CN103721748B - High-efficiency oxygen molecule reduction base metal catalyst and preparation thereof - Google Patents
High-efficiency oxygen molecule reduction base metal catalyst and preparation thereof Download PDFInfo
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Abstract
本发明提供了一类高效氧分子还原贱金属催化剂的制备方法。具体地,本发明提供了一种具有以下式I结构的复合物催化体系:其中,各结构组成部分的定义如说明书中所述。本发明的复合物体系可以用于催化氧分子还原反应,作为氧分子还原电催化剂,催化性能优异,可替代现有的贵金属铂催化剂,在燃料电池电动汽车等领域具有极大的潜在应用前景和商业价值。Carrier‑(Linker‑Ligand‑Metal complex)n 式I。The invention provides a preparation method of a class of high-efficiency oxygen molecule reduction base metal catalyst. Specifically, the present invention provides a composite catalytic system having the following structure of formula I: wherein, the definition of each structural component is as described in the specification. The composite system of the present invention can be used to catalyze the reduction reaction of oxygen molecules. As an electrocatalyst for the reduction of oxygen molecules, it has excellent catalytic performance and can replace the existing precious metal platinum catalysts. It has great potential application prospects in the fields of fuel cell electric vehicles and the like. commercial value. Carrier‑(Linker‑Ligand‑Metal complex) nFormula I.
Description
技术领域technical field
本发明涉及燃料电池催化剂领域,具体地,本发明提供了一类高效氧分子还原贱金属催化剂,及其制备方法。The invention relates to the field of fuel cell catalysts, in particular, the invention provides a class of high-efficiency oxygen molecule reduction base metal catalysts and a preparation method thereof.
背景技术Background technique
燃料电池是一种通过电极化学反应持续的将燃料(如氢气)和氧气的化学能直接转化成电能的装置,其阳极为氢电极(氢气氧化分解为质子和电子:H2→2H++2e-),阴极为氧电极(氧气还原为水:1/2O2+2H++2e-→H2O),阳极和阴极上负载有一定量的催化剂用来加速电极上发生的电化学反应。燃料电池特别是质子交换膜燃料电池(Polymer ElectrolyteMembrane Fuel Cells,PEMFC)具有运行温度低、启动时间短、转换效率高、清洁排放(产物为水)等特点,在未来的交通工具应用中具有极大潜力。虽然燃料电池的研发技术已非常成熟,但困扰燃料电池电动车实现大规模商业化生产的一个“瓶颈”便是电池造价太昂贵(主要来自于其电极电催化剂费用太高)。目前燃料电池电催化剂主要为铂系贵金属。由于稀有金属铂的价格昂贵及将来的持续供应问题,开发新型的贱金属电催化剂便显得尤其重要。A fuel cell is a device that directly converts the chemical energy of fuel (such as hydrogen) and oxygen into electrical energy through an electrode chemical reaction, and its anode is a hydrogen electrode (hydrogen is oxidized and decomposed into protons and electrons: H 2 → 2H + +2e - ), the cathode is an oxygen electrode (oxygen is reduced to water: 1/2O 2 +2H + +2e - →H 2 O), and a certain amount of catalyst is loaded on the anode and cathode to accelerate the electrochemical reaction on the electrode. Fuel cells, especially proton exchange membrane fuel cells (Polymer Electrolyte Membrane Fuel Cells, PEMFC), have the characteristics of low operating temperature, short start-up time, high conversion efficiency, clean emission (product is water), etc., and have great potential in future transportation applications. potential. Although the research and development technology of fuel cells is very mature, a "bottleneck" that plagues the large-scale commercial production of fuel cell electric vehicles is that the cost of batteries is too high (mainly due to the high cost of its electrode electrocatalyst). Currently, fuel cell electrocatalysts are mainly platinum-group noble metals. Due to the high price of the rare metal platinum and the problem of continuous supply in the future, it is particularly important to develop new base metal electrocatalysts.
非铂系催化剂即贱金属催化剂一直是氧分子还原电催化剂研究的重点方向。钴、铁、锰等过渡金属配合物包括它们的大环配合物等都曾用作ORR催化剂,有的活性还不错。这些贱金属催化剂最终都需经过高温处理(≥500摄氏度)才能体现出较高的催化活性和稳定性,但经过高温热处理后初始加入的金属(大环)配合物已分解,导致催化剂活性中心物种不明。另外,催化剂的耐久性不佳。近年来贱金属催化剂的研究得到了进一步的广泛重视和突破。美国的Zelenay研究组通过往聚吡咯(PPY)包裹的碳粉上添加醋酸钴然后经过NaBH4还原的方式得到吡咯与钴配位的碳负载催化剂Co-PPY-C,该催化剂表现出很高的ORR催化活性,不过持续稳定性不高。该研究组随后进一步改进了催化剂的制备,他们改用先将苯胺、碳粉、含钴和铁的盐类混合,然后通过氧化聚合→氮气和氨气氛围下高温处理→酸漂洗等步骤得到了与铂催化剂几乎相媲美的高催化活性和耐久性的贱金属电催化剂。最近,他们通过将碳纳米管、含氮前驱体及金属铁盐通过简单混合煅烧制备了氮参杂N-Fe-CNT/CNP复合催化剂。该复合催化剂在碱性条件下表现出与商业铂/碳类似的ORR催化活性。加拿大的Dodelet研究小组报道了通过球碾磨技术往微晶碳的微孔结构中添加含氮的配体(如邻菲啰啉)和醋酸铁,然后经过氩气和氨气氛围下高温处理得到高活性的ORR电催化剂,但催化剂稳定性仍不高,无法与铂催化剂抗衡。最近,他们用MOFs框架结构包裹含铁盐和氮的前驱体,然后通过高温煅烧制备了新的ORR催化剂,该催化剂表现出较高的体积活性和传质性能。另外,不含金属的(metal-free)氮、氟参杂碳材料ORR催化剂也有大量研究,这类催化剂一般在碱性条件下有较好的ORR催化性能,酸性环境中鲜有与铂/碳催化剂相当的催化性能,碳材料中氮、氟参杂量的多少及参杂过程往往难于控制。Non-platinum catalysts, that is, base metal catalysts, have always been the focus of research on electrocatalysts for the reduction of oxygen molecules. Cobalt, iron, manganese and other transition metal complexes, including their macrocyclic complexes, have been used as ORR catalysts, and some of them have good activity. These base metal catalysts finally need to be treated at high temperature (≥500 degrees Celsius) to show high catalytic activity and stability, but after high temperature heat treatment, the metal (macrocyclic) complex initially added has been decomposed, resulting in catalyst active center species unknown. In addition, the durability of the catalyst is poor. In recent years, the research on base metal catalysts has received further extensive attention and breakthroughs. The Zelenay research group in the United States obtained Co-PPY-C, a carbon-supported catalyst coordinated by pyrrole and cobalt, by adding cobalt acetate to polypyrrole (PPY)-wrapped carbon powder and then reducing it with NaBH 4 . ORR catalytic activity, but the