CN112397734B - Preparation method and application of a high-density Fe-N4 active site oxygen reduction electrocatalyst - Google Patents

Preparation method and application of a high-density Fe-N4 active site oxygen reduction electrocatalyst Download PDF

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CN112397734B
CN112397734B CN202011280943.6A CN202011280943A CN112397734B CN 112397734 B CN112397734 B CN 112397734B CN 202011280943 A CN202011280943 A CN 202011280943A CN 112397734 B CN112397734 B CN 112397734B
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宋玉江
张云龙
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Abstract

The invention provides high-density Fe-N4Preparation method of active site oxygen reduction electrocatalyst and active site oxygen reduction electrocatalystThe application belongs to the field of polymer electrolyte membrane fuel cell catalysts. Uniformly dispersing metal zirconium salt in a solvent, wherein Zr in the zirconium salt4+Adding two macrocyclic compounds including macrocyclic compound I, metal macrocyclic compound II and organic acid into solvent at concentration of 2-8mg/ml, ultrasonic treating at 20-40 deg.C for 10-30min, reacting at 120 deg.C for 8-12h, vacuum filtering, washing until the filtrate is colorless, oven drying, and pyrolyzing at 600-900 deg.C for 1-2h to obtain high-density Fe-N4An active site oxygen reduction electrocatalyst. The method is simple to operate, easy to control and environment-friendly, and the prepared high-density Fe-N is4The active site oxygen reduction electrocatalyst has excellent oxygen reduction activity and can be used for polymer electrolyte membrane fuel cells.

Description

一种高密度Fe-N4活性位点氧还原电催化剂的制备方法及应用Preparation method and application of a high-density Fe-N4 active site oxygen reduction electrocatalyst

技术领域technical field

本发明涉及聚合物电解质膜燃料电池阴极氧还原电催化剂领域,具体是一种高密度Fe-N4活性位点氧还原电催化剂的制备方法及应用。The invention relates to the field of a polymer electrolyte membrane fuel cell cathode oxygen reduction electrocatalyst, in particular to a preparation method and application of a high-density Fe- N4 active site oxygen reduction electrocatalyst.

背景技术Background technique

自近代工业化发展至今,煤、石油、天然气不可再生化石燃料的大量及不合理使用导致全球含氮、含硫、含碳(NOx、SOx、CO)等有害气体的排放量急剧增加,引发了全球气温升高、环境恶化、人类健康及全球能源危机等一系列全球关注问题。因此,开发环境友好型、可持续发展型、安全及高效型的能源技术迫在眉睫。聚合物电解质膜燃料电池(PEMFCs)具有能量转化效率高、环境友好、室温快速启动、无电解液流失、比功率与比能量高等优点受到了世界各国的关注。Since the development of modern industrialization, the massive and unreasonable use of non-renewable fossil fuels such as coal, oil, and natural gas has led to a sharp increase in the global emissions of harmful gases such as nitrogen, sulfur, and carbon (NO x , SO x , CO ), causing It addresses a series of global concerns such as global temperature rise, environmental degradation, human health and the global energy crisis. Therefore, it is urgent to develop environmentally friendly, sustainable, safe and efficient energy technologies. Polymer electrolyte membrane fuel cells (PEMFCs) have attracted worldwide attention due to their high energy conversion efficiency, environmental friendliness, rapid start-up at room temperature, no electrolyte loss, and high specific power and specific energy.

高活性、高稳定的电催化剂是PEMFCs的重要构成材料之一。铂(Pt)基催化剂的出现极大地促进了燃料电池的发展,推进了燃料电池的实际应用。然而,Pt的全球储量低导致其价格相对高,此外,Pt基电催化剂在燃料电池的实际工况下稳定性差(易溶解和再聚集)、对反应质的耐受性差(如:甲醇),这些问题使得电催化剂成为阻碍燃料电池商业化的关键因素之一。面对以上问题,科学家提出两种策略,第一种策略:开发Pt-M1(M1可为Pd、Au等贵金属,也可为Fe、Co、Ni等过渡金属)材料,通过形貌控制、开发合金,降低Pt的用量,同时提高电催化剂的催化活性及耐久性;第二种策略:开发非贵金属氧还原电催化剂,在这类电催化中,M2-N-C(M2主要为Fe、Co、Mn等过渡金属) 类非贵金属电催化剂由于其低成本、高活性、高耐久性和抗甲醇性等优点而得到了广泛关注。Electrocatalysts with high activity and high stability are one of the important constituent materials of PEMFCs. The emergence of platinum (Pt)-based catalysts has greatly promoted the development of fuel cells and advanced the practical application of fuel cells. However, the low global reserves of Pt lead to its relatively high price. In addition, Pt-based electrocatalysts suffer from poor stability (prone to dissolution and re-aggregation) and poor tolerance to reactive species (e.g., methanol) in the actual working conditions of fuel cells, These problems make electrocatalysts one of the key factors hindering the commercialization of fuel cells. Faced with the above problems, scientists propose two strategies. The first strategy is to develop Pt-M 1 (M 1 can be noble metals such as Pd, Au, or transition metals such as Fe, Co, and Ni) materials, which can be controlled by morphology. , develop alloys, reduce the amount of Pt, and improve the catalytic activity and durability of electrocatalysts; the second strategy: develop non-noble metal oxygen reduction electrocatalysts, in this type of electrocatalysis, M 2 -NC (M 2 is mainly Fe , Co, Mn and other transition metals) non-precious metal electrocatalysts have received extensive attention due to their low cost, high activity, high durability, and methanol resistance.

