WO2022087784A1 - 一种均相催化剂及阴离子交换膜燃料电池催化层 - Google Patents

一种均相催化剂及阴离子交换膜燃料电池催化层 Download PDF

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WO2022087784A1
WO2022087784A1 PCT/CN2020/123686 CN2020123686W WO2022087784A1 WO 2022087784 A1 WO2022087784 A1 WO 2022087784A1 CN 2020123686 W CN2020123686 W CN 2020123686W WO 2022087784 A1 WO2022087784 A1 WO 2022087784A1
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catalyst
homogeneous
side chain
molecular
polymer
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和庆钢
任荣
王晓江
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浙江大学
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • 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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  • the invention belongs to the field of fuel cells, and relates to a homogeneous catalyst and an anion exchange membrane fuel cell catalyst layer.
  • the membrane electrode assembly consists of a gas diffusion layer, a catalytic layer and an ion exchange membrane.
  • ionomers In the catalytic layer of the fuel cell, there are nano-catalysts such as Pt/C to complete the catalytic reaction, and there are also ionomers (Ionomers) having a structure similar to that of the ion-exchange membrane. Ionomers act as both a binder and an ionic conductor, thereby constituting a steric site where ionically conducting materials, electronically conducting materials, and reactants are together confined to the catalytic site, enabling catalytic reactions.
  • Ionomers act as both a binder and an ionic conductor, thereby constituting a steric site where ionically conducting materials, electronically conducting materials, and reactants are together confined to the catalytic site, enabling catalytic reactions.
  • the Pt surface would be uniformly covered by a thin film of Ionomer, but the reality is that no matter how much the ink is stirred, a considerable portion of the Pt particles will not be covered by the ionomer when forming the catalytic layer, so there is no ionic conduction channels, resulting in low catalyst utilization.
  • agglomeration or excessive coverage of ionomers can also hinder the diffusion of gases, thereby affecting the catalytic efficiency.
  • electrocatalysis is a surface interface reaction, the internal atoms of the nanoparticles cannot be effectively used.
  • the difficulty in realizing homogeneous catalysis in the catalytic layer of fuel cells lies in how to uniformly and stably intercalate molecular catalysts into the medium where oxygen, ions and electrons reach.
  • phase separation occurs through hydrophilic-hydrophobic interactions, where the hydrophilic part of the ionic group constitutes ionic nanochannels, a homogeneous system from a local perspective. Therefore, in order to apply the concept of homogeneous catalysis to the fuel cell catalyst layer, molecular catalysts must be placed in the ion channels where the electroactive species are located.
  • the invention discloses a class of ionomers containing molecular catalysts in the side chains.
  • the molecular catalysts are distributed on the side chains, so the obtained catalyst complexes have high-density active sites, which are randomly dispersed in an ion-conducting medium. .
  • This strategy establishes a novel stable homogeneous catalytic system, such as interconnected nanoreactors, and most importantly, each catalyst molecule anchored in the ion channel can serve as an active center at the "three-phase interface"
  • the parts can theoretically be fully utilized 100%.
  • the object of the present invention is to provide a homogeneous catalyst and an anion exchange membrane fuel cell catalytic layer in view of the deficiencies of the prior art, by designing and synthesizing a class of ionic polymers containing molecular catalysts and quaternary ammonium salts in their side chains, and using them as The homogeneous catalyst is applied to the catalyst layer of the fuel cell, which greatly improves the utilization rate of the catalyst, improves the mass transfer of the catalyst layer, and improves the performance of the fuel cell.
  • a homogeneous catalyst is a kind of ionic polymer containing molecular catalysts and quaternary ammonium salt groups in the side chain, which is obtained by introducing a fuel cell cathode or anode molecular catalyst into the side chain of the bromoalkyl group-containing polymer.
  • the bromoalkyl group is quaternized to obtain;
  • the molecular catalyst is a metal complex catalyst containing porphyrin, phthalocyanine or carrole; the side chain contains a bromoalkyl group.