sustained stability is not high. The research group then further improved the preparation of the catalyst by first mixing aniline, carbon powder, cobalt and iron-containing salts, and then through oxidative polymerization → high temperature treatment under nitrogen and ammonia atmosphere → acid rinsing and other steps. Base metal electrocatalysts with high catalytic activity and durability nearly comparable to platinum catalysts. Recently, they prepared nitrogen-doped N-Fe-CNT/CNP composite catalysts by simply mixing and calcining carbon nanotubes, nitrogen-containing precursors, and metal iron salts. The composite catalyst exhibits ORR catalytic activity similar to that of commercial Pt/C under alkaline conditions. The Dodelet research group in Canada reported that nitrogen-containing ligands (such as o-phenanthroline) and iron acetate were added to the microporous structure of microcrystalline carbon by ball milling technology, and then obtained by high-temperature treatment under argon and ammonia atmospheres. Highly active ORR electrocatalysts, but the catalyst stability is still not high enough to compete with platinum catalysts. Recently, they encapsulated iron salt and nitrogen-containing precursors with MOFs framework structure, and then prepared a new ORR catalyst by high-temperature calcination, which exhibited high volume activity and mass transfer performance. In addition, metal-free (metal-free) nitrogen and fluorine-doped carbon material ORR catalysts have also been studied a lot. Such catalysts generally have better ORR catalytic performance in alkaline conditions, and rarely compare with platinum/carbon in acidic environments. The catalytic performance of the catalyst, the amount of nitrogen and fluorine doping in the carbon material and the doping process are often difficult to control.
总之,随着人们对新能源需求的增加,贱金属ORR电催化剂的研究近年来取得蓬勃发展。但贱金属ORR催化剂的制备过程往往需经过高温处理,这一热处理过程完全破坏了初始配合物的结构特性,无法通过催化剂结构性能的改变来调控催化剂的反应活性。另外,目前报道的贱金属ORR电催化剂大多数只在碱性环境下表现较高的催化活性,其中只有极少数的催化活性与铂/碳催化剂相当。In conclusion, with the increasing demand for new energy sources, the research on base metal ORR electrocatalysts has flourished in recent years. However, the preparation process of base metal ORR catalysts often requires high-temperature treatment. This heat treatment process completely destroys the structural characteristics of the initial complexes, and the reactivity of the catalyst cannot be adjusted by changing the structure and properties of the catalyst. In addition, most of the base metal ORR electrocatalysts reported so far only show high catalytic activity in alkaline environment, and only a few of them have comparable catalytic activity to Pt/C catalysts.
综上所述,本领域迫切需要开发一种价格低廉,制备方法简单,反应易控,且在碱性和酸性条件下均表现较高的催化活性的氧分子还原反应催化剂。To sum up, there is an urgent need in this field to develop a low-cost, simple preparation method, easy-to-control reaction, and high catalytic activity under both alkaline and acidic conditions for the reduction of oxygen molecules.
发明内容Contents of the invention
本发明的目的是提供一种制备方法简单,反应易控,且在碱性和酸性条件下均表现较高的催化活性的氧分子还原反应催化剂。The object of the present invention is to provide a catalyst for the reduction reaction of oxygen molecules which has a simple preparation method, is easy to control the reaction, and exhibits high catalytic activity under both alkaline and acidic conditions.
本发明的第一方面,提供了一种具有以下结构的复合催化剂:A first aspect of the present invention provides a composite catalyst with the following structure:
Carrier-(Linker-Ligand-Metal complex)n 式ICarrier-(Linker-Ligand-Metal complex) n formula I
其中,in,
"-"表示化学键,所述的化学键为共价键或配位键;"-" represents a chemical bond, and the chemical bond is a covalent bond or a coordination bond;
Carrier为碳基基质载体;Carrier is a carbon-based matrix carrier;
Ligand为含氮的五元或六元杂环配位基团;Ligand is a nitrogen-containing five-membered or six-membered heterocyclic coordination group;
Linker为连接分子,所述的连接分子通过共价键分别与碳基载体和含氮的五元或六元杂环配位基团相连;Linker is a linking molecule, and the linking molecule is respectively connected to a carbon-based carrier and a nitrogen-containing five-membered or six-membered heterocyclic coordination group through a covalent bond;
Metal complex选自下组:取代或未取代的铁、钴、锰卟啉分子;取代或未取代的铁、钴、锰酞菁分子;取代或未取代的铁、钴、锰咕啉分子;含氮配体配位的铜、铁、钴、锰配合物;所述的Metal complex与含氮的五元或六元杂环上的氮原子形成配位键;Metal complex is selected from the following group: substituted or unsubstituted iron, cobalt, manganese porphyrin molecules; substituted or unsubstituted iron, cobalt, manganese phthalocyanine molecules; substituted or unsubstituted iron, cobalt, manganese corrin molecules; Copper, iron, cobalt, and manganese complexes coordinated by nitrogen ligands; the Metal complex forms a coordination bond with the nitrogen atom on the nitrogen-containing five-membered or six-membered heterocyclic ring;
n≥1。n≥1.
在另一优选例中,所述的Carrier选自下组:单壁碳纳米管、多壁碳纳米管、石墨烯;较佳地,所述的Carrier为多壁碳纳米管。In another preferred example, the carrier is selected from the group consisting of single-walled carbon nanotubes, multi-walled carbon nanotubes, and graphene; preferably, the carrier is multi-walled carbon nanotubes.
在另一优选例中,所述的Ligand选自下组:咪唑基、吡啶基或多吡啶基。In another preferred example, the Ligand is selected from the group consisting of imidazolyl, pyridyl or polypyridyl.
