CN100522355C - Preparation method of oxygen electric reduction catalyst for direct methanol fuel battery - Google Patents

Preparation method of oxygen electric reduction catalyst for direct methanol fuel battery Download PDF

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CN100522355C
CN100522355C CN 200610102270 CN200610102270A CN100522355C CN 100522355 C CN100522355 C CN 100522355C CN 200610102270 CN200610102270 CN 200610102270 CN 200610102270 A CN200610102270 A CN 200610102270A CN 100522355 C CN100522355 C CN 100522355C
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catalyst
clusters
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CN100998948A (en )
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刘世斌
孙彦平
张忠林
段东红
牛秀红
郝晓刚
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太原理工大学
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Abstract

本发明属于直接甲醇燃料电池用氧电还原催化剂的制备方法。 The present invention is in the direct methanol fuel cell preparation of the catalyst reduced with electrically oxygen. 该工艺方法是在反应器内加入有机溶剂并通入氮气,后按比例加入Se粉、Ru<sub>3</sub>(CO)<sub>12</sub>、M(CO)<sub>x</sub>、Pt(CO)<sub>2</sub>回流、抽滤、洗涤、干燥,制得氧电还原催化剂;然后加入碳载体,再加蒸馏水配成乳液,超声均化,洗涤、干燥,得到碳载纳米铂掺杂的M-Ru-Se簇合物催化剂。 The process is to add an organic solvent in the reactor and purged with nitrogen, after the proportion added Se powder, Ru <sub> 3 </ sub> (CO) <sub> 12 </ sub>, M (CO) <sub > x </ sub>, Pt (CO) <sub> 2 </ sub> reflux, filtered off with suction, washed and dried to obtain an oxygen electro-reduction catalyst; followed by addition of carbon carriers, formulated together with distilled water emulsion, an ultrasonic homogenizer , washed, and dried, to give the nano-Pt doped M-Ru-Se catalyst clusters. 本发明利用铂和钌簇合物对氧还原具有较高的催化活性及钌簇合物还拥有良好的抗甲醇能力和稳定性,将铂掺杂于钌簇合物中,得到一类氧电还原催化活性高、抗甲醇能力强的碳载铂掺杂钌簇合物电催化剂,而且制备方法简单、成本低,电池输出功率大,可应用于燃料电池电极的制备。 Platinum and ruthenium clusters utilizing the present invention has high oxygen reduction activity and catalytic ruthenium Clusters also has good resistance to methanol and stability, ruthenium-doped platinum clusters to obtain a category of oxygen electrically reducing high catalytic activity, high resistance to methanol and carbon-supported platinum ability of ruthenium doped clusters electrocatalyst, and simple preparation process, low cost, battery output power, preparing a fuel cell electrode may be applied.

Description

直接甲醇燃料电池用氧电还原催化剂的制备方法 The catalyst preparation process direct methanol fuel cell with an oxygen reduction power

技术领域 FIELD

本发明涉及一种直接甲醇燃料电池用抗甲醇氧电还原催化剂----铂掺杂的纳米钌簇硒化合物催化剂的制备方法,属于燃料电池材料科学技术领域和电催化技术领域。 The present invention relates to a direct methanol fuel cell with an anti-oxo electrically methanol platinum catalyst preparation process ---- ruthenium nano-cluster doped selenium compound reduction catalyst, belonging to the technical field of fuel science and technology electrocatalytic cell material. 背景技术 Background technique

直接甲醇燃料电池(Direct Methanol Fuel Cells , DMFC)以其燃料来源丰富、储存方便、结构简单、质量轻、体积小、能量密度高、操作安全、有利于环境等优点而日益受到广泛关注,是最有希望成为便携式电子设备、移动电话和电动汽车理想的动力电源。 Direct methanol fuel cells (Direct Methanol Fuel Cells, DMFC) fuel source for its rich, easy to store, simple structure, light weight, small size, high energy density, safe operation, and the advantages of an environment conducive to increasingly widespread concern, is the most there is hope for portable electronic devices, mobile phones and electric cars ideal power supply. 但目前DMFC的发展面临着一个严重障碍——"甲醇透过"问题,即甲醇从阳极穿过电解质膜扩散到阴极,在阴极Pt/C催化剂上, 氧还原和甲醇氧化同时发生反应,产生"混合电位",严重降低电池的输出功率和甲醇的利用率。 But the DMFC faces a serious obstacle to the development - "methanol crossover" problem, i.e., diffusion of methanol through the electrolyte membrane from the anode to the cathode, the cathode in the Pt / C catalyst, the oxygen reduction and methanol oxidation reactions occur simultaneously, to produce " mixed potential ', seriously reduce the efficiency of the output power of the battery and methanol. 此外,甲醇及其氧化中间产物还会使Pt/C催化剂中毒,导致阴极极化增加,由此引起的电动势损失约为100mV〜200mV。 In addition, methanol and its oxidation intermediates would poison the Pt / C catalyst, resulting in increased cathodic polarization, thereby causing loss of the electromotive force of about 100mV~200mV. 所以,"甲醇透过"是阻碍Nafion膜电解质直接甲醇燃料电池应用的主要技术问题之一。 Therefore, the "methanol crossover" is hindering Nafion membrane electrolyte direct methanol one of the major technical problems for fuel cell applications. 解决该问题的方法之一是研制选择性好的阴极电催化剂,即催化剂只对氧还原有活性,而对甲醇氧化无活性或活性小,且自身也不会受到甲醇毒化。 One solution to this problem is to develop a cathode electrocatalyst good selectivity, i.e. only the oxygen reduction catalyst is active, and inactive or less active for the oxidation of methanol, and methanol itself will not be poisoned.