  • the polymer is a polybromoalkyl fluorene with the following structure:
  • n is the degree of aggregation.
  • Described molecular catalyst is selected from:
  • M is Fe, Co, Cu, Ni or Pt.
  • the method adopted for introducing the molecular catalyst into the side chain of the polymer is: first, the molecular catalyst is subjected to a substitution reaction, and then reacted with the bromine in the brominated alkyl side chain on the polymer to form a co-polymer. valence bonds, thereby attaching the molecular catalyst to the side chains of the polymer.
  • the molecular catalyst can be subjected to a substitution reaction to form a phenolic hydroxyl group on the molecular catalyst, and then the phenolic hydroxyl group of the molecular catalyst can react with the bromine on the bromoalkyl group on the polymer to form an ether bond, thereby connecting the molecular catalyst to the on the side chains of the polymer.
  • the molar ratio of the molecular catalyst to the bromoalkyl group on the polymer is 1:10-1:2.
  • An anion-exchange membrane fuel cell catalytic layer based on a homogeneous catalyst is prepared by configuring the above-mentioned homogeneous catalyst, conductive carbon black, and N,N-dimethylformamide into a catalyst slurry, which is coated on a gas diffusion layer material After drying, a catalytic layer is obtained.
  • the homogeneous catalyst in the catalytic layer is phase-separated due to the hydrophilic-hydrophobic interaction (hydrophilic side chain and hydrophobic main chain), while the molecular catalyst is distributed in the hydrophilic ion channel formed by the side chain.
  • a microreactor similar to a solution homogeneous system is formed, and the microreactors are connected by hydrophilic ion channels.
  • the present invention obtains a homogeneous catalytic system in the catalyst layer of an anion exchange membrane fuel cell by immobilizing the molecular catalyst in the side chain of the ionomer and distributing it in the ion channel.
  • molecular catalysts are distributed along ion channels, greatly increasing catalyst utilization and improving mass transfer.
  • Molecular catalysts are covalently bonded to ionomers, and the catalysts exhibit excellent electrochemical stability.
  • the homogeneous system also improves atomic efficiency and exhibits higher peak power density in fuel cell single-cell tests, indicating improved mass transfer in the homogeneous catalyst layer.
  • the design strategy of catalytic layers based on homogeneous catalysts can also be extended to other electrochemical energy conversion devices to fully fill practical applications of non-noble metal materials by simply improving mass transfer and utilization of catalytic sites.
  • FIG. 1 is a comparison diagram of a traditional heterogeneous catalyst-based catalytic layer (A) and a homogeneous catalyst-based catalytic layer (B) proposed by the present invention, and a schematic structural diagram (C) of the homogeneous catalyst in the present invention.
  • Fig. 2 is the synthetic route of homogeneous catalyst PF-TMPPCo.
  • Fig. 3 is the synthetic route of homogeneous catalyst PF-PcFe.
  • Figure 4 shows the basic characterization of the homogeneous catalyst PF-TMPPCo, demonstrating the successful synthesis of the material.
  • Figure 5 shows the microscopic topography of the homogeneous catalyst after carbon loading.
  • Figure 6 shows the microscopic morphology and element distribution of the homogeneous catalyst. Molecular catalysts are uniformly distributed in ion channels composed of side-chain quaternary ammonium salt groups.
  • Figure 7 is a comparison of the oxygen reduction activity of the homogeneous catalyst and other heterogeneous catalysts.
  • Figure 8 is the switching frequency (TOF) of metal centers in different catalysts. Among them, the homogeneous catalyst exhibited the highest TOF.
  • Figure 9 shows the stability of the homogeneous catalyst PF-TMPPCo.
  • Figure 10 shows the fuel cell polarization curves of homogeneous catalyst PF-TMPPCo, heterogeneous blend catalyst PFI-TMPPCo and PFBr-TMPPCo without quaternary ammonium salt.
  • Figure 11 is the hydrogen oxidation curve of the molecular catalyst TMPPPt at different rotational speeds.