在另一优选例中,所述的Linker选自下组:取代或未取代的C1-C5的烷基、取代或未取代的芳香基、取代或未取代的的杂环芳香基。In another preferred example, the Linker is selected from the group consisting of substituted or unsubstituted C1-C5 alkyl, substituted or unsubstituted aryl, substituted or unsubstituted heterocyclic aromatic.
在另一优选例中,所述的Linker为取代或未取代的杂环芳香基,其中,所述的杂环芳香基具有3-9个氮原子。In another preferred example, the Linker is a substituted or unsubstituted heterocyclic aromatic group, wherein the heterocyclic aromatic group has 3-9 nitrogen atoms.
在另一优选例中,所述的Linker中存在至少一个芳香环状结构单元。In another preferred example, there is at least one aromatic ring structural unit in the Linker.
在另一优选例中,所述的Linker具有以下结构:In another preferred example, the Linker has the following structure:
在另一优选例中,所述的Metal complex具有以下结构的铁基卟啉:In another preferred example, the Metal complex has an iron-based porphyrin with the following structure:
式中,Ar选自下组:取代或未取代的芳香基、取代或未取代的氮杂环芳香基。In the formula, Ar is selected from the group consisting of substituted or unsubstituted aryl groups, substituted or unsubstituted azacyclic aromatic groups.
在另一优选例中,所述的Metal complex为具有以下结构的铁卟啉:In another preference, the Metal complex is iron porphyrin with the following structure:
其中,R1、R2、R3、R4、R5、R6、R7各自独立地选自下组:H、卤素、取代或未取代的C1-C4的烷基、取代或未取代的C1-C4的烷基-氧基、羧基、氨基、酰氨基。Wherein, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 are each independently selected from the following group: H, halogen, substituted or unsubstituted C1-C4 alkyl, substituted or unsubstituted C1-C4 alkyl-oxyl, carboxyl, amino, amido.
在另一优选例中,R1、R2、R3、R4、R5、R6、R7各自独立地选自下组:H、F、Cl、Br、CH3、CF3、羧基、COOCH3。In another preferred example, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 are each independently selected from the following group: H, F, Cl, Br, CH 3 , CF 3 , carboxyl , COOCH 3 .
在另一优选例中,R1、R2、R3、R4、R5、R6、R7均为H。In another preferred example, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are all H.
在另一优选例中,R1、R2、R3、R4、R5、R6、R7均为F。In another preferred example, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 are all F.
在另一优选例中,R1、R3、R4、R6、R7均为CH3,且R2、R5均为H。In another preferred example, R 1 , R 3 , R 4 , R 6 and R 7 are all CH 3 , and R 2 and R 5 are all H.
在另一优选例中,R1、R4、R7均为F,且R2、R3、R5、R6均为H。In another preferred example, R 1 , R 4 , and R 7 are all F, and R 2 , R 3 , R 5 , and R 6 are all H.
在另一优选例中,R1、R2、R4、R5、R7均为H,且R3、R6均为CF3。In another preferred example, R 1 , R 2 , R 4 , R 5 , and R 7 are all H, and R 3 and R 6 are all CF 3 .
在另一优选例中,R1、R2、R3、R5、R6、R7均为H,且R4为COOH或COOCH3。In another preferred example, R 1 , R 2 , R 3 , R 5 , R 6 , and R 7 are all H, and R 4 is COOH or COOCH 3 .
在另一优选例中,R1、R2、R3、R5、R6均为H,且R4、R7为COOH或COOCH3。In another preferred example, R 1 , R 2 , R 3 , R 5 and R 6 are all H, and R 4 and R 7 are COOH or COOCH 3 .
在另一优选例中,R1为F,R2、R3、R5、R6、R7均为H,且R4为COOH或COOCH3。In another preferred example, R 1 is F, R 2 , R 3 , R 5 , R 6 and R 7 are all H, and R 4 is COOH or COOCH 3 .
在另一优选例中,R1为F,R2、R3、R5、R6均为H,且R4、R7为COOH或COOCH3。In another preferred example, R 1 is F, R 2 , R 3 , R 5 and R 6 are all H, and R 4 and R 7 are COOH or COOCH 3 .
在另一优选例中,R1为F,R2、R3、R5、R6均为H,且R4、R7为COOH或COOCH3。In another preferred example, R 1 is F, R 2 , R 3 , R 5 and R 6 are all H, and R 4 and R 7 are COOH or COOCH 3 .
在另一优选例中,R1、R2、R3、R5、R6、R7均为F,且R4为COOH或COOCH3。In another preferred example, R 1 , R 2 , R 3 , R 5 , R 6 , and R 7 are all F, and R 4 is COOH or COOCH 3 .
在另一优选例中,R1、R2、R3、R5、R6均为F,且R4、R7为COOH或COOCH3。In another preferred example, R 1 , R 2 , R 3 , R 5 , and R 6 are all F, and R 4 , R 7 are COOH or COOCH 3 .
在另一优选例中,R1、R2、R5、R6、R7均为H,R3为CF3,且R4为COOH或COOCH3。In another preferred example, R 1 , R 2 , R 5 , R 6 , and R 7 are all H, R 3 is CF 3 , and R 4 is COOH or COOCH 3 .
在另一优选例中,R1、R2、R5、R6均为H,R3为CF3,且R4、R7为COOH或COOCH3。In another preferred example, R 1 , R 2 , R 5 , and R 6 are all H, R 3 is CF 3 , and R 4 , R 7 are COOH or COOCH 3 .
