WO2021018268A1 - 一种碳负载纳米银催化剂的制备方法 - Google Patents
一种碳负载纳米银催化剂的制备方法 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 45
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- 150000004696 coordination complex Chemical class 0.000 claims abstract description 14
- 238000001354 calcination Methods 0.000 claims abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 21
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 14
- 239000002244 precipitate Substances 0.000 claims description 14
- 125000000524 functional group Chemical group 0.000 claims description 12
- 229920000642 polymer Polymers 0.000 claims description 12
- 101710134784 Agnoprotein Proteins 0.000 claims description 11
- 239000003960 organic solvent Substances 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 10
- 239000012298 atmosphere Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- NXUXMYNKTQLQDH-UHFFFAOYSA-N 5-[2,3-bis(2,3,4,5-tetraaminophenyl)phenyl]benzene-1,2,3,4-tetramine Chemical compound C1=CC(=C(C(=C1)C2=CC(=C(C(=C2N)N)N)N)C3=CC(=C(C(=C3N)N)N)N)C4=CC(=C(C(=C4N)N)N)N NXUXMYNKTQLQDH-UHFFFAOYSA-N 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 5
- -1 tris(tetraaminophenyl)amine Chemical compound 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- 229920002873 Polyethylenimine Polymers 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 6
- 239000002105 nanoparticle Substances 0.000 abstract description 5
- 239000002904 solvent Substances 0.000 abstract description 3
- 238000011282 treatment Methods 0.000 abstract description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 abstract 3
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 238000011068 loading method Methods 0.000 description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 239000000446 fuel Substances 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 4
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- 229940050176 methyl chloride Drugs 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000009827 uniform distribution Methods 0.000 description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000010671 solid-state reaction Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000001075 voltammogram Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/50—Silver
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
- B01J35/399—Distribution of the active metal ingredient homogeneously throughout the support particle
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/084—Decomposition of carbon-containing compounds into carbon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
Definitions
- the invention belongs to the technical field of organic synthesis electrochemistry, and specifically relates to a method for preparing a carbon-loaded nano-silver catalyst.
- Platinum (Pt)-based catalysts are currently the most widely used and most effective ORR catalysts, but they still face many problems, such as: high cost; easy to CO poisoning; Pt nanoparticles are easy to be oxidized and easy to agglomerate in acidic media. All these make the catalyst service life limited and hinder the commercial development of fuel cells. In order to accelerate the commercialization of fuel cells, a variety of carbon-supported catalysts with other metal particles have emerged. Among the many precious metals, Ag has relatively high activity in alkaline media due to its relatively low price and wide sources, making it the best candidate for ORR electrocatalysts. Soo L T etc. [Soo L T, Loh K S, Mohamad A B, et al.
- Ag/N-rGO catalyst was prepared by high temperature calcination using metal salt, graphene oxide and melamine as raw materials. This method is simple and easy to operate, but the Ag/N-rGO catalyst prepared with a mixture of small molecules as a precursor has uneven distribution of active sites and low catalytic efficiency. Guo J et al. [Guo J, Hsu A, Chu D, et al. Improving oxygen reduction reaction activities on carbon-supported Ag nanoparticles in alkaline solutions[J].
- the purpose of the present invention is to overcome the defects of the prior art and provide a method for preparing a carbon-supported nano-silver catalyst.
- a preparation method of carbon-loaded nano silver catalyst includes the following steps:
- step (3) Add the material obtained in step (2) dropwise to the material obtained in step (1) at a uniform speed, stir and react at room temperature for 10-15 hours after the addition is complete, and then centrifuge to obtain a precipitate. After the precipitate is vacuum dried, a high Molecular metal complexes;
- the above -NH 2 functional group-containing compound is tris(tetraaminophenyl)benzene, tris(tetraaminophenyl)amine or polyethyleneimine.
- the -NH 2 functional group-containing compound is tris(tetraaminophenyl)benzene or tris(tetraaminophenyl)amine.
- the organic solvent is dichloromethane, chloroform or 1-methyl-2-pyrrolidone.
- the organic solvent is dichloromethane or chloroform.
- the molar ratio of the -NH 2 functional group-containing compound to AgNO 3 is 1:1-6.
- the ratio of the -NH 2 functional group-containing compound and the organic solvent is 0.1 mmol: 15-25 mL.