抗甲醇氧还原电催化材料的研究主要集中在非贵金属方面,主要有过渡金属大环化合物、过渡金属氧化物、过渡金属原子簇合物。 Anti Methanol electrocatalytic oxygen reduction material is concentrated in the non-precious metals, transition metals mainly macrocyclic compounds, transition metal oxides, transition metal atom clusters. 过渡金属大环化合物在作为DMFC阴极催化剂材料时,其固有活性相对纯金属Pt或Pt/C要低,而且在大环化合物催化氧还原过程中会产生不同程度的1«)2,并且随着反应时间的延长而不断聚集,严重腐蚀大环化合物和载体,破坏催化剂的结构,因此大环化合物催化剂的稳定性较差,阻碍其向实用化的进一步发展。 The transition metal macrocyclic compound as DMFC cathode catalyst material which intrinsic activity or relatively pure metal Pt Pt / C lower, but also in the macrocycle to catalyze oxygen reduction process will produce different degrees of 1 «) 2, and with reaction time and continue to gather, severe corrosion of the macrocyclic compound and the carrier, destruction of catalyst structure, and therefore less stable catalyst macrocyclic compound, which hindered further development of the practical. 过渡金属氧化物作为燃料电池阴极催化材料,其稳定性、活性均有待进一步提高,其抗甲醇性能尚待进一步证实。 Transition metal oxide catalytic material as a fuel cell cathode, the stability, activity was to be further improved, which properties should be further confirmed by the anti-methanol. 从目前研究的结果看,过渡金属簇合物是最有希望的氧电还原催化材料。 See from the results of the present study, the transition metal clusters is the most promising oxygen electro-reduction catalytic material. 这类催化剂是纳米过渡金属簇与硫族元素形成纳米金属簇化合物, Such catalysts are transition metal nano-clusters with chalcogen nano metal cluster compound is formed,

其通式可表示为Mo6—复Xs(X二Se、 Te、 Se0、 S等,M二0s、 Re、 Rh、 Ru等)。 Mo6- general formula can be expressed as complex Xs (X two Se, Te, Se0, S, etc., M two 0s, Re, Rh, Ru, etc.). i亥类催化剂的主要特性是对甲醇氧化呈惰性,即抗甲醇性。 Key features i Hai catalyst for methanol oxidation is inert, i.e. anti methanol resistance. 已有的研究表明,负载在活性碳上的无定型钌簇硒化合物Mo-Ru-Se用作氧还原电催化材料,具有良好的 Previous studies showed, supported on activated carbon, ruthenium cluster amorphous selenium compounds Mo-Ru-Se used as the oxygen-reduction catalytic material, having good

催化活性和抗甲醇毒化的能力,其稳定性基本达到电池运行的要求,是很有前途的DMFC阴极催化材料。 Methanol catalytic activity and resistance to poisoning, which substantially meet the requirements of stability of the battery operation, is promising DMFC cathode catalytic material. 从综合性能看,该类催化材料的电催化活性虽有了较大的提高,但仍不及纯金属Pt。 From the overall performance perspective, electro-catalytic activity of such catalytic materials, although greatly improved, but still not pure metal and Pt. 随着DMFC向实用化和商品化方向的进一步发展, 有关"甲醇透过"的问题将会越来越突出,因此,氧电还原催化活性高、抗甲醇能力强的阴极电催化剂的研制必将越来越受到人们的重视。 With the further development and commercialization of DMFC into practical direction, issues related to "methanol crossover" will become increasingly prominent, therefore, highly active oxygen-reducing catalytic power, strong anti-methanol ability of the cathode catalyst development will More and more attention has been paid. 发明内容 SUMMARY

本发明的目的是提供一种直接甲醇燃料电池用氧电还原催化剂的制备方法。 Object of the present invention is to provide a method for preparing a direct methanol fuel cell with oxygen reduction catalyst electricity. 以解决直接甲醇燃料电池"甲醇渗透"引起的混合电位问题,提高燃料电池的输出功率。 To address the direct methanol fuel cell "methanol crossover" mixed potential problems caused by increasing the output power of the fuel cell.