本发明的第二方面,提供了一种如本发明第一方面所述的催化剂的制备方法,所述方法包括步骤:A second aspect of the present invention provides a method for preparing a catalyst as described in the first aspect of the present invention, said method comprising the steps of:
(i)提供一如式Ia所示的,表面修饰有连接分子和含氮的五元或六元杂环配位基团的碳基载体Carrier-(Linker-Ligand)n,其中所述连接分子Linker通过共价化学键连接于碳基载体Carrier的表面,且所述含氮的五元或六元杂环基团Ligand通过共价化学键与所述连接分子Linker相连;(i) Provide a carbon-based carrier Carrier-(Linker-Ligand) n as shown in formula Ia, the surface of which is modified with a linker molecule and a nitrogen-containing five-membered or six-membered heterocyclic coordination group, wherein the linker molecule The Linker is connected to the surface of the carbon-based carrier Carrier through a covalent chemical bond, and the nitrogen-containing five-membered or six-membered heterocyclic group Ligand is connected to the linker molecule Linker through a covalent chemical bond;
Carrier-(Linker-Ligand)m 式IaCarrier-(Linker-Ligand) m type Ia
(ii)用取代或未取代的Metal complex与所述的Carrier-(Linker-Ligand)m进行反应,形成式I所示的化合物;(ii) using a substituted or unsubstituted Metal complex to react with the Carrier-(Linker-Ligand) m to form a compound shown in formula I;
Carrier-(Linker-Ligand-Metal complex)n 式ICarrier-(Linker-Ligand-Metal complex) n formula I
其中,Carrier、Linker、Ligand、Metal complex、n的定义如本发明第一方面所述;m≥1,且m与n可相等或不相等。Wherein, the definitions of Carrier, Linker, Ligand, Metal complex, and n are as described in the first aspect of the present invention; m≥1, and m and n may be equal or unequal.
在另一优选例中,在所述的制备方法中,步骤(i)和(ii)均在≤80℃的条件下进行。In another preferred example, in the preparation method, both steps (i) and (ii) are carried out at ≤80°C.
在另一优选例中,m≥n。In another preferred example, m≥n.
在另一优选例中,在所述步骤(ii)制得的式I化合物中,所述的碳基载体carrier表面含有部分未与Metal complex配位的-Linker-Ligand表面修饰基团。In another preferred example, in the compound of formula I prepared in the step (ii), the surface of the carbon-based carrier carrier contains some -Linker-Ligand surface modification groups that are not coordinated with the Metal complex.
在另一优选例中,所述的式Ia化合物通过包括以下步骤的方法制备:In another preferred embodiment, the compound of formula Ia is prepared by a method comprising the following steps:
提供碳基载体Carrier;Provide carbon-based carrier Carrier;
用偶联试剂对所述的碳基载体Carrier进行表面修饰,形成表面具有连接分子La修饰的碳基载体;Using a coupling reagent to modify the surface of the carbon-based carrier Carrier to form a carbon-based carrier with a La modification on the surface;
在连接分子上原位形成所述的含氮的五元或六元杂环基团,得到式Ia化合物。In situ formation of said nitrogen-containing five-membered or six-membered heterocyclic group on the linker molecule yields a compound of formula Ia.
在另一优选例中,所述的La与Linker相同或不同。In another preferred embodiment, said La is the same as or different from Linker.
在另一优选例中,所述的式Ia化合物通过包括以下步骤的方法制备:In another preferred embodiment, the compound of formula Ia is prepared by a method comprising the following steps:
(a)提供碳基载体Carrier;(a) Provide carbon-based carrier Carrier;
(b)用一种或多种偶联试剂对碳基载体Carrier进行表面修饰,得到表面修饰的碳基载体Carrier-(Linker-Ligand)m;其中,在所述的偶联试剂中,至少一种的结构中含有含氮的五元或六元杂环基。(b) surface-modify the carbon-based carrier Carrier with one or more coupling reagents to obtain a surface-modified carbon-based carrier Carrier-(Linker-Ligand) m ; wherein, in the coupling reagents, at least one The structure of the species contains a nitrogen-containing five-membered or six-membered heterocyclic group.
在另一优选例中,所述的式Ia化合物通过包括以下步骤的方法制备:In another preferred embodiment, the compound of formula Ia is prepared by a method comprising the following steps:
(a)提供碳基载体Carrier;(a) Provide carbon-based carrier Carrier;
(b)用偶联试剂Linker’-X对碳基载体Carrier进行表面修饰,得到表面修饰的碳基载体Carrier-(Linker’)m;(b) surface-modify the carbon-based carrier Carrier with a coupling reagent Linker'-X to obtain a surface-modified carbon-based carrier Carrier-(Linker') m ;
(c)将结构中含有含氮的五元或六元杂环基的试剂Ligand-Linker’’与所述的表面修饰的碳基载体Carrier-(Linker’)m反应,得到表面修饰有配位基团的碳基载体Carrier-(Linker-Ligand)m;(c) react the reagent Ligand-Linker'' containing nitrogen-containing five-membered or six-membered heterocyclic group in the structure with the surface-modified carbon-based carrier Carrier-(Linker') m to obtain a surface-modified The carbon-based carrier Carrier-(Linker-Ligand) m of the group;
其中,Linker'和Linker’’为包括Linker的全部或部分结构的连接分子,且Linker’与Linker’’反应可形成Linker;Among them, Linker' and Linker'' are linking molecules including all or part of the structure of Linker, and Linker' and Linker'' can react to form Linker;
X为离去基团。X is a leaving group.
在另一优选例中,所述的Linker’为苯基。In another preferred embodiment, the Linker' is phenyl.
在另一优选例中,所述的Linker’-X为三异丙基硅炔苯基偶氮氟硼酸盐。In another preferred example, the Linker'-X is triisopropylsilynylphenylazofluoroborate.
在另一优选例中,所述的步骤(b)在还原性试剂存在下进行,较佳地,所述的还原性试剂是水合肼。In another preferred example, the step (b) is performed in the presence of a reducing agent, preferably, the reducing agent is hydrazine hydrate.
在另一优选例中,所述的Linker"为4-叠氮苯基。In another preferred example, the Linker" is 4-azidophenyl.
在另一优选例中,所述的Ligand-Linker"为1-(4-叠氮苯基)咪唑。In another preference, the Ligand-Linker "is 1-(4-azidophenyl) imidazole.
本发明的第三方面,提供了一种如本发明第一方面所述的催化剂的用途,用于作为氧分子还原反应的催化剂。The third aspect of the present invention provides the use of the catalyst according to the first aspect of the present invention as a catalyst for the reduction reaction of oxygen molecules.
在另一优选例中,所述的氧分子还原反应在碱性或酸性环境下进行。较佳地,所述的酸性环境指反应体系的pH≤5;所述的碱性环境指反应体系的pH≥13。In another preferred example, the oxygen molecule reduction reaction is carried out in an alkaline or acidic environment. Preferably, the acidic environment refers to the pH of the reaction system≤5; the alkaline environment refers to the pH of the reaction system≥13.
