is 0.009mmol of molybdenum salt or 0.06mmol platinum source or 0.06mmol iron salt;
S2、将步骤S1得到的反应前驱液倒入反应釜中，密封后置入带有旋转棒的反应炉中进行溶剂热反应，100～220℃保温10h，冷却至室温后用无水乙醇清洗多次，然后置于真空干燥箱中烘干得到黑色粉末中间产物；S2. Pour the reaction precursor solution obtained in step S1 into a reaction kettle, seal it and put it into a reaction furnace with a rotating rod for solvothermal reaction, keep it warm at 100-220°C for 10h, and wash it with absolute ethanol after cooling to room temperature times, and then placed in a vacuum oven to dry to obtain a black powder intermediate product;
S3、将步骤S2得到的黑色粉末中间产物放入到管式炉中进行煅烧，通入氮气与氢气的混合气体，加热至300～1000℃保温2～5h；S3. Put the black powder intermediate product obtained in step S2 into a tube furnace for calcination, feed a mixed gas of nitrogen and hydrogen, and heat to 300-1000° C. for 2-5 hours;
S4、将步骤S3的产物取出自然冷却至室温，得到产品M掺杂Sex-Ru/C催化剂。S4. The product in step S3is taken out and naturally cooled to room temperature to obtain a product M doped with Sex-Ru/C catalyst.
优选地，前述步骤S1中，钌盐为六水合三氯化钌或十二水合羰基钌，所述钼盐为四水合钼酸铵或六水合羰基钼，所述铂源为氯铂酸，所述铁盐为六水合氯化铁或九水合羰基铁。Preferably, in the aforementioned step S1, the ruthenium salt is ruthenium trichloride hexahydrate or ruthenium carbonyl dodecahydrate, the molybdenum salt is ammonium molybdate tetrahydrate or molybdenum carbonyl hexahydrate, and the platinum source is chloroplatinic acid. The iron salt is ferric chloride hexahydrate or carbonyl iron nonahydrate.
更优选地，前述异丙醇和无水乙醇均为分析纯级别。More preferably, the aforementioned isopropanol and absolute ethanol are of analytical grade.
再优选地，前述步骤S2中，反应前驱液在反应釜中的填充度为60％。More preferably, in the aforementioned step S2, the filling degree of the reaction precursor solution in the reactor is 60%.
进一步优选地，前述步骤S2中，所述反应釜为聚四氟乙烯反应釜。Further preferably, in the aforementioned step S2, the reactor is a polytetrafluoroethylene reactor.
进一步地，前述步骤S3中，氮气与氢气的气体流量之比为3:1。Further, in the aforementioned step S3, the gas flow ratio of nitrogen and hydrogen is 3:1.
此外，本发明还保护了由前述的制备方法得到的M掺杂Sex-Ru/C催化剂在直接甲醇燃料电池中的应用。In addition, the present invention also protects the application of the M-doped Sex-Ru/C catalyst obtainedby the aforementioned preparation method in direct methanol fuel cells.
本发明的有益之处在于：本发明在一步溶剂热下制备出了原位生长结晶性优异的M(M＝Mo,Pt,Fe)掺杂的Sex-Ru/C复合催化剂，得到在Sex-Ru/C中掺杂活性位点元素Mo、Pt或Fe且不含杂相的电催化剂，相比于其它制备方法来说，本发明的制备工艺更加简单、周期短、高效便捷且制备过程中环保无污染，所使用的化学试剂均为常用试剂，绿色环保、廉价易得、易于大规模应用及推广；经检测，本发明所制得的M掺杂尤其是Pt掺杂的Sex-Ru/C复合催化剂的氧还原、抗甲醇及稳定性能均得到优化，是一种有望在直接甲醇燃料电池中推广应用的新型复合催化剂。The benefit of the present invention is that: the present invention has prepared M(M= Mo, Pt, Fe) doped Sex-Ru/C composite catalyst with excellent in-situ growth crystallinity under one-step solvothermal, obtainedx -Ru/C is an electrocatalyst doped with active site elements Mo, Pt or Fe and does not contain heterophases. Compared with other preparation methods, the preparation process of the present invention is simpler, the cycle is short, efficient and convenient, and the preparation The process is environmentally friendly and pollution-free, and the chemical reagents used are all commonly used reagents, which are green, environmentally friendly, cheap and easy to obtain, and easy to be applied and promoted on a large scale; after testing, the M-doped, especially Pt-doped Sex prepared by the present invention is The oxygen reduction, methanol resistance and stability of the -Ru/C composite catalyst have been optimized, and it is a new composite catalyst that is expected to be popularized and applied in direct methanol fuel cells.