本发明提出的一种直接甲醇燃料电池用氧电还原催化剂的制备方法能够实现本发明上述提出目的以及解决的问题,该方法首先在反应器内加入有机溶剂并通入氮气,后按比例加入Se粉、Ru3(C0)12、 M(C0)x、 Pt(C0)2回流、抽虑、洗 The catalyst preparation process of the present invention proposed a direct methanol fuel cell with an oxygen reduction electrically forth above problem is solved and the object of the present invention can be implemented, the method first adding an organic solvent in the reactor and purged with nitrogen, was added after the proportion Se powder, Ru3 (C0) 12, M (C0) x, Pt (C0) 2 reflux, suction filtration, washed

涤、干燥,制得氧电还原催化剂;然后加入经过预处理的碳载体,再加蒸馏水配成乳液,超声均化,洗涤、干燥,得到碳载纳米铂掺杂的M-Ru-Se簇合物催化剂。 Brine, and dried, to obtain an oxygen electro-reduction catalyst; then, after addition of the carbon carrier pretreated, formulated together with distilled water emulsion, an ultrasonic homogenizer, washed, and dried, to give the Nano-Pt doped M-Ru-Se cluster bonded catalyst.

本发明提出的一种直接甲醇燃料电池用氧电还原催化剂的制备方法的具体技术方案按下列步骤进行:1) 在反应器内加入有机溶剂,通30min氮气,按3.92 : 1. 96 : 0.04 : 0. 02〜 0.5摩尔比加入Se粉、Ru"CO)12、 M(CO)" Pt(CO)"然后在110。C〜180。C温度下继续通入氮气并不断搅拌回流15〜25h,制备得到由上述四种元素组成的纳米催化剂溶胶;反应结束后,抽虑,用丙酮洗涤,室温干燥20h,即可得到黑色粉 The catalyst preparation process of the present invention proposed a direct methanol fuel cell with a reduced oxygen electrically particular technical solution according to the following steps: 1) adding an organic solvent in a reactor, pass 30min nitrogen by 3.92: 1.96: 0.04: 0. 02~ 0.5 molar ratio of Se powder is added, Ru "CO) 12, M (CO)" Pt (CO) "and then continue introducing nitrogen at a constant stirring and reflux temperature 110.C~180.C 15~25h, nanocatalyst prepared by the sol of four elements; after completion of the reaction, suction filtration, washed with acetone, and dried 20h at room temperature, to obtain a black powder

末状Pt-M-Ru-Se抗甲醇中毒的燃料电池用氧电还原催化剂; End shaped Pt-M-Ru-Se anti methanol fuel cells with oxygen reduction catalyst poisoning electricity;

2) 将碳载体在惰性气体保护下,30(TC〜60(TC烘烤1〜4小时,除去碳表面 2) the carbon support under an inert atmosphere, 30 (TC~60 (TC baked ~ 4 hours to remove the carbon surface

杂质; Impurities;

3)称取上述2)中经过预处理的碳载体和上述l)制备的催化剂粉末,其加入质量比为1:1〜2.2,加蒸馏水配成l mg • mL—1的溶液,超声波均化10 min, 至均匀分散,空气中40 'C干燥,依次用蒸馏水及丙酮洗涤,室温干燥20 h, 得到碳载纳米铂掺杂的M-Ru-Se簇合物催化剂。 3) Weigh the catalyst powder 2) after pretreatment of the carbon support and said l) prepared as above, added mass ratio of 1: 1~2.2, distilled water dubbed l mg • mL-1 solution, an ultrasonic homogenizer 10 min, until homogeneous dispersion, air 40 'C and dried, successively washed with distilled water and acetone, drying at room temperature 20 h, to give the nano-Pt doped M-Ru-Se catalyst clusters.

上述直接甲醇燃料电池用氧电还原催化剂的制备方法使用的M(COK中M为Mo、 Fe、 Co或Ni;有机溶剂为:二甲苯、甲苯、氯苯或间二氯苯。 M (M COK preparation of a catalyst in the direct methanol fuel cell power reduction of oxygen used is Mo, Fe, Co or of Ni; an organic solvent: xylene, toluene, chlorobenzene or m-dichlorobenzene.