  • Bromhexylfluorene and monohydroxybenzene-trimethoxyphenylporphyrin cobalt were synthesized by themselves.
  • Bromhexyl polyfluorene is prepared by the polymerization of bromohexyl fluorene and trifluoroacetone under the catalysis of trifluoromethanesulfonic acid.
  • FIG. 1 is a comparison between the traditional platinum-based catalytic layer and the carbon-doped PF-TMPPCo catalytic layer of the present invention.
  • a traditional catalytic layer and its sites where the reaction cannot be completed i, platinum uncovered by Ionomer ii, unused nano-platinum center; iii, overly covered Ionomer affects the transport of reaction gas;
  • B novel homogeneous catalytic layer Schematic diagram of molecular catalysts distributed in ion channels composed of ionomers to form interconnected microreactors.
  • PF-TMPPCo by one-pot modification of bromohexylpolyfluorene: hydroxyphenyl-trimethoxyphenylporphyrin cobalt TMPPCo - OH (588 mg), K2CO3 (150 mg ), bromohexylpolyfluorene PF (1.44 mg) g) and DMF (100 mL) solution were stirred under nitrogen atmosphere at 80°C for 24 h. After TMPPCo was attached to the PF side chain, 2 mL of trimethylamine (30 wt% in ethanol) was added and the mixture was allowed to react at 50°C for 24 hours under a sealed system.
  • reaction solution was poured into water to precipitate, sonicated, washed and centrifuged 3 times with 0.1 M hydrochloric acid and deionized water to remove the reactants.
  • the obtained catalyst was vacuum-dried at 60 °C for 24 h, and was directly used as an electrochemical catalyst after being mixed with carbon materials.
  • reaction solution was poured into water to precipitate, sonicated, washed and centrifuged 3 times with 0.1 M hydrochloric acid and deionized water to remove the reactants.
  • the obtained catalyst was vacuum-dried at 60 °C for 24 h, and was directly used as an electrochemical catalyst after being mixed with carbon materials.
  • Figure 3 is a synthetic route diagram of a representative homogeneous PF-PcFe catalyst.
  • Electrochemical measurements were performed by using an Autolab PGSTAT302N potentiometer with a freshly fabricated reversible hydrogen electrode (RHE) as the reference electrode and platinum wire as the counter electrode in 0.1 M KOH solution.
  • Catalyst Ink was prepared by mixing catalyst powder (1 mg), PF ionomer (1 mg) and ECP carbon (10 mg) in a mixture of 4 mL of DMF (when the catalyst powder is the homogeneous catalyst prepared in the present invention, it can be No need to add PF ionomer).
  • GC glassy carbon
  • the electrodes were dried in an isopropanol-saturated atmosphere. Each suspension was freshly prepared before experiments were performed. The electrolyte was filled with Ar or O 2 by bubbling Ar or O 2 30 minutes before starting each measurement. A stream of Ar or O2 was continuously bubbled over the electrolyte during the test to ensure Ar or O2 saturation. Both CV and RDE measurements were performed in Ar-saturated or O - saturated 0.1 M KOH solution with a scan rate of 10 mV s ⁇ 1 .
  • the electrocatalyst slurry To prepare the electrocatalyst slurry, weigh the catalyst (10 mg), PF ionomer (10 mg) and ECP carbon (100 mg) in a mixture of 40 mL of DMF to prepare catalyst Ink (when the catalyst powder is prepared by the present invention) In the case of a homogeneous catalyst, the addition of a PF ionomer may not be required). The mixture was then transferred to a glass vial, which was immersed in a water ultrasonic bath and left to stand for 30 minutes to form a homogeneous slurry mixture.
  • the galvanostatic polarization curves of the fuel cells were recorded using Fuel Cell Software Version 4 (Scribner Associates).
  • Figure 4 is the characterization of the PF-TMPPCo catalyst structure. In the picture:
  • Figure 5 shows the microphase separation structure of the catalyst.
  • A SEM image of PF-TMPPCo
  • B TEM image
  • C PF-TMPPCo
  • D elemental image of PFI-TMPPCo.