本发明的第四方面,提供了一种氧分子还原催化剂,所述的催化剂中包括如本发明第一方面所述的催化剂。The fourth aspect of the present invention provides an oxygen molecule reduction catalyst, which includes the catalyst as described in the first aspect of the present invention.
本发明的第五方面,提供了一种燃料电池,其特征在于,所述的燃料电池中包括本发明第一方面所述的催化剂。A fifth aspect of the present invention provides a fuel cell, characterized in that the fuel cell includes the catalyst described in the first aspect of the present invention.
在另一优选例中,所述的燃料电池的电极催化剂中包括本发明第一方面所述的催化剂In another preferred example, the electrode catalyst of the fuel cell includes the catalyst described in the first aspect of the present invention
应理解,在本发明范围内中,本发明的上述各技术特征和在下文(如实施例)中具体描述的各技术特征之间都可以互相组合,从而构成新的或优选的技术方案。限于篇幅,在此不再一一累述。It should be understood that within the scope of the present invention, the above-mentioned technical features of the present invention and the technical features specifically described in the following (such as embodiments) can be combined with each other to form new or preferred technical solutions. Due to space limitations, we will not repeat them here.
附图说明Description of drawings
图1碱性环境中催化剂的ORR极化曲线。黑色实线:20%Pt/C;红色实线:CNTImFeF2TPP(0.1M KOH,@1600rpm;CNTImFeF2TPP:对应表1中第4个化合物,即R1=R4=R7=F,R2=R3=R5=R6=H)。Fig. 1 ORR polarization curves of catalysts in alkaline environment. Black solid line: 20%Pt/C; Red solid line: CNTImFeF 2 TPP (0.1M KOH,@1600rpm; CNTImFeF 2 TPP: corresponding to the fourth compound in Table 1, that is, R 1 =R 4 =R 7 =F, R 2 =R 3 =R 5 =R 6 =H).
图2碱性环境中盘工作电极上生成H2O2的百分比随电位变化曲线。黑色实线:20%Pt/C;红色实线:CNTImFeF2TPP(0.1M KOH,@1600rpm)。Fig. 2 Curve of the percentage of H 2 O 2 generated on the disk working electrode in alkaline environment versus potential. Black solid line: 20%Pt/C; red solid line: CNTImFeF 2 TPP (0.1M KOH, @1600rpm).
图3碱性环境中催化剂的稳定性。黑色实线:20%Pt/C;红色实线:CNTImFeF2TPP(0.1M KOH,@0.7V vs RHE,900rpm)。Figure 3 Stability of catalysts in alkaline environments. Black solid line: 20%Pt/C; red solid line: CNTImFeF 2 TPP (0.1M KOH, @0.7V vs RHE, 900rpm).
图4酸性环境中催化剂的ORR极化曲线,黑色实线:20%Pt/C;红色实线:CNTImFeF2TPP(0.1M HClO4,@1600rpm)。Figure 4 ORR polarization curves of catalysts in acidic environment, black solid line: 20%Pt/C; red solid line: CNTImFeF 2 TPP (0.1M HClO 4 ,@1600rpm).
图5酸性环境中盘工作电极上生成H2O2的百分比随电位变化曲线。黑色实线:20%Pt/C;红色实线:CNTImFeF2TPP(0.1M HClO4,@1600rpm)。Fig. 5 The percentage of H 2 O 2 generated on the disk working electrode in an acidic environment varies with potential. Black solid line: 20%Pt/C; red solid line: CNTImFeF 2 TPP (0.1M HClO 4 ,@1600rpm).
图6酸性环境中催化剂的稳定性,黑色实线:20%Pt/C;红色实线:CNTImFeF2TPP(0.1M HClO4,@0.7V vs RHE,900rpm)。Figure 6 Stability of catalysts in acidic environment, black solid line: 20%Pt/C; red solid line: CNTImFeF 2 TPP (0.1M HClO 4 ,@0.7V vs RHE,900rpm).
具体实施方式detailed description
术语the term
如本文所用,术语“连接分子”或“连接基团”指通过共价键与碳基载体连接的修饰基团。其中,所述的“通过化学键”既包括直接与碳基载体表面通过共价键相连,也包括与碳基载体表面上的修饰基团通过共价键相连。As used herein, the term "linker molecule" or "linker group" refers to a modifying group attached to a carbon-based support by a covalent bond. Wherein, the "through a chemical bond" includes not only being directly connected to the surface of the carbon-based support through a covalent bond, but also including being connected with a modification group on the surface of the carbon-based support through a covalent bond.
如本文所用,术语“烷基”指具有1~30个碳原子的直链、支链或环烷基,例如甲基、乙基、丙基、异丙基、丁基、异丁基、仲丁基、叔丁基、环丙基、或类似基团。As used herein, the term "alkyl" refers to a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec Butyl, tert-butyl, cyclopropyl, or similar groups.
术语“C1-C4的烷基”指具有1~4个碳原子的直链、支链或环烷基,例如甲基、乙基、丙基、异丙基、丁基、异丁基、仲丁基、叔丁基、环丙基、或类似基团。The term "C1-C4 alkyl" refers to a straight chain, branched or cyclic alkyl group with 1 to 4 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec Butyl, tert-butyl, cyclopropyl, or similar groups.
术语“芳基(芳香基”指具有6~30个碳原子的芳基,包括单环或二环芳基,例如苯基、萘基,或类似基团。The term "aryl" refers to an aryl group having 6 to 30 carbon atoms, including monocyclic or bicyclic aryl groups such as phenyl, naphthyl, or the like.
术语“杂芳基(杂环芳香基)”指具有2~30个碳原子的杂芳基,例如吡咯基、吡啶基、呋喃基,或类似基团。The term "heteroaryl (heterocyclic aromatic group)" refers to a heteroaryl group having 2 to 30 carbon atoms, such as pyrrolyl, pyridyl, furyl, or the like.
术语“酰氨基”指具有2-8个碳原子的酰胺基,例如乙酰胺基,或类似基团。The term "acylamino" refers to an amide group having 2 to 8 carbon atoms, such as acetamido, or the like.
术语“氮杂环芳香基”指具有2-30个碳原子的氮杂环芳香基,如吡啶、吡咯,或类似基团。The term "nitroaromatic group" refers to a nitrogen heterocyclic aromatic group having 2-30 carbon atoms, such as pyridine, pyrrole, or similar groups.