利用本发明制得的直接甲醇燃料电池用氧电还原催化剂采用透射电镜观察催化剂微观形貌,利用本发明的制备方法得到的直接甲醇燃料电池用氧电还原催化剂颗粒粒径在3〜6nm;采用光电子能谱分析样品表面元素及其价态;催化剂活性及抗甲醇性的评价采用三电极体系,进行动电位扫描方法测试。 The present invention is made using the direct methanol fuel cell with an oxygen reduction catalyst was electrically catalyst morphology was observed by transmission electron microscopy, direct methanol fuel cell using the method of the present invention obtained with oxygen reduction catalyst particle size electrical 3~6nm; using photoelectron spectroscopy and elemental valence of the sample surface; catalyst activity and resistance to methanol evaluation of a three-electrode system, potentiodynamic scan test method. 工作电极的制备方法:称取5mg催化剂,加入2ml乙醇和50u 1的5%Nafion溶液,超声波分散成墨汁状,用微量进样器取1涂覆于经处理的干净旋转圆盘玻碳电极表面,烘干。 The method of preparing the working electrode: Weigh 5mg catalyst was added 2ml of ethanol and 1 50U 5% Nafion solution, ultrasonic dispersion into ink form, taken with a micro-syringe applied to a clean processed rotating disk glassy carbon electrode ,drying. 参比电极为Hg/Hg2S04,对电极为Pt丝环,使用的电极工作面积为玻碳电极的面积,为0.3cm2。 Reference electrode of Hg / Hg2S04, Pt wire counter electrode is a ring electrode used in the work area to the area of ​​the glassy carbon electrode, is 0.3cm2. 由测得的阴极极化曲线得到,本发明制得的催化剂与未掺杂铂的钌簇硒化合物催化剂相比,峰电流高UO mA'mg—1;在含甲醇电解液中,峰电流高85 mA • mg—、说明本发明制得的直接甲醇燃料电池用氧电还原催化剂具有优异的氧电还原催化活性和抗甲醇中毒性能。 Obtained from the cathodic polarization curve measured, the catalyst prepared by the invention in comparison with undoped platinum ruthenium catalyst cluster selenium compound, the peak current is high UO mA'mg-1; methanol containing electrolyte, the peak current is high 85 mA • mg-, described direct methanol fuel cell of the present invention is prepared with an oxygen reduction catalyst having electrically excellent oxygen-reducing catalytic activity and electrical performance of anti-poisoning methanol. 本发明利用铂和钌簇合物都对氧还原具^较高的催化活性,并且钌簇合物还拥有良好的抗甲醇性能和稳定性,将铂掺杂于钌簇合物,制成的直接甲醇燃料电池用氧电还原催化剂后,Pt以氧化物形式存在于Ru金属核表面,形成一层极薄的Pt氧化物层,使原来的氧还原活性中心原子排列的几何形状、原子的电子结构都发生一定变化,Pt的变价性质使其可通过结合氧原子与释放氧原子的方式进行助催化,从而起到协助Ru催化转化吸附态氧的作用。 The present invention utilizes both platinum and ruthenium clusters ^ oxygen reduction having higher catalytic activity, and ruthenium clusters also has good resistance to methanol and stability properties, doped platinum ruthenium clusters, made after the direct methanol fuel cell with an oxygen reduction catalyst power, Pt is present in oxide form in the surface of the core metal Ru, a Pt thin layer of oxide, so that the original geometry of the oxygen reduction activity center arrangement of atoms, electrons atoms structures changed differently, the price change properties so that it can be co-Pt catalyzed by binding an oxygen atom releasing oxygen atom way catalytic converter which play assisting Ru adsorbed oxygen effect. 由于氧在Pt活性位上具有较高的电还原活性,因而Ru金属核对氧的电催化还原活性有所提高。 Since having a high oxygen reduction activity in the electrically active sites on the Pt, Ru metal thus electrocatalytic oxygen reduction activity collation improved. 另外,钌簇合物在铂表面的特殊分散方式,使得铂表面的活性位只能与分子结构较小的氧相互作用,而甲醇由于分子位阻较大而无法与铂的活性位接触,因此提高了催化剂的抗甲醇性能。 Further, in particular ruthenium clusters dispersed manner the platinum surface, the platinum surface so that the active sites can interact with the molecular structure of the smaller oxygen molecules due to the steric hindrance of methanol and a large active site and can not contact with the platinum, thus improved resistance to methanol catalyst performance. 与现有技术相比,本发明所用的直接甲醇燃料电池用氧电还原催化剂制备方法简单、成本较低,对膜的要求低,电池的输出功率高。 Compared with the prior art, the direct methanol fuel cell used in the present invention is a method of preparing an oxygen reduction catalyst electrical simple, low cost, low requirements for the film, a high-output battery. 附图说明图1是实施例1合成的Pt-Mo-Ru-Se催化剂的透射电镜(TEM)照片;图中: 有许多直径在3〜5 nm之间的圆斑,斑中布满规则条纹,该圆斑为钌纳米簇, 条纹为金属纳米簇的晶格。 