  • PF Ionomer is coated on the outside of carbon nanospheres to form a porous catalytic layer structure.
  • the Co element distribution of PF-TMPPCo is more uniform than that of PFI-TMPPCo.
  • Figure 6 shows the microscopic morphology of the catalyst.
  • A Atomic-resolution high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) image of PF-TMPPCo (single Co atoms show sharp contrast).
  • B Energy dispersive X-ray spectroscopic image of PF-TMPPCo.
  • C Net scan intensity profile of the area indicated by the green rectangle in Fig. 3b, the light blue rectangle corresponds to the ion channel area.
  • D Simulated configurations of PF-TMPPCo and E, PFI-TMPPCo (a mixture of PF ionomer and TMPPCo): Co (yellow), O (red), N (purple), F (green) and C (grey). Left: full image; right: only Co atoms are shown for clarity. The red cycle highlights the aggregation of porphyrin rings in PFI-TMPPCo.
  • FIG. 7 shows the ORR polarization curves of different catalysts at a rotational speed of 900 rpm.
  • PF-TMPPCo exhibited the highest half-wave potential.
  • Figure 8 shows the switching frequency (TOF) of metal centers in different catalysts. Among them, the homogeneous catalyst exhibited the highest TOF.
  • Figure 9 shows the stability of the homogeneous catalyst PF-TMPPCo. After 20,000 cycles of testing, PF-TMPPCo has only a half-wave attenuation of 15mV, proving its excellent stability.
  • FIG. 10 is the fuel cell polarization curves of the homogeneous catalyst PF-TMPPCo, the heterogeneous blend catalyst PFI-TMPPCo and the PFBr-TMPPCo without quaternary ammonium salt. Homogeneous catalysts show higher advantages in fuel cells.