除非特别说明,术语“取代”指基团上的一个或多个氢原子被选自下组的取代基取代:C1~C10烷基、C1~C10烷基-氧基、卤素、羟基、羧基(-COOH)、C1~C10烷基-醛基、C1~C10烷基-酰基、C2~C10酯基、氰基、硝基、氨基、苯基;所述的苯基包括未取代的苯基或具有1-3个取代基的取代苯基,所述取代基选自:卤素、C1-C10烷基、氰基、OH、硝基、C1~C10烷基-氧基、氨基。Unless otherwise specified, the term "substituted" means that one or more hydrogen atoms on the group are replaced by substituents selected from the group consisting of: C1~C10 alkyl, C1~C10 alkyl-oxyl, halogen, hydroxyl, carboxyl ( -COOH), C1~C10 alkyl-aldehyde group, C1~C10 alkyl-acyl group, C2~C10 ester group, cyano group, nitro group, amino group, phenyl group; the phenyl group includes unsubstituted phenyl or A substituted phenyl group having 1-3 substituents selected from the group consisting of: halogen, C1-C10 alkyl, cyano, OH, nitro, C1-C10 alkyl-oxyl, amino.
术语“多吡啶基”指结构内具有两个以上吡啶环结构的基团,如联吡啶或联三吡啶。The term "polypyridyl" refers to a group having two or more pyridine ring structures in the structure, such as bipyridine or terpyridine.
术语“碳基基质载体”或“碳基载体”可互换使用,均指本发明的载体carrier。The terms "carbon-based matrix support" or "carbon-based support" are used interchangeably to refer to the carrier of the present invention.
各字母缩写对应的名称如下:The names corresponding to the abbreviations are as follows:
氧分子还原反应催化剂Molecular oxygen reduction reaction catalyst
所述的式I化合物可用于催化氧分子还原反应,制备氧分子还原反应的催化剂。The compound of formula I can be used to catalyze the reduction reaction of oxygen molecules and prepare a catalyst for the reduction reaction of oxygen molecules.
一类优选的本发明的贱金属ORR催化剂由表面咪唑基团功能化的碳纳米管和仿生血红素模型金属铁卟啉组成。碳纳米管表面的咪唑基团通过与铁卟啉的轴向配位完成仿生催化剂在碳纳米管上的共价负载。本发明实现了碳纳米管表面咪唑基团功能化,其特点在于碳纳米管表面的单分子层功能化修饰后实现了仿生血红素模型催化剂在碳纳米管上的有效组装,大大增加了碳纳米管表面的ORR活性反应位点,从而大副提升ORR催化性能。A preferred class of base metal ORR catalysts of the present invention consists of carbon nanotubes with surface imidazole groups functionalized and biomimetic heme model metalloiron porphyrins. The imidazole groups on the surface of carbon nanotubes complete the covalent loading of biomimetic catalysts on carbon nanotubes through axial coordination with iron porphyrin. The invention realizes the functionalization of imidazole groups on the surface of carbon nanotubes, and is characterized in that after the functional modification of the monomolecular layer on the surface of carbon nanotubes, the effective assembly of the bionic heme model catalyst on the carbon nanotubes is realized, which greatly increases the carbon nanotube ORR active reaction sites on the surface of the tube, thereby greatly improving the ORR catalytic performance.
一类优选的碳基载体为多壁碳纳米管。A preferred class of carbon-based supports are multi-walled carbon nanotubes.
一类优选的连接分子和配位基团(Linker-Ligand)为:A preferred class of linker molecules and coordination groups (Linker-Ligand) are:
一类优选的铁卟啉及其衍生物为:A class of preferred iron porphyrins and derivatives thereof are:
式中,Ar选自下组:取代或未取代的C6-C30芳基、取代或未取代的C1-C30杂芳基。优选地,铁卟啉衍生物部分具有如表1所示的结构:In the formula, Ar is selected from the following group: substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C1-C30 heteroaryl. Preferably, the iron porphyrin derivative part has a structure as shown in Table 1:
表1铁基卟啉类化合物Table 1 Iron-based porphyrin compounds
本发明实现了碳纳米管表面咪唑基团功能化修饰及仿生ORR催化剂在其表面的共价负载。该发明以催化剂结构可控、不经过高温煅烧的方式制备出ORR贱金属催化剂,所制备的催化剂在酸、碱性环境中的ORR催化活性均优于商业铂/碳催化剂。The invention realizes the functional modification of the imidazole group on the surface of the carbon nanotube and the covalent loading of the biomimetic ORR catalyst on the surface. The invention prepares an ORR base metal catalyst in a manner in which the catalyst structure is controllable and does not undergo high-temperature calcination. The ORR catalytic activity of the prepared catalyst is better than that of commercial platinum/carbon catalysts in both acidic and alkaline environments.
本发明的主要优点包括:The main advantages of the present invention include:
(1)本发明制备的催化剂结构可控,催化活性中心明了。(1) The structure of the catalyst prepared by the present invention is controllable, and the catalytic active center is clear.
(2)本发明制备的催化剂性能优于所有报道过的贱金属ORR催化剂和商业铂/碳催化剂。本发明制备的电催化剂的ORR半波电位、ORR起始电位、ORR电流密度、抗甲醇中毒能力等在酸、碱环境中均优于商业20%铂/碳催化剂。(2) The performance of the catalyst prepared by the present invention is superior to all reported base metal ORR catalysts and commercial platinum/carbon catalysts. The ORR half-wave potential, ORR onset potential, ORR current density, and methanol poisoning resistance of the electrocatalyst prepared in the present invention are all better than commercial 20% platinum/carbon catalysts in acid and alkali environments.
(3)由于本发明ORR电催化剂的催化性能优于商业20%铂/碳催化剂,将来有可能作为贱金属ORR电催化剂替代现有贵金属铂催化剂,在燃料电池电动汽车等领域具有极大的潜在应用前景和商业价值。新能源汽车生产公司可能对该发明技术有潜在需求。(3) Since the catalytic performance of the ORR electrocatalyst of the present invention is superior to commercial 20% platinum/carbon catalysts, it may be used as a base metal ORR electrocatalyst to replace the existing precious metal platinum catalyst in the future, and has great potential in the fields of fuel cell electric vehicles and the like Application prospect and commercial value. New energy vehicle production companies may have potential demand for the invented technology.