附图说明Description of drawings
图1是本发明的实施例1所制备的中间产物的XRD图谱；Fig. 1 is the XRD spectrum of the intermediate product prepared by the embodiment of the present invention 1;
图2是本发明的实施例1所制备的最终产品M(M＝Mo,Pt,Fe)掺杂的Sex-Ru/C复合催化剂的XRD图谱；Fig. 2 is the XRD spectrum of the final product M (M= Mo, Pt, Fe) doped Sex-Ru/C composite catalyst prepared by embodiment 1 of the present invention;
图3本发明中实施例1的所制备的最终产品M(M＝Mo,Pt,Fe)掺杂的Sex-Ru/C复合催化剂的氧还原性能测试图(LSV)；The oxygen reduction performance test figure (LSV) of the Sex-Ru/C composite catalyst of the prepared final product M (M= Mo, Pt, Fe) doping of embodiment 1 in Fig. 3 of the present invention;
图4为本发明中实施例1的所制备的Pt掺杂的Sex-Ru/C复合催化剂的抗甲醇性能测试图；Fig. 4 is the anti-methanol performance test figure of the prepared Pt-doped Sex-Ru/C composite catalyst of embodiment1 in the present invention;
图5为本发明中实施例1所制备的Pt掺杂的Sex-Ru/C复合催化剂的稳定性测试图。Fig. 5 is a stability test graph of the Pt-doped Sex-Ru/C composite catalyst prepared in Example1 of the present invention.
具体实施方式detailed description
以下结合附图和具体实施例对本发明作具体的介绍。The present invention will be specifically introduced below in conjunction with the accompanying drawings and specific embodiments.
实施例1Example 1
S1、取0.6mmol钌盐、0.2mmol亚硒酸、95.6mg活性炭及M源加入到异丙醇溶剂中，超声搅拌得到混合均匀的反应前驱液，其中，M源为0.009mmol钼盐或0.06mmol铂源或0.06mmol铁盐；S1. Add 0.6mmol ruthenium salt, 0.2mmol selenous acid, 95.6mg activated carbon and M source into isopropanol solvent, and ultrasonically stir to obtain a uniformly mixed reaction precursor, wherein the M source is 0.009mmol molybdenum salt or 0.06mmol Platinum source or 0.06mmol iron salt;
S2、将步骤S1得到的反应前驱液倒入25mL的聚四氟乙烯反应釜中，密封后置入带有旋转棒的反应炉中进行溶剂热反应，150℃保温10h，冷却至室温后用无水乙醇清洗3次，然后置于真空干燥箱中烘干得到黑色粉末中间产物；S2. Pour the reaction precursor solution obtained in step S1 into a 25mL polytetrafluoroethylene reactor, seal it and put it into a reaction furnace with a rotating rod for solvothermal reaction, keep it at 150°C for 10h, cool it to room temperature, and use Washed with water and ethanol for 3 times, then placed in a vacuum drying oven to dry to obtain a black powder intermediate product;
S3、将步骤S2得到的黑色粉末中间产物放入到管式炉中进行煅烧，通入氮气与氢气(气体流量之比为3:1)的混合气体，加热至300℃保温2h；S3. Put the black powder intermediate product obtained in step S2 into a tube furnace for calcination, feed a mixed gas of nitrogen and hydrogen (the gas flow ratio is 3:1), and heat to 300° C. for 2 hours;
S4、将步骤S3的产物取出自然冷却至室温，得到产品M掺杂Sex-Ru/C催化剂。S4. The product in step S3is taken out and naturally cooled to room temperature to obtain a product M doped with Sex-Ru/C catalyst.
实施例2Example 2
本实施例中，亚硒酸取量为0.4mmol，其余均与实施例1相同。In the present embodiment, the amount of selenous acid taken is 0.4 mmol, and the rest are all the same as in Example 1.
实施例3Example 3
本实施例中，亚硒酸取量为0.6mmol，其余均与实施例1相同。In the present embodiment, the amount of selenous acid taken is 0.6 mmol, and all the others are the same as in Example 1.
实施例4Example 4
本实施例中，步骤S2中的保温温度为100℃，其余均与实施例1相同。In this embodiment, the heat preservation temperature in step S2 is 100° C., and the rest are the same as in embodiment 1.
实施例5Example 5
本实施例中，步骤S2中的保温温度为120℃，其余均与实施例1相同。In this embodiment, the heat preservation temperature in step S2 is 120° C., and the rest are the same as in embodiment 1.
实施例6Example 6
本实施例中，步骤S2中的保温温度为200℃，其余均与实施例1相同。In this embodiment, the heat preservation temperature in step S2 is 200° C., and the rest are the same as in embodiment 1.
实施例7Example 7
本实施例中，步骤S2中的保温温度为220℃，其余均与实施例1相同。In this embodiment, the heat preservation temperature in step S2 is 220° C., and the rest are the same as in embodiment 1.