  • Figure 11 is the hydrogen oxidation curve of the molecular catalyst TMPPPt at different rotational speeds. It can be seen that the homogeneous catalyst prepared by the

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Abstract

本发明公开了一种均相催化剂及阴离子交换膜燃料电池催化层，所述均相催化剂是一类侧链含分子催化剂和季铵盐基团的离子聚合物，是通过将燃料电池阴极或阳极分子催化剂引入到侧链含溴代烷基的聚合物的侧链中，再将溴代烷基进行季铵化得到的；所述均相催化剂由疏水性多芳烃主链和亲水性季铵盐侧链组成，可形成微相分离；分子催化剂分布于侧链所构成的亲水离子通道中，形成类似于溶液均相体系的微反应器，微反应器之间通过亲水离子通道连接，基于该新型均相催化剂的燃料电池比传统非均相催化剂燃料电池的功率密度提升了三倍，稳定性也得到了极大的提升。

Description

一种均相催化剂及阴离子交换膜燃料电池催化层 技术领域
本发明属于燃料电池领域，涉及一种均相催化剂及阴离子交换膜燃料电池催化层。
背景技术
燃料电池作为一种清洁、高效、安全绿色的能量转换装置，有望成为新能源应用中最突出的一种新技术。其中，碱性阴离子交换膜燃料电池具有比功率高、发电效率高、环境友好性的优点，同时避免了质子交换膜燃料电池贵金属催化剂成本较高，甲醇透过率高的劣势，从而成为备受关注的新能源技术。作为燃料电池的核心，膜电极组件由气体扩散层，催化层和离子交换膜构成。
在燃料电池催化层中，存在诸如Pt/C之类的纳米催化剂以完成催化反应，同时还有具有与离子交换膜相似结构的离聚物(Ionomer)。Ionomer既充当粘合剂又充当离子导体，从而构成一个空间位点，在该空间位点，离子导电材料、电子导电材料和反应物一起被限制在催化位点上，从而实现催化反应。在理想条件下，Pt表面将被Ionomer的薄膜均匀覆盖，但是实际情况是，无论搅拌油墨的程度如何，在形成催化层时，相当一部分Pt颗粒都不会被离聚物覆盖，因此没有离子传导通道，导致催化剂利用率低。另一方面，离聚物的附聚或过度覆盖也会阻碍气体的扩散，从而影响催化效率。另外，即使对于可以被离聚物均匀地覆盖的催化剂纳米粒子，由于电催化是表 面界面反应，所以不能有效地使用纳米粒子的内部原子。例如，对于3.9nm球形纳米Pt颗粒，可以发挥催化作用的最外层原子的比例仅为26％。因此，可以看出，当前基于非均相催化的催化层结构具有几个根深蒂固的缺点：(i)三相界面的局限性，例如未被离聚物覆盖或位于微小孔中的Pt纳米颗粒载体，均不能完成催化反应，(ii)离聚物的团聚导致对氧传质的抵抗，(iii)纳米粒子核心内部的原子不能被有效地利用。
这些问题促使我们思考能否对催化层的结构进行改变，引入均相分子催化的概念。在均相催化中，催化剂与反应物质以分子状态存在于相同的介质中，因此均相催化剂具有较高的利用率，避免了非均相催化剂的传质问题，并具有较好的催化选择性。然而，尽管有分子催化剂固定在碳载体或气体扩散电极表面的研究，关于在燃料电池中实现均相催化系统的报道很少。在燃料电池催化层中实现均相催化的困难在于，如何将分子催化剂均匀稳定的嵌入氧气、离子和电子到达的介质中。在催化剂层的离聚物膜中，通过亲水-疏水相互作用进行相分离，其中离子基团的亲水部分构成离子纳米通道，从局部角度来看是均匀的系统。因此，为了将均相催化的概念应用于燃料电池催化剂层，必须将分子催化剂置于电活性物质所在的离子通道中。
本发明公开了一类侧链含分子催化剂的离聚物，分子催化剂分布在侧链上，因此所获得的催化剂配合物具有高密度的活性位点，这些活性位点随机分散在离子导电介质中。该策略建立了一个新颖的稳定的均相催化体系，如相互连接的纳米反应器，最重要的是，每个 锚定在离子通道中的催化剂分子都可以用作“三相界面”的活性中心部位，理论上可以100％充分利用。
发明内容