TEM Pt-Mo-Ru-Se catalyst BRIEF DESCRIPTION OF DRAWINGS FIG. 1 is synthesized in Example 1 (TEM) photograph; FIG: Many circular spot diameter between 3~5 nm, plaques covered with stripes rules the circular spot ruthenium nanoclusters, the metal nanoclusters fringes lattice. 图2是Pt-Mo-Ru-Se催化剂的XRD图,从由图可知,该样品的衍射角在2 P=42° ,判断应为块状Ru原子的(002)和(100)晶面,颗粒粒径在3〜6 nm。 FIG 2 is a XRD pattern Pt-Mo-Ru-Se catalyst from the figure shows, the diffraction angle of the sample in 2 P = 42 °, should be determined (002) (100) crystal plane and a bulk Ru atoms, the particle size 3~6 nm. 图中没有出现Mo、 Se、 Pt等掺杂元素单质衍射峰,表明掺杂元素未能形成单质金属颗粒。 FIG no Mo, Se, Pt and other doping element elemental diffraction peaks were unable doping element elemental metal particles. 图3和表1是Pt-Mo-Ru-Se催化剂样品的XPS分析结果。 Figure 3 and Table 1 are the results of XPS analysis Pt-Mo-Ru-Se catalyst samples. 可以看出,合成催化剂中有Ru、 Mo、 Se及Pt元素存在。 As can be seen, there is synthesis catalyst Ru, Mo, Se and Pt elements present. 由各元素峰结合能分析得知,Ru结合能为280. 03eV,以Ru金属体心立方晶体形式存在;Se以Se。 Each element analysis showed that the peak binding energy, binding energy Ru, Ru in the presence of a metal body centered cubic crystalline form as 280. 03eV; Se to Se. 形式存在;Mo以氧化物Mo20s存在;Pt以Pt02形式存在。 Existence; Mo20s presence of Mo oxide; Pt02 present in the form of Pt. Mo、 Pt可能以氧化物形式附着于Ru金属核的表面。 Mo, Pt may be attached to a surface in the form of oxides of Ru metal core. Pt的电子结合能(与纯Pt相比)发生了变化,即电子结构发生了变化,这可能是导致所得的催化剂具有优异的抗甲醇中毒性能的原因之一。 Pt electron binding energy (compared to pure Pt) changes, i.e. electronic structure change, which may be one cause of the resulting catalyst has excellent methanol poisoning resistance performance. 图4是六种催化剂在60。 FIG 4 is a six kinds of catalyst 60. C下0.5 mol'L—1 H2S04中的动电位扫描曲线。 0.5 mol'L-1 under potentiodynamic curve H2S04 C. 如图可见,本发明的催化剂Pt-Mo-Ru-Se对氧还原的电流峰值可达213 mA*mg—1以上, 而未掺杂铂的Mo-Ru-Se峰电流仅在100 mA • mg—1左右。 As can be seen, the catalyst of the present invention is Pt-Mo-Ru-Se oxygen reduction peak current up to 213 mA * mg-1 or more, whereas the platinum-doped Mo-Ru-Se peak current is only 100 mA • mg -1 around. 可见掺杂铂钌簇硒化合物催化活性比未掺杂铂的大大提高,具有良好的氧电还原催化性能。 Visible selenium compound doped platinum-ruthenium cluster catalytic activity than platinum undoped greatly improved, good electrical performance of the oxygen reduction catalyst. 图5是六种催化剂在甲醇浓度为0.2 mol • L—'的0.5 mol • L—1 H2S04中的动电位扫描曲线。 FIG 5 is six kinds of catalyst in a methanol concentration of 0.2 mol • L- 'of 0.5 mol • L-1 potentiodynamic curve of H2S04. 由图可知,六种催化剂的峰电流都有所下降,起始还原过电位都负移,电流密度大小顺序与无甲醇电解质情形相同。 The figure shows that the peak current has decreased six kinds of catalysts, the onset reduction potential are negative shifted over a current density of the order of the same case and methanol-free electrolyte. 但掺杂铂的钌簇硒化合物Pt-Mo-Ru-Se峰电流密度为165 mA . mg—、比未摻杂钼的Mo-Ru-Se (峰电流密度79 mA • mg—0高1倍,铂掺杂的钌簇合物抗甲醇性能较高。 具体实施方式本发明结合附图及实施例能够对本发明作出进一步的详细说明如下: 实施例l1) 在反应器内加入100 ml 二甲苯,通30 min氮气,按3,92 : 1.96 : 0。04 : 0.23摩尔比加入Se粉、Ru3(C0)12、 Mo(CO)e、 Pt(C0)236mg, 在139匸温度下继续通入氮气搅拌回流20 h,制备得到由Pt-Mo-Se-Ru四种元素组成的纳米催化剂溶胶,然后抽虑,用丙酮洗涤,室温干燥20 h,即可得到黑色粉末状Pt-Mo-Se-Ru抗甲醇中毒的燃料电池用用氧电还原催化剂。 However, the platinum ruthenium doped selenium compound cluster Pt-Mo-Ru-Se peak current density of 165 mA. Mg-, molybdenum than the undoped Mo-Ru-Se (peak current density of 79 mA • mg-0 is 1 times platinum clusters anti-doping ruthenium high performance methanol embodiment of the present invention in conjunction with the accompanying drawings and embodiments can be made in further detail of the present invention is described as follows: Example l1 embodiment) Add 100 ml of xylene in the reactor, through 30 min with nitrogen, by 3,92: 1.96: 0.04: 0.23 molar ratio of Se powder was added, Ru3 (C0) 12, Mo (CO) e, Pt (C0) 236mg, continuing to pass nitrogen at a temperature of 139 Xi was stirred at reflux for 20 h, prepared by the sol nano catalyst Pt-Mo-Se-Ru four elements, and then suction filtration, washed with acetone and dried at room temperature 20 h, to give a black powder Pt-Mo-Se-Ru anti methanol poisoning the fuel cell power reducing catalyst with oxygen. 