CN114836787B - Preparation method of molybdenum supported biomass-derived carbon-based hydrogen evolution electrocatalyst - Google Patents
Preparation method of molybdenum supported biomass-derived carbon-based hydrogen evolution electrocatalyst Download PDFInfo
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- 239000002028 Biomass Substances 0.000 title claims abstract description 43
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 34
- 239000001257 hydrogen Substances 0.000 title claims abstract description 34
- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 33
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 27
- 239000011733 molybdenum Substances 0.000 title claims abstract description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 25
- 239000000203 mixture Substances 0.000 claims abstract description 24
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 20
- 238000000498 ball milling Methods 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000012298 atmosphere Substances 0.000 claims abstract description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 8
- 238000003837 high-temperature calcination Methods 0.000 claims abstract description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000011593 sulfur Substances 0.000 claims abstract description 6
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 5
- 239000000843 powder Substances 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract 3
- 238000010438 heat treatment Methods 0.000 claims description 29
- 239000011701 zinc Substances 0.000 claims description 14
- 229910052725 zinc Inorganic materials 0.000 claims description 12
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 11
- 235000011201 Ginkgo Nutrition 0.000 claims description 8
- 235000008100 Ginkgo biloba Nutrition 0.000 claims description 8
- 235000017060 Arachis glabrata Nutrition 0.000 claims description 7
- 244000105624 Arachis hypogaea Species 0.000 claims description 7
- 235000010777 Arachis hypogaea Nutrition 0.000 claims description 7
- 235000018262 Arachis monticola Nutrition 0.000 claims description 7
- 235000020232 peanut Nutrition 0.000 claims description 7
- 235000015393 sodium molybdate Nutrition 0.000 claims description 7
- 239000011684 sodium molybdate Substances 0.000 claims description 7
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 7
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 6
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 6
- 239000011609 ammonium molybdate Substances 0.000 claims description 6
- 229940010552 ammonium molybdate Drugs 0.000 claims description 6
- 235000021374 legumes Nutrition 0.000 claims description 3
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 claims description 3
- 244000194101 Ginkgo biloba Species 0.000 claims 1
- 238000001354 calcination Methods 0.000 claims 1
- 239000003361 porogen Substances 0.000 abstract description 15
- 230000008569 process Effects 0.000 abstract description 11
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 239000002699 waste material Substances 0.000 abstract description 7
- 239000005416 organic matter Substances 0.000 abstract description 6
- 238000000197 pyrolysis Methods 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 229910000510 noble metal Inorganic materials 0.000 abstract description 2
- 238000001308 synthesis method Methods 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 241000218628 Ginkgo Species 0.000 description 7
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 239000002243 precursor Substances 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 244000068988 Glycine max Species 0.000 description 4
- 235000010469 Glycine max Nutrition 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 150000001247 metal acetylides Chemical class 0.000 description 2
- -1 platinum group metals Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
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- 238000005530 etching Methods 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
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- 239000005078 molybdenum compound Substances 0.000 description 1
- 150000002752 molybdenum compounds Chemical class 0.000 description 1
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- 238000004064 recycling Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
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Abstract
本发明涉及一种钼负载生物质衍生碳基析氢电催化剂的制备方法，包括：将破碎的富含氮、硫有机质的生物质原料粉末与含钼化合物混合，在惰性气氛中进行球磨；向充分球磨后的混合物中加入模板剂和致孔剂，进一步在惰性气氛中混合球磨；将步骤二球磨获得的混合物，在惰性气氛下高温煅烧，冷却后获得所述析氢电催化剂。本发明通过简单的球磨和高温煅烧方法制备具备高催化活性的钼负载析氢电催化剂，既可以完成生物质废弃物的资源化利用，同时也能够制备出高性能的非贵金属析氢电催化剂。相比于现有的MoS2合成工艺，无需使用复杂且耗能高的水热反应过程，仅需要与生物质进行混合球磨热解，不仅原料来源广泛、合成方法简便，而且能耗低提高了经济性。
The invention relates to a method for preparing a molybdenum-loaded biomass-derived carbon-based hydrogen evolution electrocatalyst, which includes: mixing crushed biomass raw material powder rich in nitrogen and sulfur organic matter with a molybdenum-containing compound, and performing ball milling in an inert atmosphere; The template agent and porogen are added to the ball-milled mixture, and further mixed and ball-milled in an inert atmosphere; the mixture obtained by ball milling in step 2 is calcined at high temperature in an inert atmosphere, and after cooling, the hydrogen evolution electrocatalyst is obtained. The present invention prepares a molybdenum-supported hydrogen evolution electrocatalyst with high catalytic activity through simple ball milling and high-temperature calcination methods, which can not only complete the resource utilization of biomass waste, but also prepare a high-performance non-noble metal hydrogen evolution electrocatalyst. Compared with the existing MoS 2 synthesis process, there is no need to use a complex and energy-consuming hydrothermal reaction process. It only needs to be mixed with biomass for ball milling and pyrolysis. Not only does it have a wide range of raw material sources, the synthesis method is simple, but also low energy consumption improves Economy.