实施例8Example 8
本实施例中，步骤S3中的保温温度为500℃，保温时间为2h，其余均与实施例1相同。In this embodiment, the holding temperature in step S3 is 500° C., the holding time is 2 hours, and the rest are the same as in Example 1.
实施例9Example 9
本实施例中，步骤S3中的保温温度为800℃，保温时间为2h，其余均与实施例1相同。In this embodiment, the holding temperature in step S3 is 800° C., the holding time is 2 hours, and the rest are the same as in Example 1.
实施例10Example 10
本实施例中，步骤S3中的保温温度为1050℃，保温时间为2h，其余均与实施例1相同。In this embodiment, the holding temperature in step S3 is 1050° C., the holding time is 2 hours, and the rest are the same as in Example 1.
实施例11Example 11
本实施例中，步骤S3中的保温温度为300℃，保温时间为5h，其余均与实施例1相同。In this embodiment, the holding temperature in step S3 is 300° C., the holding time is 5 hours, and the rest are the same as in Example 1.
实施例12Example 12
本实施例中，步骤S3中的保温温度为500℃，保温时间为5h，其余均与实施例1相同。In this embodiment, the holding temperature in step S3 is 500° C., the holding time is 5 hours, and the rest are the same as in Example 1.
实施例13Example 13
本实施例中，步骤S3中的保温温度为800℃，保温时间为5h，其余均与实施例1相同。In this embodiment, the holding temperature in step S3 is 800° C., the holding time is 5 hours, and the rest are the same as in Example 1.
实施例14Example 14
本实施例中，步骤S3中的保温温度为1000℃，保温时间为5h，其余均与实施例1相同。In this embodiment, the holding temperature in step S3 is 1000° C., the holding time is 5 hours, and the rest are the same as in Example 1.
产品表征和性能检测Product Characterization and Performance Testing
本发明制备的M(M＝Mo,Pt,Fe)掺杂的Sex-Ru/C复合催化剂通过以下手段进行结构及形貌表征：选用日本理学UltimaIV的X射线衍射仪(XRD)对样品进行物相结构表征分析；选用日本HDHOKUTODENKO旋转圆盘电极对催化剂的氧还原性能、抗甲醇性能及稳定性进行测试。The M (M=Mo, Pt, Fe) doped Sex -Ru/C composite catalyst prepared by the present invention is characterized by structure and morphology by the following means: select the X-ray diffractometer (XRD) of Japan Rigaku UltimaIV to carry out the sample Characterization and analysis of phase structure; Japan HDHOKUTODENKO rotating disc electrode was used to test the oxygen reduction performance, methanol resistance performance and stability of the catalyst.
图1和图2为实施例1所制备的M(M＝Mo,Pt,Fe)掺杂的Sex-Ru/C复合催化剂煅烧前后的XRD图谱，对比可见，煅烧后催化剂均呈现出良好的Ru的特征宽峰，且M源的加入降低了催化剂的结晶性能。Fig. 1 and Fig. 2 are the XRD patterns of the M (M= Mo, Pt, Fe) doped Sex-Ru/C composite catalyst before and after calcination prepared in Example 1, and it can be seen from the comparison that the catalysts all present a good The characteristic broad peak of Ru, and the addition of M source reduces the crystallization performance of the catalyst.
图3为实施例1所制备的M(M＝Mo,Pt,Fe)掺杂的Sex-Ru/C复合催化剂的氧还原性能测试图(LSV)，图中Mo、Fe掺杂后氧还原性能有所降低，Pt掺杂后催化剂的极限电流增大，催化性能优于Sex-Ru/C催化剂。Fig. 3 is the oxygen reduction performance test diagram (LSV) of the M (M= Mo, Pt, Fe) doped Sex-Ru/C composite catalyst prepared in Example 1, and the oxygen reduction after Mo and Fe doping in the figure The performance decreased, and the limiting current of the catalyst increased after Pt doping, and the catalytic performance was better than that of the Sex -Ru/C catalyst.
图4为实施例1所制备的Pt掺杂的Sex-Ru/C复合催化剂的抗甲醇性能的测试图，在该图中，加入1M甲醇后出现了更为明显的氧还原峰，表明Pt掺杂的Sex-Ru/C复合催化剂的性能得到了提升。Fig. 4 is the test chart of the anti-methanol performance of the Pt-doped Sex-Ru/C composite catalyst prepared in Example1 , in this figure, after adding 1M methanol, a more obvious oxygen reduction peak appears, indicating that Pt The performance of the doped Sex -Ru/C composite catalyst has been improved.