- the ratio of AgNO 3 to the organic solvent is 1 mmol: 10-20 mL.
- the inert gas is argon.
- the temperature of the vacuum drying is 55-65°C, and the time is 10-15h.
- the calcination temperature is 850-950°C.
- the raw materials used in the present invention have a wide range of sources, low prices, and simple experimental operations.
- the catalyst prepared by the present invention has a uniform distribution of Ag nanoparticles at active sites and exhibits excellent ORR performance.
- the present invention has universal applicability and can be prepared by using different NH 2 functional group-containing compounds and solvents.
- Fig. 1 is a transmission electron micrograph of carbon-supported nano-silver catalysts with different Ag loadings in Examples 1 and 2 of the present invention.
- Example 2 is a graph of electrochemical performance of a carbon-supported nano-silver catalyst with an Ag loading of 1 eq in Example 1 of the present invention.
- Figure 3 is a transmission electron microscope image of the carbon-supported iron catalyst in Comparative Example 1.
- Figure 1 is a transmission electron micrograph of the carbon-supported nanosilver catalysts with different Ag loadings prepared in Examples 1 and 2.
- Figure a is a transmission electron microscope image of Example 1, that is, a carbon-supported nanosilver catalyst with a loading amount of Ag of 1 eq. It can be seen that the particle size and distribution of the simple substance of Ag is relatively uniform, and its size is about 50 nm.
- Figure b is a transmission electron microscope image of Example 2, that is, a carbon-supported nanosilver catalyst with a loading of Ag of 1.5eq. The particle size of Ag elementary substance is different.
- the size of large particles can reach 90-100nm, while the size of small particles is only There are 10-20nm, indicating that the loading amount has an effect on the morphology of the synthesized carbon-based material loaded with metal Ag, which may affect its electrochemical catalytic performance.
- Figure 2 is the cyclic voltammogram (CV) of the carbon-supported nanosilver catalyst prepared in Example 1 in 0.1M KOH, where the dotted line represents the condition of argon saturation, and the solid line represents the condition of oxygen saturation. It can be seen that, The CV diagram measured under oxygen saturation has obvious oxygen reduction peaks, which proves that the catalyst catalyzes the ORR reaction under oxygen saturation conditions.
- the figure shows the linear scanning voltammogram (LSV) of the samples in Comparative Example 1 and Example 1. The test conditions are 0.1 M KOH saturated with oxygen at a scanning speed of 5 mV/s at 1600 rpm.
- the catalytic ORR activity of the carbon-supported nano-silver catalyst of Example 1 is significantly higher than that of the carbon-supported iron catalyst, and the performance is equivalent to that of the commercial Pt/C catalyst (in terms of price and cost, it is much higher than the product of Example 1).
- the half-wave potential and the limiting diffusion current density are shown in Table 1.
- Figure 3 is a transmission electron microscope image of the carbon-supported iron catalyst in Comparative Example 1.
- the invention discloses a method for preparing a carbon-loaded nano-silver catalyst. It uses a compound containing -NH 2 functional group and AgNO 3 as raw materials to synthesize a polymer metal complex through coordination reaction, and then High-temperature calcination and other post-treatments prepare carbon-supported nano-silver catalysts that can be used for ORR.
- the raw materials used in the invention have wide sources, low prices, and simple experimental operations.
- the catalyst prepared by the invention has a uniform distribution of active site Ag nanoparticles and shows excellent ORR performance.