上世纪60年代,Jasinski首次报道了N4-螯合物酞菁钴在碱性电解液中具有氧还原活性后,打开了非贵金属氧还原电催化剂研究的新领域。(Nature,1964, 201,1212-1213)自此之后,诸多基于金属酞菁和金属卟啉类大环化合物的 M2-N-C非贵金属氧还原电催化剂被广泛研究报道。如:Wei团队通过将铁卟啉以共价键的作用负载在碳材料上,得到了具有较高氧还原活性和较好耐久性的电催化剂(Angew.Chem.,2014,126,6777-6781)。金属大环化合物由于其独特的 M2-N4结构使其成为一种良好的非贵金属氧还原电催化剂的前驱体,目前,基于金属酞菁或金属卟啉类大环化合物的氧还原电催化剂的制备原理主要是通过诸多作用力来完成分子间的堆积(如:π-π作用、正负电荷相互作用、氢键),然后在惰性气氛下高温热解碳化提高材料稳定性,然而,热解过程中的不可控性会经常导致金属聚集,导致材料的利用率降低。因此,急需一种策略提升金属大环化合物在制备氧还原电催化剂过程中的利用率,金属有机框架(MOFs)的出现实现了金属酞菁或金属卟啉类大环化合物由无序的分子堆积到有序的分子排列。In the 1960s, Jasinski first reported the oxygen reduction activity of N 4 -chelate cobalt phthalocyanine in alkaline electrolytes, which opened a new field of research on non-noble metal oxygen reduction electrocatalysts. (Nature, 1964, 201, 1212-1213) Since then, many M 2 -NC non-noble metal oxygen reduction electrocatalysts based on metallophthalocyanine and metalloporphyrin macrocyclic compounds have been widely reported. For example, Wei's team obtained an electrocatalyst with high oxygen reduction activity and good durability by loading iron porphyrin on carbon materials by covalent bond (Angew.Chem., 2014, 126, 6777-6781 ). Metal macrocycles are good precursors for non-noble metal oxygen reduction electrocatalysts due to their unique M2 - N4 structure. Currently, oxygen reduction electrocatalysts based on metallophthalocyanine or metalloporphyrin-based macrocycles The preparation principle is mainly to complete the intermolecular stacking through many forces (such as: π-π interaction, positive and negative charge interaction, hydrogen bonding), and then high temperature pyrolysis carbonization in an inert atmosphere to improve the stability of the material, however, thermal Uncontrollability in the solution process can often lead to metal aggregation, resulting in reduced material utilization. Therefore, there is an urgent need for a strategy to improve the utilization of metal macrocycles in the preparation of oxygen reduction electrocatalysts. The emergence of metal-organic frameworks (MOFs) realizes metal phthalocyanine or metalloporphyrin-like macrocycles from disordered molecular stacking into an ordered molecular arrangement.

MOFs是由有机配体通过配位键与金属离子或者多核金属团簇形成的有机无机杂化材料,由于有较强导向性的配位键连接,在几何学和结晶学上都有着定义明确的拓扑结构。MOFs具有多孔性、易功能化、良好的可设计性及高比表面积等特性。MOFs的两个重要组成单元-金属离子或团簇与有机配体,为该类材料的合成提供了多种可能。随着对合成和结构表征的深入研究,越来越多的 MOFs材料被发现并应用于光学、磁学和电学,同时在催化、气体存储及分离等领域也有应用价值。MOFs are organic-inorganic hybrid materials formed by organic ligands and metal ions or polynuclear metal clusters through coordination bonds. Due to the strong oriented coordination bonds, they are well defined in geometry and crystallography. Topology. MOFs have the characteristics of porosity, easy functionalization, good designability, and high specific surface area. The two important constituent units of MOFs—metal ions or clusters and organic ligands—provide a variety of possibilities for the synthesis of such materials. With the in-depth research on synthesis and structural characterization, more and more MOFs materials have been discovered and applied in optics, magnetism, and electricity, as well as in catalysis, gas storage, and separation.

MOFs材料发展迅速,2008年,Xu团队首次报道了使用MOF-5作为前驱体,通过高温热解后制备多孔碳载体并应用于氧还原领域(JOURNAL OF THE AMERICAN CHEMICALSOCIETY,2008,130(16):5390-5391.)。MOFs结构稳定,将其高温热解碳化之后,可极大地提升其导电性并保留多孔特性,有利于O2的传输,易发生四电子还原过程提升催化活性,减少二电子产生的H2O2物种对催化剂活性位点的攻击,延长电催化的使用寿命。MOFs materials have developed rapidly. In 2008, Xu's team first reported the use of MOF-5 as a precursor to prepare porous carbon supports after high temperature pyrolysis and applied in the field of oxygen reduction (JOURNAL OF THE AMERICAN CHEMICALSOCIETY, 2008, 130(16): 5390-5391.). The structure of MOFs is stable. After high - temperature pyrolysis carbonization, its electrical conductivity can be greatly improved and its porous properties can be retained, which is beneficial to the transport of O 2 . Species attack on the active sites of catalysts, extending the lifetime of electrocatalysis.