Description
技术领域Technical field
本发明涉及析氢电催化剂技术领域，尤其是一种钼负载生物质衍生碳基析氢电催化剂的制备方法。The invention relates to the technical field of hydrogen evolution electrocatalysts, in particular to a preparation method of a molybdenum-loaded biomass-derived carbon-based hydrogen evolution electrocatalyst.
背景技术Background technique
生物质废弃物由于富含有机质造成了其易腐的特质，导致其在消纳处理过程中会产生V℃，同时其焚烧处理过程中也会造成烟尘和氮氧化物的污染，因此生物质废弃物的资源化利用不仅能够提高废弃物的循环再利用率，同时也会缓解其处理过程中可能引起的环境问题。生物质中的氮、硫有机质在热解过程中能够进入碳晶格中，打破碳结构中的电子平衡，从而赋予碳材料更好的电化学特性。Because biomass waste is rich in organic matter, it is perishable, causing V°C to be produced during the treatment process. At the same time, its incineration process will also cause smoke and nitrogen oxide pollution. Therefore, biomass waste The resource utilization of materials can not only improve the recycling rate of waste, but also alleviate the environmental problems that may be caused during its processing. Nitrogen and sulfur organic matter in biomass can enter the carbon lattice during the pyrolysis process, breaking the electron balance in the carbon structure, thus giving the carbon material better electrochemical properties.
钼基化合物由于其能带结构与铂族金属相似，具备替代铂族金属成为析氢催化剂的可能性。现有技术中，多采用水热法制备碳基钼化合物复合载体，不仅操作复杂而且能耗高，而且制备获得的催化剂表面的比表面积和孔隙率低，催化活性低。Since its band structure is similar to that of platinum group metals, molybdenum-based compounds have the potential to replace platinum group metals as hydrogen evolution catalysts. In the existing technology, hydrothermal method is often used to prepare carbon-based molybdenum compound composite carriers, which is not only complex to operate and consumes high energy, but also the prepared catalyst surface has low specific surface area and porosity, and low catalytic activity.
发明内容Contents of the invention
针对现有技术的不足，本发明提供一种钼负载生物质衍生碳基析氢电催化剂的制备方法，目的是提高钼负载生物质衍生碳基析氢电催化剂的催化性能。In view of the shortcomings of the existing technology, the present invention provides a preparation method of a molybdenum-loaded biomass-derived carbon-based hydrogen evolution electrocatalyst, with the purpose of improving the catalytic performance of the molybdenum-loaded biomass-derived carbon-based hydrogen evolution electrocatalyst.