- the present invention is universal, various compounds containing the functional group NH 2 and a solvent system, has industrial applicability can be employed.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
一种碳负载纳米银催化剂的制备方法，以含-NH 2官能团化合物与AgNO 3为原料，通过配位反应合成高分子金属络合物，然后，将该高分子金属络合物高温煅烧，经过其他后处理，制备可用于ORR的碳负载纳米银催化剂。该催化剂使用的原料来源广泛，价格低廉，且实验操作简单，其活性位点Ag纳米颗粒分布均匀，表现出优秀的ORR性能，具有普适性，可以采用不同含NH 2官能团化合物及溶剂制。
Description
本发明属于有机合成电化学技术领域，具体涉及一种碳负载纳米银催化剂的制备方法。
能源是人类赖以生存和发展的基础，伴随社会不断发展，能源过度消耗，多种非可再生资源濒临枯竭，人们面临的能源危机日渐严重，寻找新的替代能源迫在眉睫。燃料电池作为一种高效、清洁的能源装置，受到科研人员广泛关注。但是，燃料电池阴极的氧气还原反应动力学迟缓，比阳极氢气氧化反应慢6个数量级，这一特性极大阻碍了燃料电池的商业发展。因此，研究出高效的氧还原反应(ORR)催化剂至关重要。
铂(Pt)基催化剂是目前使用最广泛且效果最好的ORR催化剂，但其依然面临诸多问题，如：成本高；容易CO中毒；在酸性介质中Pt纳米粒子易被氧化且易团聚等。这些都使得催化剂使用寿命有限，阻碍燃料电池商业化发展。为加快燃料电池的商业化发展，多种碳负载其他金属粒子的催化剂应运而生。在众多的贵金属中，Ag由于价格相对低廉，来源广泛，在碱性介质中具有相对较高的活性，成为ORR电催化剂的最佳候选者。Soo L T等[Soo L T,Loh K S,Mohamad A B,et al.Synthesis of silver/nitrogen-doped reduced graphene oxide through a one-step thermal solid-state reaction for oxygen reduction in an alkaline medium[J].Journal of Power Sources,2016,324:412-420.]以金属盐、氧化石墨烯以及三聚氰胺为原料，通过高温煅烧，制备了Ag/N-rGO催化剂。该方法简单易操作，但是以小分子混合物为前驱体制备的Ag/N-rGO催化剂的活性位点分布不均，催化效率不高。Guo J等[Guo J,Hsu A,Chu D,et al.Improving oxygen reduction reaction activities on carbon-supported Ag nanoparticles in alkaline solutions[J].The Journal of Physical Chemistry C,2010,114(10):4324-4330.]通过柠檬酸盐保护方法制备了四种不同金属Ag负载量的Ag/C催化剂，研究了碱性条件下影响Ag/C催化剂ORR活性的因素，对如何设计高效的Ag/C催化剂有重要的指导意义。近年来，尽管金属纳米粒子/C催化剂在诸多方面取得了长足进步，但仍未研发出可以取代Pt/C(20wt％)的催化剂。因此，采用简单易操作的方法设计金属配位络合物，进而制备ORR性能优异的催化剂对促进燃料电池的商业化进展具有重 要的意义。
发明内容
本发明的目的在于克服现有技术缺陷，提供一种碳负载纳米银催化剂的制备方法。
本发明的技术方案如下：
一种碳负载纳米银催化剂的制备方法，包括如下步骤：
(1)将含-NH
2官能团化合物与适量有机溶剂混合后，于室温下搅拌至完全溶解；
(2)将AgNO
3溶解于适量有机溶剂；
(3)将步骤(2)所得的物料匀速滴加至步骤(1)所得的物料中，滴加完毕后于室温搅拌反应10-15h，接着离心得沉淀，将该沉淀真空干燥后，得到高分子金属络合物；