随着MOFs材料的发展,科学家实现了以大环化合物作为MOFs的有机配体,合成了一系列锆基金属团簇MOFs(Angew.Chem.Int.Ed.2012,51, 10307-10310),并逐渐应用于电催化领域。如:2017年姜海龙团队以Zr6团簇为金属团簇,以间-四(4-羧基苯基)卟吩(TCPP)为配体,合成了PCN-224MOFs 材料,经过Fe、Co金属盐吸附,高温热解、酸洗刻蚀获得了结构稳定的催化剂,其耐久性得到了极大的提升(ChemSusChem,2017,10,1-7)。通过与MOFs结构结合,虽然极大的提升了金属大环化合物的活性及其耐久性,但由此方法制备的电催化剂催化活性仍然不能满足PEMFCs的活性需求,难以应用于质子交换膜燃料电池。因此,急需一种策略来提高电催化剂的活性位点密度以提升其催化活性来加快PEMFCs的发展。With the development of MOFs materials, scientists have realized the use of macrocyclic compounds as organic ligands of MOFs, and synthesized a series of zirconium-based metal cluster MOFs (Angew.Chem.Int.Ed.2012,51, 10307-10310), and Gradually applied in the field of electrocatalysis. For example, in 2017, Jiang Hailong's team synthesized PCN-224MOFs materials using Zr 6 clusters as metal clusters and m-tetrakis(4-carboxyphenyl) porphine (TCPP) as ligands. Adsorption, high-temperature pyrolysis, and acid wash etching resulted in structurally stable catalysts whose durability was greatly improved (ChemSusChem, 2017, 10, 1-7). By combining with the structure of MOFs, although the activity and durability of metal macrocyclic compounds are greatly improved, the catalytic activity of electrocatalysts prepared by this method still cannot meet the activity requirements of PEMFCs, and it is difficult to be applied to proton exchange membrane fuel cells. Therefore, a strategy to increase the active site density of electrocatalysts to enhance their catalytic activity is urgently needed to accelerate the development of PEMFCs.

发明内容SUMMARY OF THE INVENTION

本发明的目的是提供了一种高密度Fe-N4活性位点氧还原电催化剂的制备方法及应用,该方法操作简单、易于控制、环境友好。所述的高密度Fe-N4活性位点氧还原电催化剂以两种大环化合物为原料,其中一种大环化合物Ⅰ(命名为Zr6-Porphyrin)与Zr6金属团簇以离子配位键的形式结合形成三维多孔高度结晶的材料,该材料比表面积高且具有微孔(<2nm)、介孔(2-50nm)两种孔径,在形成MOFs三维结构之前,另一种具有氧还原催化能力的金属大环化合物Ⅱ (命名为Precursor-porphyrin)通过离子配位键与Zr6金属团簇结合,在合成MOFs 材料的同时将Precursor-porphyrin同步嵌入到MOFs材料的介孔中,作为催化活性位点,后经过高温热解碳化制备得到具有优良的氧还原综合性能的高密度 Fe-N4活性位点氧还原电催化剂,适用于质子交换膜燃料电池。The purpose of the present invention is to provide a preparation method and application of a high-density Fe- N4 active site oxygen reduction electrocatalyst, which is simple to operate, easy to control, and environmentally friendly. The described high-density Fe- N4 active site oxygen reduction electrocatalyst uses two macrocyclic compounds as raw materials, among which one macrocyclic compound I (named Zr6 -Porphyrin) is ionically coordinated with Zr6 metal clusters. Bonded in the form of bonds to form a three-dimensional porous highly crystalline material with a high specific surface area and two pore sizes of micropores (<2nm) and mesopores (2-50nm), and another with oxygen reduction before the three-dimensional structure of MOFs was formed. The catalytically capable metal macrocyclic compound II (named Precursor-porphyrin) binds to Zr 6 metal clusters through ionic coordination bonds, and simultaneously inserts Precursor-porphyrin into the mesopores of MOFs while synthesizing MOFs. The active site is then prepared by high-temperature pyrolysis carbonization to obtain a high-density Fe- N4 active site oxygen reduction electrocatalyst with excellent oxygen reduction comprehensive performance, which is suitable for proton exchange membrane fuel cells.

为了达到上述目的,本发明的技术方案为:In order to achieve the above object, the technical scheme of the present invention is:

一种高密度Fe-N4活性位点氧还原电催化剂的制备方法,包括如下步骤:A preparation method of a high-density Fe-N 4 active site oxygen reduction electrocatalyst, comprising the following steps:

将锆的金属盐(锆盐)均匀分散于溶剂中,其中,锆盐中Zr4+在溶剂中的浓度为2-8mg/ml,加入二种大环化合物包括大环化合物Ⅰ(命名为Zr6-Porphyrin)、金属大环化合物Ⅱ(命名为Precursor-Porphyrin))和有机酸,在20-40℃条件下,超声处理10-30min,于120℃下反应8-12h,抽滤,洗涤至滤液为无色,烘干,于600-900℃下热解1-2h,得到高密度Fe-N4活性位点氧还原电催化剂;The metal salt of zirconium (zirconium salt) is uniformly dispersed in the solvent, wherein the concentration of Zr 4+ in the solvent in the zirconium salt is 2-8 mg/ml, and two macrocyclic compounds including macrocyclic compound I (named Zr 6 -Porphyrin), metal macrocyclic compound II (named Precursor-Porphyrin)) and organic acid, at 20-40 ℃, ultrasonic treatment for 10-30min, react at 120 ℃ for 8-12h, suction filtration, wash until The filtrate is colorless, dried, and pyrolyzed at 600-900 °C for 1-2 h to obtain a high-density Fe-N 4 active site oxygen reduction electrocatalyst;

所述的大环化合物Ⅰ(Zr6-Porphyrin)和锆盐物质的量比为(0.1-0.4):1,优选为0.37:1;The mass ratio of the macrocyclic compound I (Zr 6 -Porphyrin) to the zirconium salt is (0.1-0.4):1, preferably 0.37:1;

所述的金属大环化合物Ⅱ(Precursor-Porphyrin)与大环化合物Ⅰ (Zr6-Porphyrin)的质量比为(0.25-1):1;The mass ratio of the metal macrocyclic compound II (Precursor-Porphyrin) to the macrocyclic compound I (Zr 6 -Porphyrin) is (0.25-1):1;

所述的有机酸和锆盐的物质的量比为(20-30):1;The material ratio of described organic acid and zirconium salt is (20-30): 1;

基于以上技术方案,优选的,所述的锆盐包括ZrCl4、ZrOCl2·8H2O、 ZrO(NO3)2·H2O中的一种或两种以上。Based on the above technical solutions, preferably, the zirconium salt includes one or more of ZrCl 4 , ZrOCl 2 ·8H 2 O, and ZrO(NO 3 ) 2 ·H 2 O.