本发明的目的在于针对现有技术的不足，提供一种均相催化剂及阴离子交换膜燃料电池催化层，通过设计合成一类侧链含分子催化剂和季铵盐的离子聚合物，并将其作为均相催化剂应用到燃料电池催化层中，极大的提高的催化剂的利用率，并改善了催化层的传质，提高了燃料电池的性能。
一种均相催化剂，是一类侧链含分子催化剂和季铵盐基团的离子聚合物，其是通过将燃料电池阴极或阳极分子催化剂引入到侧链含溴代烷基的聚合物的侧链中，再将溴代烷基进行季铵化得到的；其中，所述的分子催化剂为含卟啉、酞菁或咔咯的金属配合物催化剂；所述的侧链含溴代烷基的聚合物为聚溴代烷基芴，结构如下所示：
Figure PCTCN2020123686-appb-000001
其中n为聚合度。
所述的分子催化剂选自：
Figure PCTCN2020123686-appb-000002
Figure PCTCN2020123686-appb-000003
其中，M为Fe、Co、Cu、Ni或Pt。
所述的将分子催化剂引入到所述聚合物的侧链中所采用的方法是：先将分子催化剂进行取代反应，再与所述聚合物上的溴代烷基侧链中的溴反应生成共价键，从而将分子催化剂连接到所述聚合物的侧链上。如：可以先将分子催化剂进行取代反应在分子催化剂上形成酚羟基，再通过分子催化剂的酚羟基与所述聚合物上的溴代烷基上的溴反应生成醚键，从而将分子催化剂连接到所述聚合物的侧链上。
进一步的，所述的分子催化剂与所述聚合物上溴代烷基的摩尔比为1:10-1:2。
一种基于均相催化剂的阴离子交换膜燃料电池催化层，是将上述的均相催化剂和导电炭黑、N,N-二甲基甲酰胺配置成催化剂浆料，涂布于气体扩散层材料上，干燥后得到催化层，所述催化层中均相催化剂由于亲疏水相互作用(亲水的侧链与疏水的主链)产生相分离，而分子催化剂分布于侧链所构成的亲水离子通道中，形成类似于溶液均相体系的微反应器，微反应器之间通过亲水离子通道连接。
本发明的有益效果是：
本发明通过将分子催化剂固定在离聚物的侧链中并分布在离子通道中，从而在阴离子交换膜燃料电池催化剂层中获得均相催化体系。 在构造的均相催化剂层中，分子催化剂沿离子通道分布，大大提高了催化剂利用率，改善了传质。分子催化剂是通过共价键键接到离聚物上的，催化剂表现优异的电化学稳定性。均相体系还可以提高原子效率，并且在燃料电池单电池测试中表现出更高的峰值功率密度，表明在均相催化剂层中传质得到了改善。基于均相催化剂的催化层的设计策略也可以扩展到其他电化学能量转换装置，以通过简单地改善传质和催化位点的利用来完全填充非贵金属材料的实际应用。
附图说明
图1为传统的基于非均相催化剂的催化层(A)和本发明提出的基于均相催化剂的催化层(B)的对比图以及本发明中均相催化剂的结构示意图(C)。
图2为均相催化剂PF-TMPPCo的合成路线图。
图3为均相催化剂PF-PcFe的合成路线图。
图4为均相催化剂PF-TMPPCo的基础表征，证明材料的成功合成。
图5为均相催化剂碳负载后的微观形貌图。
图6为均相催化剂的微观形态及元素分布情况。分子催化剂均匀分布于侧链季铵盐基团组成的离子通道中。
图7为均相催化剂与其他非均相催化剂的氧还原活性对比。
图8为金属中心在不同催化剂中的转换频率(TOF)。其中均相催化剂表现出最高的TOF。
图9为均相催化剂PF-TMPPCo的稳定性。
图10为均相催化剂PF-TMPPCo与非均相共混催化剂PFI-TMPPCo及不含季铵盐的PFBr-TMPPCo的燃料电池极化曲线。
图11为分子催化剂TMPPPt在不同转速下的氢气氧化曲线。
具体实施方式
仪器与材料
氢氧化钠，二甲基甲酰胺(DMF)，无水乙醚，三甲胺，碳酸钾，甲醇，乙酸钴，氯化铁等均购于国药化学试剂有限公司。溴己基芴和一羟基苯-三甲氧基苯基卟啉钴自己合成。溴己基聚芴是通过溴己基芴与三氟丙酮在三氟甲磺酸催化下聚合而成。
附图1为传统铂基催化层与本发明碳掺杂PF-TMPPCo催化层的比较。图中：A传统催化层及其不能完成反应的位点：i，Ionomer未覆盖的铂ii，未使用的纳米铂中心；iii，过度覆盖的Ionomer影响反应气体的传输；B新型均相催化层的示意图，分子催化剂分布于离聚物构成的离子通道中，构成互相连通的微反应器。