(4)将上述高分子金属络合物在氮气气氛、惰性气体气氛或惰性气体与氢气的混合气氛下，以4-6℃/min的升温速率升温至750-950℃煅烧1.5-3h，即得所述碳负载纳米银催化剂；
上述含-NH
2官能团化合物为三(四氨基苯基)苯、三(四氨基苯基)胺或聚乙烯亚胺。
在本发明的一个优选实施方案中，所述含-NH
2官能团化合物为三(四氨基苯基)苯或三(四氨基苯基)胺。
在本发明的一个优选实施方案中，所述有机溶剂为二氯甲烷、氯仿或1-甲基-2-吡咯烷酮。
进一步优选的，所述有机溶剂为二氯甲烷或氯仿。
在本发明的一个优选实施方案中，所述含-NH
2官能团化合物和AgNO
3的摩尔比为1:1-6。
在本发明的一个优选实施方案中，所述步骤(1)中，含-NH
2官能团化合物和有机溶剂的比例为0.1mmol:15-25mL。
在本发明的一个优选实施方案中，所述步骤(2)中，AgNO
3和有机溶剂的比例为1mmol:10-20mL。
在本发明的一个优选实施方案中，所述惰性气体为氩气。
在本发明的一个优选实施方案中，所述真空干燥的温度为55-65℃，时间为10-15h。
在本发明的一个优选实施方案中，所述煅烧的温度为850-950℃。
本发明的有益效果是：
1、本发明使用的原料来源广泛，价格低廉，且实验操作简单。
2、本发明制备的催化剂，其活性位点Ag纳米颗粒分布均匀，表现出优秀的ORR性能。
3、本发明具有普适性，可以采用不同含NH
2官能团化合物及溶剂制。
图1为本发明实施例1和2中不同Ag负载量的碳载纳米银催化剂的透射电镜图。
图2为本发明实施例1中Ag负载量为1eq的碳载纳米银催化剂的电化学性能图。
图3为对比例1中碳载铁催化剂的透射电镜图。
以下通过具体实施方式结合附图对本发明的技术方案进行进一步的说明和描述。
实施例1
将70.2mg(0.2mmol)三(四氨基苯基)苯，35mL二氯甲烷加入到100mL圆底烧瓶中，室温下磁力搅拌至完全溶解；称量102mg(0.6mmol)AgNO
3固体，用10mL二氯甲烷溶解，匀速滴加至上述圆底烧瓶中；滴加完毕后，室温搅拌反应12h，离心得到沉淀。所得沉淀于60℃恒温烘箱中真空干燥12h，得到高分子金属络合物。
将0.2g上述步骤获得的高分子金属络合物置于马弗炉中，于Ar气体氛围下，以5℃/min的升温速率升温至850℃煅烧120min，自然冷却至室温得到Ag负载量为1eq的碳载纳米银催化剂。(起始电势：0.92V；半波电势：0.72V)
实施例2
将70.2mg(0.2mmol)三(四氨基苯基)苯，35mL二氯甲烷加入到100mL圆底烧瓶中，室温下磁力搅拌至完全溶解；称量153mg(0.9mmol)AgNO
3固体，用18mL 二氯甲烷溶解，匀速滴加至上述圆底烧瓶中；滴加完毕后，室温搅拌反应12h，离心得到沉淀。所得沉淀于60℃恒温烘箱中真空干燥12h，得到高分子金属络合物。
将0.2g上述步骤获得的高分子金属络合物置于马弗炉中，于Ar气体氛围下，以5℃/min的升温速率升温至850℃煅烧120min，自然冷却至室温得到Ag负载量为1.5eq的碳载纳米银催化剂。(起始电势：0.93V；半波电势：0.73V)
实施例3
将58mg(0.2mmol)三(四氨基苯基)胺，29mL氯仿加入到100mL圆底烧瓶中，室温下磁力搅拌至完全溶解；称量102mg(0.6mmol)AgNO
3固体，用10mL氯仿溶解，匀速滴加至上述圆底烧瓶中；滴加完毕后，室温搅拌反应12h，离心得到沉淀。所得沉淀于60℃恒温烘箱中真空干燥12h，得到高分子金属络合物。
将0.2g上述步骤获得的高分子金属络合物置于马弗炉中，于Ar气体氛围下，以5℃/min的升温速率升温至850℃煅烧120min，自然冷却至室温得到Ag负载量为1eq的碳载纳米银催化剂。(起始电势：0.91V；半波电势：0.70V)
实施例4
将58mg(0.2mmol)三(四氨基苯基)胺，29mL氯仿加入到100mL圆底烧瓶中，室温下磁力搅拌至完全溶解；称量102mg(0.6mmol)AgNO
3固体，用10mL氯仿溶解，匀速滴加至上述圆底烧瓶中；滴加完毕后，室温搅拌反应12h，离心得到沉淀。所得沉淀于60℃恒温烘箱中真空干燥12h。