基于以上技术方案,优选的,所述的有机酸包括CH2O2、C2H4O2、C2HF3O2、 C3H6O2、C4H8O2、C2H2Cl2O2、C7H6O2、C8H8O2中的一种或两种以上的混合物。Based on the above technical solutions, preferably, the organic acid includes CH 2 O 2 , C 2 H 4 O 2 , C 2 HF 3 O 2 , C 3 H 6 O 2 , C 4 H 8 O 2 , C 2 H One or a mixture of two or more of 2 Cl 2 O 2 , C 7 H 6 O 2 and C 8 H 8 O 2 .

基于以上技术方案,优选的,所述的大环化合物Ⅰ(Zr6-Porphyrin)为侧链含四个羧基的卟啉或酞菁,其中所述的大环化合物的中心无金属元素和/或包括金属元素,若涉及使用金属卟啉或酞菁,所述的金属为铁;所述的金属大环化合物Ⅱ(Precursor-porphyrin)为血晶素(Heme)。Based on the above technical solutions, preferably, the macrocyclic compound I (Zr 6 -Porphyrin) is a porphyrin or phthalocyanine with four carboxyl groups in the side chain, wherein the center of the macrocyclic compound is free of metal elements and/or Including metal elements, if metal porphyrin or phthalocyanine is involved, the metal is iron; the metal macrocyclic compound II (Precursor-porphyrin) is Heme.

基于以上技术方案,优选的,所述的溶剂包括乙醇、丙醇、异丙醇、二甲基亚砜(DMSO)、N,N-二甲基甲酰胺(DMF)、N,N-二甲基乙酰胺(DMAC) 中的一种或两种以上的混合物。Based on the above technical solutions, preferably, the solvent includes ethanol, propanol, isopropanol, dimethyl sulfoxide (DMSO), N,N-dimethylformamide (DMF), N,N-dimethylformamide One or a mixture of two or more of acetamide (DMAC).

基于以上技术方案,优选的,升温至热解温度的速率为1-10℃/min。Based on the above technical solutions, preferably, the rate of heating up to the pyrolysis temperature is 1-10°C/min.

本发明还涉及保护采用上述制备方法得到的高密度Fe-N4活性位点氧还原电催化剂。The present invention also relates to protecting the high-density Fe-N 4 active site oxygen reduction electrocatalyst obtained by the above preparation method.

本发明还涉及保护上述高密度Fe-N4活性位点氧还原电催化剂在质子交换膜燃料电池中的应用。The present invention also relates to the application of protecting the above-mentioned high-density Fe- N4 active site oxygen reduction electrocatalyst in a proton exchange membrane fuel cell.

本发明提出一种高密度Fe-N4活性位点氧还原电催化剂的制备方法,以两种大环化合物为原料,其中一种大环化合物(命名为Zr6-Porphyrin)与Zr6金属团簇以离子配位键的形式结合生长为具有立体空间结构的MOFs材料,另一种金属大环化合物(命名为Precursor-porphyrin)作为增加活性位点密度的前驱体,在不影响传质的基础上将Precursor-porphyrin嵌入到MOFs材料的孔道内,提高氧还原电催化剂的活性位点密度,通过此方法制备得到高密度Fe-N4活性位点氧还原电催化剂展现出优异的氧还原催化活性和稳定性。The invention proposes a preparation method of a high-density Fe- N4 active site oxygen reduction electrocatalyst, which uses two macrocyclic compounds as raw materials, wherein one macrocyclic compound (named as Zr 6 -Porphyrin) and Zr 6 metal group Clusters are combined in the form of ionic coordination bonds to grow into MOFs with three-dimensional spatial structure, and another metal macrocyclic compound (named Precursor-porphyrin) is used as a precursor to increase the density of active sites without affecting mass transfer. Precursor-porphyrin was embedded into the pores of MOFs materials to improve the active site density of oxygen reduction electrocatalysts. The high density Fe- N4 active site oxygen reduction electrocatalysts prepared by this method exhibited excellent oxygen reduction catalytic activity. and stability.

与现有技术相比,本发明的突出特点在于:1)将具有催化活性的金属大环化合物嵌入到以另一种大环化合物为有机配体生成的MOFs材料的介孔中,提高了电催化剂的活性位点密度;2)MOFs具有多孔性,其介孔结构并不会被金属大环化合物完全填充,仍然有利于O2的传输;3)MOFs经过热解后其导电性提升,同时,其三维结构也会部分保留,有助于提升氧还原催化活性;4)MOFs 结构的利用,可能有利于四电子氧还原过程的进行,减少产生可对卟啉环进攻的H2O2,延长电催化剂的使用寿命。5)本发明操作简单、易于控制、环境友好,制备得到的高密度Fe-N4活性位点氧还原电催化剂具有优异的氧还原活性,可用于聚合物电解质膜燃料电池。Compared with the prior art, the outstanding features of the present invention are: 1) The metal macrocyclic compound with catalytic activity is embedded in the mesopores of the MOFs material generated by using another macrocyclic compound as an organic ligand, which improves the electrical conductivity. The active site density of the catalyst; 2) MOFs are porous, and their mesoporous structure is not completely filled by metal macrocyclic compounds, which is still conducive to O transport; 3 ) After the MOFs are pyrolyzed, their electrical conductivity is improved, and at the same time , its three-dimensional structure will also be partially retained, which is helpful to improve the catalytic activity of oxygen reduction; 4) the utilization of MOFs structure may be beneficial to the four-electron oxygen reduction process, reducing the generation of H 2 O 2 that can attack the porphyrin ring, Extend the life of electrocatalysts. 5) The present invention is simple to operate, easy to control, and environmentally friendly, and the prepared high-density Fe-N 4 active site oxygen reduction electrocatalyst has excellent oxygen reduction activity, which can be used in polymer electrolyte membrane fuel cells.