实施例1
四甲氧基卟啉钴基聚芴离聚物(PF-TMPPCo)均相催化剂的制备
通过一锅法改性溴己基聚芴来制备PF-TMPPCo：羟基苯基-三甲氧基苯基卟啉钴TMPPCo-OH(588mg)，K 2CO 3(150mg)，溴己基聚芴PF(1.44g)和DMF(100mL)溶液在氮气气氛下80℃搅拌24h。将TMPPCo连接到PF侧链后，添加2mL三甲胺(30wt％的乙醇溶液)，并使混合物在密封系统下于50℃反应24小时。随后，将反应溶液倒入水中以沉淀，超声处理，洗涤并用0.1M盐酸和去离 子水离心3次以除去反应物。将获得的催化剂在60℃下真空干燥24h，并与碳材料混合后直接用作电化学催化剂。
附图2为代表性均相PF-TMPPCo催化剂的合成路线图，溴代烷基芴与三氟丙酮在超酸催化作用下得到聚溴代烷基芴，随后侧链的溴代烷基与羟基取代的四苯基卟啉钴反应，将催化中心键接到PF侧链中，最后将剩余的溴代烷基与三甲胺反应，得到季铵化的聚合物催化剂。
实施例2
酞菁铁基聚芴离聚物(PF-PcFe)均相催化剂的制备
通过两步法改性溴己基聚芴来制备PF-PcFe：羟基酞菁铁(500mg)，K 2CO 3(150mg)，溴己基聚芴PF(1.44g)和DMF(100mL)溶液在氮气气氛下80℃搅拌24h后在甲醇中沉淀，得到墨绿色聚合物固体。将PcFe连接到PF侧链后，添加2mL三甲胺(30wt％的乙醇溶液)，并使混合物在密封系统下于50℃反应24小时。随后，将反应溶液倒入水中以沉淀，超声处理，洗涤并用0.1M盐酸和去离子水离心3次以除去反应物。将获得的催化剂在60℃下真空干燥24h，并与碳材料混合后直接用作电化学催化剂。
附图3为代表性均相PF-PcFe催化剂的合成路线图。
实施例3
催化剂的电化学表征
电化学测量是通过使用Autolab PGSTAT302N电势仪，以新鲜制作的可逆氢电极(RHE)作为参比电极，铂丝为对电极，在0.1M KOH 溶液中进行的。通过将催化剂粉末(1mg)，PF离聚物(1mg)和ECP碳(10mg)在4mL DMF的混合物中混合来制备催化剂Ink(当所述催化剂粉末为本发明所制备的均相催化剂时，可无需加入PF离聚物)。将得到的悬浮液超声处理1小时，然后通过10μL微量移液管滴铸到玻璃碳(GC)电极(OD＝5.61mm，PINE)的表面上。电极在异丙醇饱和的气氛中干燥。在进行实验之前，每种悬浮液都是新鲜制备的。在开始每次测量30分钟之前，通过将Ar或O 2鼓泡使电解质充满Ar或O 2。测试时将Ar或O 2的气流连续鼓泡到电解液上方，以确保Ar或O 2饱和。CV和RDE测量均在Ar饱和或O 2饱和的0.1M KOH溶液中进行，扫描速率为10mV s -1。
实施例4
阴离子交换膜燃料电池催化层的制备及单电池测试
为了制备电催化剂浆料，称量催化剂(10mg)、PF离聚物(10mg)和ECP碳(100mg)在4 0mL DMF的混合物中混合制备催化剂Ink(当所述催化剂粉末为本发明所制备的均相催化剂时，可无需加入PF离聚物)。然后将混合物转移到玻璃小瓶中，将其浸入水超声浴中，静置30分钟，以形成均质的浆料混合物。超声处理完成后，使用与氮气管线相连的手持喷枪将混合物喷涂到Toray碳纸(25cm 2，非特氟龙，TGP-H-60)上，以加压获得催化剂金属负载量为0.80mg±0.08mg/cm -2，以类似的方式制备了PtRu/C阳极，达到上述金属负载量。首先将所有喷涂催化剂和膜HDPE-25μm浸泡在1M KOH溶液中1小时，然后将KOH溶液与中途的新鲜溶液交换，以激活季铵盐基团， 然后将其组装在电池作为膜电极组件(MEA)。将准备好的MEA相应地夹在两个垫片之间(厚度＝0.15mm)，并使用固定螺栓和扭矩起子以5.5Nm的恒定扭矩密封到测试单元中。使用燃料电池软件版本4(Scribner Associates)记录燃料电池的恒流极化曲线。