下面结合具体实施例,进一步阐述本发明。应理解,这些实施例仅用于说明本发明而不用于限制本发明的范围。下列实施例中未注明具体条件的实验方法,通常按照常规条件,或按照制造厂商所建议的条件。除非另外说明,否则百分比和份数按重量计算。Below in conjunction with specific embodiment, further illustrate the present invention. It should be understood that these examples are only used to illustrate the present invention and are not intended to limit the scope of the present invention. For the experimental methods without specific conditions indicated in the following examples, the conventional conditions or the conditions suggested by the manufacturer are usually followed. Percentages and parts are by weight unless otherwise indicated.
实施例1碳纳米管表面咪唑基团功能化修饰Example 1 Functional modification of imidazole groups on the surface of carbon nanotubes
将经过纯化处理的多壁碳纳米管(MWCNT,length~50μm,OD8-15nm,ID3-5nm,Chengdu Organic Chemical Co.Ltd,Chinese Academy of Sciences)与对三异丙基硅炔苯基偶氮氟硼酸盐于水中超声分散均匀,加入一定量的水合肼溶液,加热至80℃,反应过夜。过滤所得的滤饼,分别用DMF和超纯水洗涤。Purified multi-walled carbon nanotubes (MWCNT, length ~ 50 μm, OD8-15nm, ID3-5nm, Chengdu Organic Chemical Co.Ltd, Chinese Academy of Sciences) and p-triisopropylsilylyl azofluorine The borate is ultrasonically dispersed in water, and a certain amount of hydrazine hydrate solution is added, heated to 80°C, and reacted overnight. The resulting filter cake was filtered and washed with DMF and ultrapure water, respectively.
将一定量的三异丙基硅炔苯基MWCNT分散于DMF中,冰水浴下,加入四丁基氟化胺,于室温氮气氛围下反应2h。然后,往其中分别加入一定量的五水合硫酸铜,抗坏血酸钠和1-(4-叠氮苯基)咪唑,在氮气氛围下50℃反应36h。过滤所得的滤饼,分别用DMF,50mmol/LEDTA水溶液,超纯水洗涤,得到咪唑功能化的碳纳米管MWCNTIm。Disperse a certain amount of triisopropylsilynylphenyl MWCNT in DMF, add tetrabutylammonium fluoride under ice-water bath, and react at room temperature under nitrogen atmosphere for 2 hours. Then, a certain amount of copper sulfate pentahydrate, sodium ascorbate and 1-(4-azidophenyl)imidazole were respectively added therein, and reacted at 50° C. for 36 hours under a nitrogen atmosphere. Filter the obtained filter cake, wash with DMF, 50mmol/LEDTA aqueous solution, and ultrapure water respectively to obtain imidazole-functionalized carbon nanotube MWCNTIm.
实施例2铁基卟啉类化合物在碳纳米管表面的配位负载Example 2 Coordination loading of iron-based porphyrins on the surface of carbon nanotubes
将4.0mg修饰好的MWCNTIm与1.0mg铁卟啉类化合物分散于1.0mL甲醇中,于氮气氛围下室温搅拌15h。将复合物过滤,用少量甲醇洗涤3次,真空干燥3h,氮气氛围中暗处保存。铁卟啉选自上述表1中所列化合物。Disperse 4.0 mg of modified MWCNTIm and 1.0 mg of iron porphyrin compound in 1.0 mL of methanol, and stir at room temperature for 15 h under nitrogen atmosphere. The complex was filtered, washed three times with a small amount of methanol, dried in vacuum for 3 h, and stored in a dark place under nitrogen atmosphere. The iron porphyrin is selected from the compounds listed in Table 1 above.
实施例3催化剂性能测试Embodiment 3 Catalyst performance test
(a)催化剂油墨(catalyst ink)的制备:将适量5%Nafion溶液(Aldrich,USA)与异丙醇(体积比1:9)超声混合5min,然后加入适量本发明制备的催化剂(CNTImFeF2TPP,对应表1中第4个化合物,R1=R4=R7=F,R2=R3=R5=R6=H),超声分散均匀。取10~15μL催化剂油墨滴在玻碳电极表面,待溶剂室温挥发后作为工作电极。(a) Preparation of catalyst ink (catalyst ink): an appropriate amount of 5% Nafion solution (Aldrich, USA) was ultrasonically mixed with isopropanol (volume ratio 1:9) for 5 min, and then an appropriate amount of the catalyst prepared by the present invention (CNTImFeF 2 TPP , corresponding to the fourth compound in Table 1, R 1 =R 4 =R 7 =F, R 2 =R 3 =R 5 =R 6 =H), ultrasonic dispersion is uniform. Take 10-15 μL of catalyst ink and drop it on the surface of the glassy carbon electrode, and use it as the working electrode after the solvent evaporates at room temperature.
(b)ORR催化性能电化学测试:(b) Electrochemical test of ORR catalytic performance:
催化剂电催化性能的测试通过旋转电极装置(MSR,Pine公司产品,USA)和CHI760D电化学工作站实现。测试是在三电极体系中完成(均为Pine公司产品,USA),玻碳电极为工作盘电极(OD:5mm),Pt环为工作环电极(ID:6.5mm,OD:7.5mm),Pt丝为对电极,Hg/HgO(碱性条件下)或Ag/AgCl(酸性条件下)为参比电极。碱性测试环境为0.1mol/L KOH溶液,酸性测试环境为0.1mol/L HClO4溶液。作为对照的Pt系催化剂的ORR测定是在相同条件下利用含20%Pt/C催化剂(JMHiSPEC3000,Jonhnson Matthey Fuel Cells,USA)完成。最终的电位均系已转化为相对于可逆氢电极(RHE)的电位。The test of the electrocatalytic performance of the catalyst was realized by a rotating electrode device (MSR, product of Pine Company, USA) and a CHI760D electrochemical workstation. The test is completed in a three-electrode system (both products of Pine Company, USA), the glassy carbon electrode is the working disk electrode (OD: 5mm), the Pt ring is the working ring electrode (ID: 6.5mm, OD: 7.5mm), the Pt The wire is the counter electrode, and Hg/HgO (under alkaline conditions) or Ag/AgCl (under acidic conditions) is the reference electrode. The alkaline test environment is 0.1mol/L KOH solution, and the acidic test environment is 0.1mol/L HClO 4 solution. The ORR measurement of the Pt-based catalyst as a control was done under the same conditions using a 20% Pt/C catalyst (JMHiSPEC3000, Johnson Matthey Fuel Cells, USA). The final potentials have been converted to potentials relative to the reversible hydrogen electrode (RHE).