附图说明Description of drawings

图1为本发明所得电催化剂前驱体的SEM图,其中a为对比例1所得电催化剂前驱体PCN-222;b为实施例1所得电催化剂前驱体 20-Heme@Fe10-PCN-222;1 is a SEM image of the electrocatalyst precursor obtained in the present invention, wherein a is the electrocatalyst precursor PCN-222 obtained in Comparative Example 1; b is the electrocatalyst precursor 20-Heme@Fe 10 -PCN-222 obtained in Example 1;

图2为对比例1所得电催化剂前驱体PCN-222与实施例1所得电催化剂前驱体20-Heme@Fe10-PCN-222和模拟的PCN-222XRD对比图;Figure 2 is an XRD comparison diagram of the electrocatalyst precursor PCN-222 obtained in Comparative Example 1, the electrocatalyst precursor 20-Heme@Fe 10 -PCN-222 obtained in Example 1, and the simulated PCN-222;

图3为对比例1所得电催化剂前驱体PCN-222、实施例3所得电催化剂前驱体20-Heme@PCN-222及实施例1所得电催化剂前驱体 20-Heme@Fe10-PCN-222的孔径分布图;Figure 3 is the electrocatalyst precursor PCN-222 obtained in Comparative Example 1, the electrocatalyst precursor 20-Heme@PCN-222 obtained in Example 3, and the electrocatalyst precursor 20-Heme@Fe 10 -PCN-222 obtained in Example 1. Pore size distribution map;

图4为对比例1所得产物PCN-222-700、实施例3所得产物 20-Heme@PCN-222-700及实施例1所得产物20-Heme@Fe10-PCN-222-700的 ORR极化曲线图。Figure 4 shows the ORR polarization of the product PCN-222-700 obtained in Comparative Example 1, the product 20-Heme@PCN-222-700 obtained in Example 3 and the product 20-Heme@Fe 10 -PCN-222-700 obtained in Example 1 Graph.

具体实施方式Detailed ways

下面结合附图和实施例对本发明作进一步的说明,以下实施例仅仅是为了更加清楚地阐述本发明,但本发明要求保护的范围并不局限于以下实施例表述的范围。The present invention will be further described below in conjunction with the accompanying drawings and examples. The following examples are only to illustrate the present invention more clearly, but the claimed scope of the present invention is not limited to the scope expressed by the following examples.

实施例1Example 1

将40mg ZrOCl2·8H2O分散于8mL的DMF溶液中,加入650mg苯甲酸 20mg Heme,30mgmeso-四(4-羧基苯基)卟吩(TCPP),10mg meso-四(4-羧基苯基)卟吩氯化铁(Fe-TCPP),25℃下超声30min,120℃下反应12h,抽滤,洗涤至滤液为无色,在65℃下烘干,得到电催化剂的前驱体,记作 20-Heme@Fe10-PCN-222,之后将前驱体以5℃/min升温速率至700℃后恒温2h,最终得到黑色粉末固体,记作20-Heme@Fe10-PCN-222-700。Disperse 40 mg of ZrOCl 2 ·8H 2 O in 8 mL of DMF solution, add 650 mg of benzoic acid, 20 mg of Heme, 30 mg of meso-tetrakis(4-carboxyphenyl) porphine (TCPP), and 10 mg of meso-tetrakis(4-carboxyphenyl) Porphine ferric chloride (Fe-TCPP), sonicated for 30 min at 25 °C, reacted at 120 °C for 12 h, suction filtered, washed until the filtrate was colorless, and dried at 65 °C to obtain the precursor of the electrocatalyst, denoted as 20 -Heme@Fe 10 -PCN-222, then the precursor was heated at a rate of 5 °C/min to 700 °C and then held at a constant temperature for 2 h, and finally a black powder solid was obtained, denoted as 20-Heme@Fe 10 -PCN-222-700.

如图1,所制备的为实施例1所得电催化剂前驱体20-Heme@Fe10-PCN-222 为棒状且尺寸均一,且与实施例2所得电催化剂前驱体初始的PCN-222形貌一致,但是其尺寸减小。As shown in Figure 1, the prepared electrocatalyst precursor 20-Heme@Fe 10 -PCN-222 obtained in Example 1 is rod-shaped and uniform in size, and is consistent with the initial PCN-222 morphology of the electrocatalyst precursor obtained in Example 2 , but its size is reduced.

如图2,所制备的电催化剂的前驱体的XRD衍射峰与模拟的MOFs的峰位置一致,说明Heme的引入并不会MOFs的结构,所得到得前驱体为高度结晶得材料。As shown in Figure 2, the XRD diffraction peaks of the precursors of the prepared electrocatalysts are consistent with the peak positions of the simulated MOFs, indicating that the introduction of Heme does not have the structure of MOFs, and the obtained precursors are highly crystalline materials.