其透射电镜(TEM)照片、XRD图、光电子能谱(XPS)分别见图l、图2、图3和表一。 Its TEM (TEM) photograph, XRD FIG photoelectron spectroscopy (XPS) are shown in Figure L, Figure 2, Figure 3 and Table. 2) 将碳载体Vulcan XC-72在惰性气体Ar保护下,600。 2) The carbon support is Vulcan XC-72 under an inert protective gas such as Ar, 600. C烘烤1小时,除去碳表面杂质。 C baked for one hour to remove the impurities carbon surface. 3)称取上述2)中经过预处理的Vulcan XC-72和上述1)制备的催化剂粉末,其加入质量比为1.2: 1,加蒸馏水配成lmg*mL—i的乳液,超声波均化10min, 至均匀分散,空气中40 'C干燥,依次用蒸馏水及丙酮洗涤,室温干燥20 h, 得到碳载纳米铂掺杂的M-Ru-Se簇合物催化剂。 3) above was weighed and Vulcan XC-72 catalyst powder prepared above 2) in the pre-processed), added mass ratio of 1.2: 1 with distilled water dubbed lmg * mL-i emulsion, an ultrasonic homogenizer 10min , until homogeneous dispersion, air 40 'C and dried, successively washed with distilled water and acetone, drying at room temperature 20 h, to give the nano-Pt doped M-Ru-Se catalyst clusters. 称取5mg上述制备的催化剂制成三电极体系中的工作电极,进行动电位扫描测定,实验结果如图4和图5的曲线"D"所示。 Weigh 5mg made catalyst prepared above three-electrode system of a working electrode, potentiodynamic scan measurement, the experimental results shown in "D" 4 and FIG. 5 is a graph in FIG. 从图可知,氧在钌簇合物Pt-Mo-Ru-Se催化剂上的还原起始电位为0. 1V(相对于标准氢电极),按单位质量催化剂电流为基准,峰电流可达213 mA'mg—、当加入甲醇在0. 2 mol'L—1甲醇+0.5mol'L—US04电解液时,氧在催化剂上的还原起始电位负移至O.OV,峰电流下降至165 mA . mg—1,降低了22. 5%。 Seen from FIG an oxygen reduction starting potential of ruthenium in clusters Pt-Mo-Ru-Se catalyst 0. 1V (vs. standard hydrogen electrode), the current per unit mass of the catalyst as a reference, the peak current up to 213 mA 'mg-, when methanol was added at 0. 2 mol'L-1 methanol + 0.5mol'L-US04 electrolyte, an oxygen reduction starting potential of the catalyst in the negative moved O.OV, the peak current is decreased to 165 mA . mg-1, decreased 22.5%. 实施例21) 在反应器内加入100ml氯苯溶剂,通30min氮气,按3.92 : 1.96 : 0.04 : 0. 29摩尔比加入Se粉、Ru3(C0)12、 Co2(C0)8、 Pt(C0)236 mg, 在132-C温度下继续通入氮气搅拌回流15h,制备得到纳米Pt-Co-Se-Ru四种元素组成的催化剂溶胶,然后抽虑,用丙酮洗涤,室温干燥20h,即可得到黑色私、 末状Pt-Co-Ru-Se抗甲醇中毒的燃料电池用氧电还原催化剂;2) 将碳载体Vulcan XC-72在惰性气体Ar保护下,480。 Example 21) was added into the reactor in the solvent chlorobenzene 100ml, 30min on nitrogen by 3.92: 1.96: 0.04: 0.29 molar ratio of Se powder was added, Ru3 (C0) 12, Co2 (C0) 8, Pt (C0) 236 mg, 132-C at a temperature of nitrogen was continuously stirred under reflux 15H, nano sol prepared catalyst Pt-Co-Se-Ru four elements, and then suction filtration, washed with acetone, and dried 20h at room temperature, to obtain private black, like the end Pt-Co-Ru-Se anti methanol poisoning the fuel cell with an oxygen reduction catalyst electric; 2) support the Vulcan XC-72 carbon in an inert gas such as Ar protection, 480. C烘烤2小时,除去碳表面杂质;3)称取上述2)中经过预处理的Vulcan XC-72和上述1)制备的催化剂粉末,其加入质量比为1.8: 1,加蒸馏水配成lmg*mL—i的乳液,超声波均化l(kin, 至均匀分散,空气中40 'C干燥,依次用蒸馏水及丙酮洗涤,室温干燥20 h, 得到碳载纳米铂掺杂的Co-Ru-Se簇合物催化剂。用同样的条件测定工作电极的动电位扫描曲线,实验结果如图4-5的曲线"B"所示。 实施例31 )在反应器内加入100ml 二甲苯溶剂,通30min氮气,按3.92 : 1.96 : 0.04 : 0. 29摩尔比加入Se粉、Rii3(C0),2、Fe3(C0),2、Pt(C0)2 36 mg, 在139。 C bake 2 hours to remove carbon impurities on the surface; 3), said Vulcan XC-72 and said catalyst powder prepared taken 2) above pretreated), added mass ratio of 1.8: 1 with distilled water lmg dubbed emulsion * mL-i, and an ultrasonic homogenizer l (kin, until homogeneous dispersion, air 40 'C and dried, successively washed with distilled water and acetone, drying at room temperature 20 h, to give the nano-Pt doped Co-Ru-Se the catalyst clusters. Determination of the working electrode with the same conditions as potentiodynamic curves, the experimental results shown by the graph of 4-5 "B" as shown in Example 31) was added 100ml of xylene solvent in the reactor, nitrogen gas through 30min , by 3.92: 1.96: 0.04: 0.29 molar ratio of Se powder was added, Rii3 (C0), 2, Fe3 (C0), 2, Pt (C0) 2 36 mg, 139. C温度下继续通入氮气搅拌回流15h,制备得到纳米Pt-Fe-Se-Ru四种元素组成的催化剂溶胶,然后抽虑,用丙酮洗涤,室温干燥20 h,即可得到黑色粉末状Pt-Fe-Ru-Se抗甲醇中毒的燃料电池用氧电还原催化剂;2)将碳载体Vulcan XC-72R在惰性气体Ar保护下,38(TC烘烤4小时,除去碳表面杂质;3)称取上述2)中经过预处理的Vulcan XC-72R和上述1)制备的催化剂粉末,其加入质量比为1.2: 1,加蒸馏水配成lmg'mL—'的乳液,超声波均化10min, 至均匀分散,空气中40 "C干燥,依次用蒸馏水及丙酮洗涤,室温干燥20 h, 得到碳载纳米铂掺杂的Fe-Ru-Se簇合物催化剂。