将0.2g上述步骤获得的高分子金属络合物置于马弗炉中，于Ar气体氛围下，以5℃/min的升温速率升温至950℃煅烧120min，自然冷却至室温得到Ag负载量为1eq的碳载纳米银催化剂。(起始电势：0.90V；半波电势：0.70V)
对比例1
将70.2mg(0.2mmol)三(四氨基苯基)苯，35mL二氯甲烷加入到100mL圆底烧瓶中，室温下磁力搅拌至完全溶解；称量54mg(0.2mmol)FeCl
3·6H
2O固体，用10mL二氯甲烷溶解，匀速滴加至上述圆底烧瓶中；滴加完毕后，室温搅拌反应12h，离心得到沉淀。所得沉淀于60℃恒温烘箱中真空干燥12h，得到高分子金属 络合物。
将0.2g上述步骤获得的高分子金属络合物置于马弗炉中，于Ar气体氛围下，以5℃/min的升温速率升温至850℃煅烧120min，自然冷却至室温得到Fe负载量为1eq的碳载铁催化剂作为对比例1。
图1为实施例1和2制得的不同Ag负载量的碳载纳米银催化剂的透射电镜图。其中图a为实施例1，即Ag的负载量为1eq的碳载纳米银催化剂的透射电镜图，可以看到Ag单质的粒径及分布较为均一，其尺寸大约为50nm左右。图b为实施例2，即Ag的负载量为1.5eq的碳载纳米银催化剂的透射电镜图，Ag单质的粒径大小不一，大的粒子尺寸可以达到90-100nm，而小粒子尺寸仅有10-20nm，说明负载量对所合成的负载金属Ag的碳基材料的形貌有所影响，进而可能影响其电化学催化性能。
图2为实施例1制得的碳载纳米银催化剂的在0.1M KOH中的循环伏安图(CV)，其中虚线代表氩气饱和条件下，实线代表氧气饱和条件下，可以看到，在氧气饱和下测得的CV图有明显的氧气还原峰，证明了在氧气饱和条件下催化剂催化ORR反应的发生。(b)图为对比例1和实施例1中样品的线性扫描伏安图(LSV)，测试条件为氧气饱和的0.1M KOH中1600rpm下以5mV/s的扫描速度。其中实施例1的碳载纳米银催化剂的催化ORR活性明显要高于碳载铁催化剂，性能与商业化Pt/C催化剂相当(在价格成本上远高于实施例1产品)，起峰电势、半波电势和极限扩散电流密度如表1所示。
图3为对比例1中碳载铁催化剂的透射电镜图。
表1
以上所述，仅为本发明的较佳实施例而已，故不能依此限定本发明实施的范围，即依本发明专利范围及说明书内容所作的等效变化与修饰，皆应仍属本发明涵盖的范围内。
本发明公开了一种碳负载纳米银催化剂的制备方法，以含-NH
2官能团化合物与AgNO
3为原料，通过配位反应合成高分子金属络合物，然后，将该高分子金属络合物高温煅烧，经过其他后处理，制备可用于ORR的碳负载纳米银催化剂。本发明使用的原料来源广泛，价格低廉，且实验操作简单。本发明制备的催化剂，其活性位点Ag纳米颗粒分布均匀，表现出优秀的ORR性能。本发明具有普适性，可以采用不同含NH
2官能团化合物及溶剂制,具有工业实用性。
Claims (6)
- 一种碳负载纳米银催化剂的制备方法，其特征在于：包括如下步骤：(1)将含-NH 2官能团化合物与适量有机溶剂混合后，于室温下搅拌至完全溶解；(2)将AgNO 3溶解于适量有机溶剂；(3)将步骤(2)所得的物料匀速滴加至步骤(1)所得的物料中，滴加完毕后于室温搅拌反应10-15h，接着离心得沉淀，将该沉淀真空干燥后，得到高分子金属络合物；(4)将上述高分子金属络合物在氮气气氛、惰性气体气氛或惰性气体与氢气的混合气氛下，以4-6℃/min的升温速率升温至750-950℃煅烧1.5-3h，即得所述碳负载纳米银催化剂；上述含-NH 2官能团化合物为三(四氨基苯基)苯、三(四氨基苯基)胺或聚乙烯亚胺。
- 如权利要求1所述的制备方法，其特征在于：所述有机溶剂为二氯甲烷、氯仿或1-甲基-2-吡咯烷酮。
- 如权利要求1所述的制备方法，其特征在于：所述含-NH 2官能团化合物和AgNO 3的摩尔比为1:1-6。
- 如权利要求1所述的制备方法，其特征在于：所述步骤(1)中，含-NH 2官能团化合物和有机溶剂的比例为0.1mmol:15-25mL。
- 如权利要求1所述的制备方法，其特征在于：所述步骤(2)中，AgNO 3和有机溶剂的比例为1mmol:10-20mL。
- 如权利要求1所述的制备方法，其特征在于：所述煅烧的温度为850-950℃。
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