如图3,所制备的为实施例1所得电催化剂前驱体20-Heme@Fe10-PCN-222、实施例2所得电催化剂前驱体初始PCN-222及实施例4所得电催化剂前驱体 20-Heme@PCN-222的孔径分布可以看出,所制备的前驱体均含有微孔及介孔二种孔径,此外,当引入Heme后,所得到的前驱体20-Heme@Fe10-PCN-222及 20-Heme@PCN-222的介孔孔体积均有所减小,直接证明Heme嵌入到了MOFs 的介孔内。As shown in Figure 3, the prepared electrocatalyst precursor 20-Heme@Fe 10 -PCN-222 obtained in Example 1, the initial PCN-222 electrocatalyst precursor obtained in Example 2 and the electrocatalyst precursor 20- It can be seen from the pore size distribution of Heme@PCN-222 that the prepared precursors contain both micropores and mesopores. In addition, when Heme is introduced, the obtained precursor 20-Heme@Fe 10 -PCN-222 The mesopore volume of 20-Heme@PCN-222 is reduced, which directly proves that Heme is embedded in the mesopores of MOFs.

如图4,氧气还原反应测试采用标准三电极法测定电化学性能,催化剂制成薄膜工作电极,测试条件:25℃下,在氧气饱和的0.1M HClO4中,以10mV/s 的扫速,在0-1.2V(vsRHE)的电压下进行电位扫描测试,电极转速为1600r/min。极化曲线显示随着Heme和Fe-TCPP的引入,电催化剂的活性逐渐增加,说明明Heme和Fe-TCPP的引入逐渐增加了电催化剂的活性位点密度,提升了电催化剂的催化活性。As shown in Figure 4 , the electrochemical performance of the oxygen reduction reaction was measured by the standard three-electrode method. The catalyst was made into a thin-film working electrode. Potential sweep tests were performed at a voltage of 0-1.2V (vsRHE), and the electrode speed was 1600 r/min. The polarization curves show that with the introduction of Heme and Fe-TCPP, the activity of the electrocatalyst gradually increases, indicating that the introduction of Heme and Fe-TCPP gradually increases the active site density of the electrocatalyst and improves the catalytic activity of the electrocatalyst.

对比例1Comparative Example 1

将40mg ZrOCl2·8H2O分散于8mL的DMF溶液中,加入650mg苯甲酸和40mg TCPP,25℃下超声30min,120℃下反应12h,抽滤,洗涤至滤液为无色,在65℃下烘干,得到电催化剂的前驱体,记作PCN-222,之后将前驱体以5℃/min升温速率至700℃后恒温2h,最终得到黑色粉末固体,记作PCN-222-700。Disperse 40 mg of ZrOCl 2 ·8H 2 O in 8 mL of DMF solution, add 650 mg of benzoic acid and 40 mg of TCPP, sonicate for 30 min at 25 °C, react at 120 °C for 12 h, filter with suction, wash until the filtrate is colorless, at 65 °C After drying, the precursor of the electrocatalyst was obtained, denoted as PCN-222, and then the precursor was heated at a rate of 5 °C/min to 700 °C and kept at a constant temperature for 2 h to finally obtain a black powder solid, denoted as PCN-222-700.

实施例2Example 2

将40mg ZrOCl2·8H2O分散于8mL的DMF溶液中,加入650mg苯甲酸 10mg Heme,40mgTCPP,25℃下超声30min,120℃下反应12h,抽滤,洗涤至滤液为无色,在65℃下烘干,得到电催化剂的前驱体,记作 10-Heme@PCN-222,之后将前驱体以5℃/min升温速率至700℃后恒温2h,最终得到黑色粉末固体,记作10-Heme@PCN-222-700。Disperse 40 mg of ZrOCl 2 ·8H 2 O in 8 mL of DMF solution, add 650 mg of benzoic acid, 10 mg of Heme, 40 mg of TCPP, sonicate for 30 min at 25 °C, react at 120 °C for 12 h, suction filtration, and wash until the filtrate is colorless, at 65 °C The precursor of the electrocatalyst was obtained by drying under low temperature, which was denoted as 10-Heme@PCN-222. After that, the precursor was heated at a rate of 5 °C/min to 700 °C and then kept at a constant temperature for 2 h, and finally a black powder solid was obtained, which was denoted as 10-Heme. @PCN-222-700.

实施例3Example 3

将40mg ZrOCl2·8H2O分散于8mL的DMF溶液中,加入650mg苯甲酸 20mg Heme,40mgTCPP,25℃下超声30min,120℃下反应12h,抽滤,洗涤至滤液为无色,在65℃下烘干,得到电催化剂的前驱体,记作 20-Heme@PCN-222,后将前驱体以5℃/min升温速率至700℃后恒温2h,最终得到黑色粉末固体,记作20-Heme@PCN-222-700。Disperse 40 mg of ZrOCl 2 ·8H 2 O in 8 mL of DMF solution, add 650 mg of benzoic acid, 20 mg of Heme, 40 mg of TCPP, sonicate for 30 min at 25 °C, react at 120 °C for 12 h, filter with suction, and wash until the filtrate is colorless, at 65 °C The precursor of the electrocatalyst was obtained by drying under low temperature, which was denoted as 20-Heme@PCN-222. Then the precursor was heated at a rate of 5 °C/min to 700 °C and kept at a constant temperature for 2 h, and finally a black powder solid was obtained, which was denoted as 20-Heme. @PCN-222-700.