图5为实施例1所制备的Pt掺杂的Sex-Ru/C复合催化剂的稳定性测试图，由图5可见，在0.4V(vs.RHE)时循环圈数高于40圈时，未掺杂Pt的催化剂出现了明显的衰减，表明Pt的掺杂大大提高了催化剂的稳定性。Fig. 5 is the stability test figure of the Pt-doped Sex-Ru/C composite catalyst prepared in embodiment 1, as seen from Fig. 5, when the cycle number is higher than 40 circles when 0.4V (vs.RHE ), The undoped Pt catalyst exhibited a significant attenuation, indicating that the Pt doping greatly improved the stability of the catalyst.
其余各实施例制得的催化剂尤其是Pt掺杂的Sex-Ru/C复合催化剂的氧还原、抗甲醇及稳定性能也都得到了优化，有望在直接甲醇燃料电池中推广应用。The catalysts prepared in other examples, especially the Pt-doped Sex -Ru/C composite catalysts, have also been optimized in oxygen reduction, methanol resistance and stability, and are expected to be popularized and applied in direct methanol fuel cells.
以上显示和描述了本发明的基本原理、主要特征和优点。本行业的技术人员应该了解，上述实施例不以任何形式限制本发明，凡采用等同替换或等效变换的方式所获得的技术方案，均落在本发明的保护范围内。The basic principles, main features and advantages of the present invention have been shown and described above. Those skilled in the industry should understand that the above-mentioned embodiments do not limit the present invention in any form, and all technical solutions obtained by means of equivalent replacement or equivalent transformation fall within the protection scope of the present invention.
| Application Number | Priority Date | Filing Date | Title |
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| CN201510650905.8ACN105363478A (en) | 2015-10-10 | 2015-10-10 | One-step solvothermal preparation and application of M doped in Sex-Ru/C |
| Application Number | Priority Date | Filing Date | Title |
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| CN201510650905.8ACN105363478A (en) | 2015-10-10 | 2015-10-10 | One-step solvothermal preparation and application of M doped in Sex-Ru/C |
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| CN105363478Atrue CN105363478A (en) | 2016-03-02 |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510650905.8APendingCN105363478A (en) | 2015-10-10 | 2015-10-10 | One-step solvothermal preparation and application of M doped in Sex-Ru/C |
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| CN (1) | CN105363478A (en) |
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| CN111545240A (en)* | 2020-05-29 | 2020-08-18 | 西安凯立新材料股份有限公司 | In-situ one-pot preparation method of Pt/Fe3O4Method and application of/C-N catalyst |
| CN114744176A (en)* | 2022-04-29 | 2022-07-12 | 东南大学 | Ruthenium-doped amorphous selenium material for anode of water-based zinc ion battery and preparation method thereof |
| CN120280508A (en)* | 2025-06-09 | 2025-07-08 | 长春黄金研究院有限公司 | High-entropy intermetallic compound bifunctional catalyst, and preparation method and application thereof |
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| CN100998948A (en)* | 2006-12-13 | 2007-07-18 | 太原理工大学 | Preparation method of oxygen electric reduction catalyst for direct methanol fuel battery |
| CN101779319A (en)* | 2007-08-09 | 2010-07-14 | 丰田自动车株式会社 | Fuel cell electrode catalyst, method for evaluating performance of oxygen-reducing catalyst, and solid polymer fuel cell comprising the fuel cell electrode catalyst |
| CN101807701A (en)* | 2010-04-23 | 2010-08-18 | 上海理工大学 | Direct methanol fuel cell anodic nano-catalyst and preparation method thereof |
| CN103050714A (en)* | 2011-10-17 | 2013-04-17 | 中国科学院大连化学物理研究所 | Nano carbon doped electrocatalyst for fuel cell, and application of nano carbon doped electrocatalyst |
| CN103143717A (en)* | 2011-12-06 | 2013-06-12 | 中国科学院大连化学物理研究所 | Platinoid bimetallic nanometer material and preparation method and application thereof |
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100998948A (en)* | 2006-12-13 | 2007-07-18 | 太原理工大学 | Preparation method of oxygen electric reduction catalyst for direct methanol fuel battery |
| CN101779319A (en)* | 2007-08-09 | 2010-07-14 | 丰田自动车株式会社 | Fuel cell electrode catalyst, method for evaluating performance of oxygen-reducing catalyst, and solid polymer fuel cell comprising the fuel cell electrode catalyst |
| CN101807701A (en)* | 2010-04-23 | 2010-08-18 | 上海理工大学 | Direct methanol fuel cell anodic nano-catalyst and preparation method thereof |
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| CN111545240A (en)* | 2020-05-29 | 2020-08-18 | 西安凯立新材料股份有限公司 | In-situ one-pot preparation method of Pt/Fe3O4Method and application of/C-N catalyst |
| CN114744176A (en)* | 2022-04-29 | 2022-07-12 | 东南大学 | Ruthenium-doped amorphous selenium material for anode of water-based zinc ion battery and preparation method thereof |
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