用同样的条件测定工作电极的动电位扫描曲线,实验结果如图4-5的曲线"A"所示。 实施例41 )在反应器内加入100ml间二氯苯溶剂,通30min氮气,按3.92 : 1.96 : 0'04 : 0.42摩尔比加入Se粉、Ru"C0)12、 Ni(C0)4、 Pt(C0)236 mg, 在147t:温度下继续通 C was continuously fed at a temperature of nitrogen is stirred at reflux for 15H, the catalyst prepared by sol nano Pt-Fe-Se-Ru four elements, and then suction filtration, washed with acetone and dried at room temperature 20 h, to give a black powder Pt- Fe-Ru-Se anti methanol poisoning the fuel cell power oxygen reduction catalyst; and 2) the carbon support Vulcan XC-72R in an inert gas such as Ar protection, 38 (TC baked for 4 hours to remove carbon impurities on the surface; 3) Weigh 2 above) was pretreated Vulcan XC-72R and said catalyst powder prepared in 1), added mass ratio of 1.2: 1 with distilled water dubbed lmg'mL- 'emulsion, an ultrasonic homogenizer 10min, until homogeneous dispersion air 40 "C and dried, successively washed with distilled water and acetone, drying at room temperature 20 h, to give the nano-Pt doped Fe-Ru-Se catalyst clusters. Determination of the working electrode with the same conditions as potentiodynamic curve , as shown in Figure 4-5 results in curve "a" in Example 41) was added m-dichlorobenzene solvent in a 100ml reactor, 30min on nitrogen by 3.92: 1.96: 0'04: 0.42 molar ratio of added Se powder, Ru "C0) 12, Ni (C0) 4, Pt (C0) 236 mg, at 147t: the temperature continues to pass 氮气搅拌回流20 h,制备得到纳米Pt-Ni-Se-Ru四种元素组成的催化剂溶胶,然后抽虑,用丙酮洗涤,室温干燥20 h,即可得到黑色粉末状Pt-Ni-Ru-Se抗甲醇中毒的燃料电池用氧电还原催化剂;2)将碳载体碳纤维在惰性气体Ar保护下,60(TC烘烤1小时,除去碳表面杂质;3)称取上述2)中经过预处理的碳纤维和上述l)制备的催化剂粉末,其加入质量比为1.2:1,加蒸馏水配成lmg'mL—i的乳液,超声波均化10min,至均匀分散,空气中40 "C干燥,依次用蒸馏水及丙酮洗涤,室温干燥20 h,得到碳纤维载纳米钼掺杂的Ni-Ru-Se簇合物催化剂。用同样的条件测定工作电极的动电位扫描曲线,实验结果如图4-5的曲线"E"所示。 实施例5其它条件同实施例l,仅所加各组分中不含羰基铂Pt(C0)2,制得碳载纳米Mo-Ru-Se簇合物催化剂。用同样的条件测定工作电极的动电位扫描曲线,实验结果如图4-5的 Nitrogen was stirred at reflux for 20 h, the catalyst prepared by sol nano-Pt-Ni-Se-Ru four elements, and then suction filtration, washed with acetone and dried at room temperature 20 h, to give a black powder Pt-Ni-Ru-Se anti methanol fuel cell with oxygen reduction catalyst poisoning electricity; 2) the carbon fibers in the carbon support under inert gas Ar protection, 60 (TC baked for one hour to remove carbon impurities on the surface; 3) 2 Weigh) above pretreated catalyst powder and said carbon fibers l) is prepared, added mass ratio of 1.2: 1 with distilled water emulsion formulated lmg'mL-i, an ultrasonic homogenizer 10min, until homogeneous dispersion, air 40 "C and dried, washed with distilled water washed with acetone and dried at room temperature 20 h, to obtain a carbon fiber doped molybdenum nano-Ni-Ru-Se catalyst clusters. Determination of the working electrode with the same conditions as potentiodynamic curve, the curve shown in Figure 4-5 results. " E "shown in Example 5 other conditions as in Example l, only the components added do not contain platinum carbonyl Pt (C0) 2, prepared by the nano-Mo-Ru-Se catalyst clusters. same measurement conditions of the working electrode potentiodynamic curves of the experimental results shown in Figure 4-5 曲线"C"所示。 实施例6其它条件同实施例1,仅改变铂的质量百分含量,加入Se粉、Ru3(C0)12、 Mo(C0)6、 Pt(C0)2,其摩尔比为Se:Ru:Mo:Pt=3. 92 : 1.96 : 0.04 : 0.5。用同样的条件测定工作电极的动电位扫描曲线,实验结果如图4-5的曲线"F"所示。 Curve "C" shown in Example 6 Other conditions were the same as in Example 1, changing only the mass percentage of platinum was added Se powder, Ru3 (C0) 12, Mo (C0) 6, Pt (C0) 2, molar ratio Se: Ru: Mo: shown in "F" curve 0.5 Determination of the working electrode with the same conditions as potentiodynamic curves, the experimental results in FIG. 4-5: Pt = 3 92:. 1.96: 0.04..