附图4为PF-TMPPCo催化剂结构的表征。图中：
A，FT-IR；
B，PF，TMPPCo和PF-TMPPCo的紫外可见光谱；
C，TMPPCo和PF-TMPPCo的高分辨率XPS Co 2p光谱；
D，TMPPCo和PF-TMPPCo的Co K边缘XANES光谱。
可以看出，PF-TMPPCo的FT-IR,紫外光谱都集合了PF和TMPPCo的信号，说明TMPPCo成功键接到了PF上，同时XPS和XANES光谱都与TMPPCo类似，键接过程保留了Co-N4活性位点。
附图5为催化剂的微相分离结构。其中：A，PF-TMPPCo的SEM图像；B，TEM图像；C，PF-TMPPCo；D，PFI-TMPPCo的元素图像。与传统PtC催化剂类似，PF Ionomer包覆在纳米碳球外面，构成多孔的催化层结构。同时PF-TMPPCo比PFI-TMPPCo的Co元素分布更加均匀。
附图6为催化剂的微观形态。图中：A，PF-TMPPCo的原子分辨率高角度环形暗场扫描透射电子显微镜(HAADF-STEM)图像(单个Co原子显示出鲜明的对比度)。B，PF-TMPPCo的能量色散X射线光谱图像。C，图3b中用绿色矩形表示的区域的净扫描强度分布图，浅蓝色矩形对应于离子通道区域。D，PF-TMPPCo和E， PFI-TMPPCo(PF离聚物与TMPPCo的混合物)的模拟配置：Co(黄色)，O(红色)，N(紫色)，F(绿色)和C(灰色)。左：全图；右：为了清楚起见，仅显示Co原子。红色循环突出显示了PFI-TMPPCo中卟啉环的聚集。
附图7为在900rpm的转速下，不同催化剂的ORR极化曲线。PF-TMPPCo表现出了最高的半波电位。附图8为金属中心在不同催化剂中的转换频率(TOF)。其中均相催化剂表现出最高的TOF。附图9为均相催化剂PF-TMPPCo的稳定性。在两万个循环测试后，PF-TMPPCo只有15mV的半波衰减，证明其极佳的稳定性。附图10为均相催化剂PF-TMPPCo与非均相共混催化剂PFI-TMPPCo及不含季铵盐的PFBr-TMPPCo的燃料电池极化曲线。均相催化剂在燃料电池中表现出了更高的优势。附图11为分子催化剂TMPPPt在不同转速下的氢气氧化曲线。可以看出采用本发明制得均相催化剂对于阳极也是适用的。

Claims (5)

  1. 一种均相催化剂，其特征在于，是一类侧链含分子催化剂和季铵盐基团的离子聚合物，其是通过将燃料电池阴极或阳极分子催化剂引入到侧链含溴代烷基的聚合物的侧链中，再将溴代烷基进行季铵化得到的；
    其中，所述的分子催化剂为含卟啉、酞菁或咔咯的金属配合物催化剂；所述的侧链含溴代烷基的聚合物为聚溴代烷基芴，结构如下所示：
    Figure PCTCN2020123686-appb-100001
    其中n为聚合度。
  2. 根据权利要求1所述的均相催化剂，其特征在于，所述的分子催化剂选自：
    Figure PCTCN2020123686-appb-100002
    其中，M为Fe、Co、Cu、Ni或Pt。
  3. 根据权利要求1所述的均相催化剂，其特征在于，所述的将分子催化剂引入到所述聚合物的侧链中所采用的方法是：先将分子催化剂进行取代反应，再与所述聚合物上的溴代烷基侧链中的溴反应生成共价键，从而将分子催化剂连接到所述聚合物的侧链上。
  4. 根据权利要求1所述的均相催化剂，其特征在于，所述的分子催化剂与所述聚合物上溴代烷基的摩尔比为1:10-1:2。
  5. 一种基于均相催化剂的阴离子交换膜燃料电池催化层，其特征在于，将如权利要求1-4任一项所述的均相催化剂和导电炭黑、N,N-二甲基甲酰胺配置成催化剂浆料，涂布于气体扩散层材料上，干燥后得到催化层，所述催化层中均相催化剂由于亲疏水相互作用产生相分离，而分子催化剂分布于侧链所构成的亲水离子通道中，形成类似于溶液均相体系的微反应器，微反应器之间通过亲水离子通道连接。
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