玻碳电极表面负载催化剂量:本发明催化剂:包含碳纳米管在内总量计为:1.0mg/cm2,以铁卟啉计为:0.2mg/cm2。Pt/C催化剂:1.0mg/cm2。The amount of catalyst supported on the surface of the glassy carbon electrode: the catalyst of the present invention: 1.0 mg/cm 2 in total including carbon nanotubes, 0.2 mg/cm 2 in iron porphyrin. Pt/C catalyst: 1.0 mg/cm 2 .
碱性环境中催化剂的ORR极化曲线如图1所示。黑色实线:20%Pt/C;红色实线:CNTImFeF2TPP(0.1M KOH,@1600rpm)。实验结果表明,与商业20%Pt/C催化剂相比,本发明催化剂CNTImFeF2TPP的ORR半波电位向正电位位移50mV,ORR电流密度增加约20%。The ORR polarization curves of the catalysts in alkaline environment are shown in Fig. 1. Black solid line: 20%Pt/C; red solid line: CNTImFeF 2 TPP (0.1M KOH, @1600rpm). The experimental results show that compared with the commercial 20%Pt/C catalyst, the ORR half-wave potential of the catalyst CNTImFeF 2 TPP of the present invention shifts 50mV to the positive potential, and the ORR current density increases by about 20%.
碱性环境中盘工作电极上生成H2O2的百分比随电位变化曲线如图2所示。黑色实线:20%Pt/C;红色实线:CNTImFeF2TPP(0.1M KOH,@1600rpm)。实验结果表明,本发明催化剂CNTImFeF2TPP所生成的H2O2的量只有商业20%Pt/C催化剂的一半左右,说明本发明催化剂对ORR有更高的四电子还原选择性,从而表现出更高的催化活性。Figure 2 shows the percentage of H 2 O 2 generated on the disk working electrode as a function of potential in an alkaline environment. Black solid line: 20%Pt/C; red solid line: CNTImFeF 2 TPP (0.1M KOH, @1600rpm). The experimental results show that the amount of H 2 O 2 generated by the catalyst CNTImFeF 2 TPP of the present invention is only about half of that of the commercial 20%Pt/C catalyst, which shows that the catalyst of the present invention has a higher four-electron reduction selectivity for ORR, thus showing higher catalytic activity.
碱性环境中催化剂的稳定性如图3所示。黑色实线:20%Pt/C;红色实线:CNTImFeF2TPP(0.1M KOH,@0.7V vs RHE,900rpm)。实验结果表明,25小时后本发明催化剂CNTImFeF2TPP仍保持有96%左右的催化活性,而商业20%Pt/C催化剂则只有55%左右。The stability of the catalyst in alkaline environment is shown in Fig. 3. Black solid line: 20%Pt/C; red solid line: CNTImFeF 2 TPP (0.1M KOH, @0.7V vs RHE, 900rpm). The experimental results show that the catalyst CNTImFeF 2 TPP of the present invention still maintains about 96% of the catalytic activity after 25 hours, while the commercial 20%Pt/C catalyst only has about 55%.
酸性环境中催化剂的ORR极化曲线如图4所示,黑色实线:20%Pt/C;红色实线:CNTImFeF2TPP(0.1M HClO4,@1600rpm)。实验结果表明,与商业20%Pt/C催化剂相比,本发明催化剂CNTImFeF2TPP的ORR半波电位向正电位位移36mV,ORR电流密度增加约20%。The ORR polarization curve of the catalyst in acidic environment is shown in Figure 4, black solid line: 20%Pt/C; red solid line: CNTImFeF 2 TPP (0.1M HClO 4 ,@1600rpm). The experimental results show that compared with the commercial 20%Pt/C catalyst, the ORR half-wave potential of the catalyst CNTImFeF 2 TPP of the present invention shifts 36mV to the positive potential, and the ORR current density increases by about 20%.
酸性环境中盘工作电极上生成H2O2的百分比随电位变化曲线如图5。黑色实线:20%Pt/C;红色实线:CNTImFeF2TPP(0.1M HClO4,@1600rpm)。实验结果表明,本发明催化剂CNTImFeF2TPP所生成的H2O2的量少于商业20%Pt/C催化剂,说明本发明催化剂对ORR有更高的四电子还原选择性,从而表现出更高的催化活性。The curve of the percentage of H 2 O 2 generated on the disk working electrode in an acidic environment versus the potential is shown in Figure 5. Black solid line: 20%Pt/C; red solid line: CNTImFeF 2 TPP (0.1M HClO 4 ,@1600rpm). The experimental results show that the amount of H 2 O 2 generated by the catalyst CNTImFeF 2 TPP of the present invention is less than that of the commercial 20%Pt/C catalyst, indicating that the catalyst of the present invention has a higher four-electron reduction selectivity for ORR, thereby showing a higher catalytic activity.
酸性环境中催化剂的稳定性实验结果如图6所示,黑色实线:20%Pt/C;红色实线:CNTImFeF2TPP(0.1M HClO4,@0.7V vs RHE,900rpm)。实验结果表明,12.5小时后本发明催化剂CNTImFeF2TPP仍保持有91%左右的催化活性,而商业20%Pt/C催化剂则只有57%左右。The stability test results of catalysts in acidic environment are shown in Figure 6, black solid line: 20%Pt/C; red solid line: CNTImFeF 2 TPP (0.1M HClO 4 ,@0.7V vs RHE,900rpm). The experimental results show that the catalyst CNTImFeF 2 TPP of the present invention still maintains about 91% of the catalytic activity after 12.5 hours, while the commercial 20%Pt/C catalyst only has about 57%.
在本发明提及的所有文献都在本申请中引用作为参考,就如同每一篇文献被单独引用作为参考那样。此外应理解,在阅读了本发明的上述讲授内容之后,本领域技术人员可以对本发明作各种改动或修改,这些等价形式同样落于本申请所附权利要求书所限定的范围。All documents mentioned in this application are incorporated by reference in this application as if each were individually incorporated by reference. In addition, it should be understood that after reading the above teaching content of the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the appended claims of the present application.
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