实施例4Example 4

将40mg ZrOCl2·8H2O分散于8mL的DMF溶液中,加入650mg苯甲酸 30mg Heme,40mgTCPP,25℃下超声30min,120℃下反应12h,抽滤,洗涤至滤液为无色,在65℃下烘干,得到电催化剂的前驱体,记作 30-Heme@PCN-222,之后将前驱体以5℃/min升温速率至700℃后恒温2h,最终得到黑色粉末固体,记作30-Heme@PCN-222-700。Disperse 40 mg of ZrOCl 2 ·8H 2 O in 8 mL of DMF solution, add 650 mg of benzoic acid, 30 mg of Heme, 40 mg of TCPP, sonicate for 30 min at 25 °C, react at 120 °C for 12 h, suction filtration, and wash until the filtrate is colorless, at 65 °C drying under low temperature to obtain the precursor of the electrocatalyst, denoted as 30-Heme@PCN-222, then the precursor was heated at a rate of 5 °C/min to 700 °C and kept at a constant temperature for 2 h, finally a black powder solid was obtained, denoted as 30-Heme @PCN-222-700.

实施例5Example 5

将40mg ZrOCl2·8H2O分散于8mL的DMF溶液中,加入650mg苯甲酸 40mg Heme,40mgTCPP,25℃下超声30min,120℃下反应12h,抽滤,洗涤至滤液为无色,在65℃下烘干,得到电催化剂的前驱体,记作40-Heme@PCN-222,之后将前驱体以5℃/min升温速率至700℃后恒温2h,最终得到黑色粉末固体,记作40-Heme@PCN-222-700。Disperse 40 mg of ZrOCl 2 ·8H 2 O in 8 mL of DMF solution, add 650 mg of benzoic acid, 40 mg of Heme, 40 mg of TCPP, sonicate for 30 min at 25 °C, react at 120 °C for 12 h, filter with suction, and wash until the filtrate is colorless, at 65 °C drying under low temperature to obtain the precursor of the electrocatalyst, denoted as 40-Heme@PCN-222, then the precursor was heated at a rate of 5 °C/min to 700 °C and kept at a constant temperature for 2 h, finally a black powder solid was obtained, denoted as 40-Heme @PCN-222-700.

实施例6Example 6

将40mg ZrOCl2·8H2O分散于8mL的DMF溶液中,加入650mg苯甲酸 20mg Heme,35TCPP,5mg Fe-TCPP,25℃下超声30min,120℃下反应12 h,抽滤,洗涤至滤液为无色,在65℃下烘干,得到电催化剂的前驱体,记作 20-Heme@Fe5-PCN-222,之后将前驱体以5℃/min升温速率至700℃后恒温2h,最终得到黑色粉末固体,记作20-Heme@Fe5-PCN-222-700。Disperse 40 mg of ZrOCl 2 ·8H 2 O in 8 mL of DMF solution, add 650 mg of benzoic acid, 20 mg of Heme, 35 TCPP, 5 mg of Fe-TCPP, sonicate for 30 min at 25 °C, react at 120 °C for 12 h, suction filtration, and wash until the filtrate is Colorless, dried at 65°C to obtain the precursor of the electrocatalyst, denoted as 20-Heme@Fe 5 -PCN-222, and then the precursor was heated at a rate of 5°C/min to 700°C and kept at a constant temperature for 2h, and finally obtained Black powder solid, denoted as 20-Heme@Fe 5 -PCN-222-700.

实施例7Example 7

将40mg ZrOCl2·8H2O分散于8mL的DMF溶液中,加入650mg苯甲酸 20mg Heme,20TCPP,20mg Fe-TCPP,25℃下超声30min,120℃下反应 12h,抽滤,洗涤至滤液为无色,在65℃下烘干,得到电催化剂的前驱体,记作20-Heme@Fe20-PCN-222,之后将前驱体以5℃/min升温速率至700℃后恒温2h,最终得到黑色粉末固体,记作20-Heme@Fe20-PCN-222-700。Disperse 40 mg of ZrOCl 2 ·8H 2 O in 8 mL of DMF solution, add 650 mg of benzoic acid, 20 mg of Heme, 20 TCPP, 20 mg of Fe-TCPP, ultrasonicate for 30 min at 25 °C, react at 120 °C for 12 h, suction filtration, and wash until the filtrate is free of After drying at 65 °C, the precursor of the electrocatalyst was obtained, which was denoted as 20-Heme@Fe 20 -PCN-222. Then the precursor was heated at a rate of 5 °C/min to 700 °C and kept at a constant temperature for 2 h, and finally a black color was obtained. Powder solid, denoted 20-Heme@Fe 20 -PCN-222-700.

实施例8Example 8

将40mg ZrOCl2·8H2O分散于8mL的DMF溶液中,加入650mg苯甲酸 20mg Heme,10TCPP,30mg Fe-TCPP,25℃下超声30min,120℃下反应 12h,抽滤,洗涤至滤液为无色,在65℃下烘干,得到电催化剂的前驱体,记作20-Heme@Fe30-PCN-222,之后将前驱体以5℃/min升温速率至700℃后恒温2h,最终得到黑色粉末固体,记作20-Heme@Fe30-PCN-222-700。Disperse 40 mg of ZrOCl 2 ·8H 2 O in 8 mL of DMF solution, add 650 mg of benzoic acid, 20 mg of Heme, 10 TCPP, 30 mg of Fe-TCPP, sonicate for 30 min at 25 °C, react at 120 °C for 12 h, suction filtration, and wash until the filtrate is free of After drying at 65 °C, the precursor of the electrocatalyst was obtained, which was denoted as 20-Heme@Fe 30 -PCN-222. Then the precursor was heated at a rate of 5 °C/min to 700 °C and kept at a constant temperature for 2 h, and finally a black color was obtained. Powder solid, denoted 20-Heme@ Fe30 -PCN-222-700.