Claims (3)

  1. 1. 直接甲醇燃料电池用氧电还原催化剂的制备方法,所制备的催化剂为碳载纳米铂掺杂的M-Ru-Se簇合物催化剂,其特征在于该方法首先在反应器内加入有机溶剂并通入氮气,后按比例加入Se粉、Ru3(C0)12、M(CO)x、Pt(CO)2回流并继续通入氮气,抽滤、洗涤、干燥,制得纳米铂掺杂的M-Ru-Se簇合物;然后加入碳载体,再加蒸馏水配成乳液,超声均化,洗涤、干燥,制得碳载纳米铂掺杂的M-Ru-Se簇合物催化剂,其中,M为Mo、Fe、Co或Ni;当M为Mo时,x为6;当M为Fe时,M(CO)x为Fe3(CO)12;当M为Co时,M(CO)x为Co2(CO)8;当M为Ni时,x为4。 The catalyst preparation process 1. direct methanol fuel cell electricity oxygen reduction, the catalyst is prepared platinum nanoparticles on carbon doped M-Ru-Se catalyst clusters, characterized in that the method of adding an organic solvent in the first reactor and purged with nitrogen, was added in proportion to the Se powder, Ru3 (C0) 12, M (CO) x, Pt (CO) 2 and reflux continued purged with nitrogen, filtration, washing and drying, to obtain a platinum-doped nano M-Ru-Se clusters; was then added to the carbon support, plus distilled water emulsion formulated, an ultrasonic homogenizer, washed, and dried to prepare a carbon-supported platinum nanoparticles doped M-Ru-Se catalyst clusters, wherein M is Mo, Fe, Co or of Ni; and when M is Mo, x is 6; when M is Fe, M (CO) x to Fe3 (CO) 12; when M is Co, M (CO) x to Co2 (CO) 8; when M is Ni, x is 4.
  2. 2. 根据权利要求1所述的直接甲醇燃料电池用氧电还原催化剂的制备方法,其特征在于所述的有机溶剂为:二甲苯、甲苯、氯苯或间二氯苯。 The direct methanol fuel cell as claimed in claim 1, said catalyst prepared by reduction of oxygen electrically, characterized in that the organic solvents are: xylene, toluene, chlorobenzene or m-dichlorobenzene.
  3. 3. 根据权利要求1所述的直接甲醇燃料电池用氧电还原催化剂的制备方法,其特征在于所述的碳载体为:Vulcan XC_72、 Vulcan XC-72R或碳纤维。 The direct methanol fuel cell according to claim 1 for preparing the catalyst oxygen reduction electrically, wherein the carbon support is: Vulcan XC_72, Vulcan XC-72R or carbon fibers.
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