实施例9Example 9

将40mg ZrOCl2·8H2O分散于8mL的DMF溶液中,加入650mg苯甲酸 20mg Heme,40mgFe-TCPP,25℃下超声30min,120℃下反应12h,抽滤,洗涤至滤液为无色,在65℃下烘干,得到电催化剂的前驱体,记作 20-Heme@Fe40-PCN-222,之后将前驱体以5℃/min升温速率至700℃后恒温2 h,最终得到黑色粉末固体,记作20-Heme@Fe40-PCN-222-700。Disperse 40 mg of ZrOCl 2 ·8H 2 O in 8 mL of DMF solution, add 650 mg of benzoic acid, 20 mg of Heme, 40 mg of Fe-TCPP, sonicate for 30 min at 25 °C, react at 120 °C for 12 h, filter with suction, wash until the filtrate is colorless, Drying at 65 °C to obtain the precursor of the electrocatalyst, denoted as 20-Heme@Fe 40 -PCN-222, then the precursor was heated at a rate of 5 °C/min to 700 °C and then kept at a constant temperature for 2 h, and finally a black powder solid was obtained. , denoted 20-Heme@Fe 40 -PCN-222-700.

Claims (6)

1.一种高密度Fe-N4活性位点氧还原电催化剂的制备方法,其特征在于,包括以下步骤:1. a high-density Fe-N 4 preparation method of active site oxygen reduction electrocatalyst, is characterized in that, comprises the following steps: 将锆盐均匀分散于溶剂中,加入大环化合物Ⅰ、金属大环化合物Ⅱ和有机酸,在20-40℃条件下,超声处理10-30min,于120℃下反应8-12h,抽滤,洗涤至滤液为无色,烘干,于600-900℃下热解1-2h,得到高密度Fe-N4活性位点氧还原电催化剂;Disperse the zirconium salt evenly in the solvent, add the macrocyclic compound I, the metal macrocyclic compound II and the organic acid, at 20-40 °C, ultrasonically treat for 10-30 min, react at 120 °C for 8-12 h, suction filtration, Wash until the filtrate is colorless, dry, and pyrolyze at 600-900 °C for 1-2 h to obtain a high-density Fe-N 4 active site oxygen reduction electrocatalyst; 所述的大环化合物Ⅰ和锆盐的物质的量比为0.1-0.4:1;The substance ratio of the macrocyclic compound I and the zirconium salt is 0.1-0.4:1; 所述的金属大环化合物Ⅱ与大环化合物Ⅰ的质量比为0.25-1:1;The mass ratio of the metal macrocyclic compound II to the macrocyclic compound I is 0.25-1:1; 所述的有机酸和锆盐的物质的量比为20-30:1;The material ratio of described organic acid and zirconium salt is 20-30:1; 所述的大环化合物Ⅰ为侧链含四个羧基的卟啉或酞菁或卟吩,其中所述的大环化合物Ⅰ的中心无金属元素和/或包括金属元素,所述的金属为铁;所述的金属大环化合物Ⅱ为血晶素;The macrocyclic compound I is a porphyrin or phthalocyanine or porphine containing four carboxyl groups in the side chain, wherein the center of the macrocyclic compound I is free of metal elements and/or includes metal elements, and the metal is iron ; the metal macrocyclic compound II is hematoxylin; 所述的锆盐为ZrCl4、ZrOCl2·8H2O、ZrO(NO3)2·H2O中的一种或两种以上;The zirconium salt is one or more of ZrCl 4 , ZrOCl 2 ·8H 2 O, and ZrO(NO 3 ) 2 ·H 2 O; 所述的有机酸为CH2O2、C2H4O2、C2HF3O2、C3H6O2、C4H8O2、C2H2Cl2O2、C7H6O2、C8H8O2中的一种或两种以上的混合物。The organic acids are CH 2 O 2 , C 2 H 4 O 2 , C 2 HF 3 O 2 , C 3 H 6 O 2 , C 4 H 8 O 2 , C 2 H 2 Cl 2 O 2 , C 7 One or a mixture of two or more of H 6 O 2 and C 8 H 8 O 2 . 2.根据权利要求1所述的一种高密度Fe-N4活性位点氧还原电催化剂的制备方法,其特征在于,所述的溶剂为乙醇、丙醇、异丙醇、二甲基亚砜、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺中的一种或两种以上的混合物。2. the preparation method of a kind of high-density Fe - N active site oxygen reduction electrocatalyst according to claim 1, is characterized in that, described solvent is ethanol, propanol, isopropanol, dimethyl methylene One or more mixtures of sulfone, N,N-dimethylformamide and N,N-dimethylacetamide. 3.根据权利要求1所述的一种高密度Fe-N4活性位点氧还原电催化剂的制备方法,其特征在于,所述的锆盐中的锆在溶剂中的浓度为2-8mg/ml。3. the preparation method of a kind of high-density Fe - N active site oxygen reduction electrocatalyst according to claim 1, is characterized in that, the concentration of the zirconium in described zirconium salt in solvent is 2-8mg/ ml. 4.根据权利要求1所述的一种高密度Fe-N4活性位点氧还原电催化剂的制备方法,其特征在于,升温至热解温度的速率为1-10℃/min。4 . The preparation method of a high-density Fe-N 4 active site oxygen reduction electrocatalyst according to claim 1 , wherein the rate of heating up to the pyrolysis temperature is 1-10° C./min. 5 . 5.权利要求1-4任一所述的制备方法制备得到的高密度Fe-N4活性位点氧还原电催化剂。5. The high-density Fe-N 4 active site oxygen reduction electrocatalyst prepared by the preparation method of any one of claims 1-4. 6.权利要求5所述的高密度Fe-N4活性位点氧还原电催化剂在燃料电池中的应用。6. Application of the high-density Fe- N4 active site oxygen reduction electrocatalyst of claim 5 in fuel cells.
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