本发明采用的技术方案如下：The technical solutions adopted by the present invention are as follows:
一种钼负载生物质衍生碳基析氢电催化剂的制备方法，包括：A method for preparing molybdenum-loaded biomass-derived carbon-based hydrogen evolution electrocatalyst, including:
步骤一：将破碎的富含氮、硫有机质的生物质原料粉末与含钼化合物混合，在惰性气氛中进行球磨；Step 1: Mix the crushed biomass raw material powder rich in nitrogen and sulfur organic matter with the molybdenum-containing compound, and perform ball milling in an inert atmosphere;
步骤二：向充分球磨后的混合物中加入模板剂和致孔剂，进一步在惰性气氛中混合球磨；Step 2: Add template agent and porogen to the fully ball-milled mixture, and further mix and ball-mill in an inert atmosphere;
步骤三：将步骤二球磨获得的混合物，在惰性气氛下高温煅烧，冷却后获得所述析氢电催化剂。Step 3: The mixture obtained by ball milling in Step 2 is calcined at high temperature under an inert atmosphere and cooled to obtain the hydrogen evolution electrocatalyst.
进一步技术方案为：Further technical solutions are:
所述模板剂和致孔剂为同种含锌化合物。The template agent and porogen are the same zinc-containing compound.
所述含锌化合物为ZnCl2、ZnO、ZnCO3中的一种或几种。The zinc-containing compound is one or more of ZnCl 2 , ZnO, and ZnCO 3 .
所述高温煅烧采用两段式加热过程：The high-temperature calcination adopts a two-stage heating process:
第一段加热过程由室温加热至800～900℃，第二段加热过程由800～900℃加热至950～1100℃。The first heating process is from room temperature to 800~900℃, and the second heating process is from 800~900℃ to 950~1100℃.
第一段加热过程，升温速率1～3℃/min，维持2～5h；第二段加热过程，升温速率5～8℃/min，维持1～2h。In the first heating process, the heating rate is 1 to 3°C/min, and the temperature is maintained for 2 to 5 hours; in the second heating process, the temperature rise rate is 5 to 8°C/min, and the temperature is maintained for 1 to 2 hours.
生物质原料与模板剂加致孔剂的质量比为1∶1～1∶3。The mass ratio of biomass raw material to template agent plus porogen is 1:1 to 1:3.
生物质原料与含钼化合物的质量比为1∶0.5～1∶2。The mass ratio of biomass raw materials and molybdenum-containing compounds is 1:0.5~1:2.
所述含钼化合物为钼酸铵、钼酸钠、磷钼酸中的一种或几种。The molybdenum-containing compound is one or more of ammonium molybdate, sodium molybdate, and phosphomolybdic acid.
生物质原料为银杏叶、花生壳、豆类植物根茎中的一种或几种。The biomass raw material is one or more of ginkgo leaves, peanut shells, and legume rhizomes.
本发明的有益效果如下：The beneficial effects of the present invention are as follows:
本发明利用成本低廉的生物质废弃物，通过简单的球磨和高温煅烧方法制备具备高催化活性的钼负载析氢电催化剂，既可以完成生物质废弃物的资源化利用，同时也能够制备出高性能的非贵金属析氢电催化剂。相比于目前多数的MoS2合成工艺，无需使用复杂且耗能高的水热反应过程，仅需要与生物质进行混合球磨热解，不仅原料来源广泛、合成方法简便，而且能耗低提高了经济性。The present invention uses low-cost biomass waste to prepare a molybdenum-loaded hydrogen evolution electrocatalyst with high catalytic activity through simple ball milling and high-temperature calcination methods. It can not only complete the resource utilization of biomass waste, but also prepare high-performance electrocatalysts. non-noble metal hydrogen evolution electrocatalyst. Compared with most current MoS 2 synthesis processes, there is no need to use a complex and energy-consuming hydrothermal reaction process. It only needs to be mixed with biomass and ball milled for pyrolysis. Not only does it have a wide range of raw material sources, the synthesis method is simple, but it also has low energy consumption. Economy.
本发明引入致孔剂和模板剂，丰富了材料的孔隙结构，增加了钼负载生物质衍生碳基析氢电催化剂的比表面积和孔隙率，从而促进材料的电子传输，提高了催化性能。The present invention introduces porogen and template agent, enriches the pore structure of the material, and increases the specific surface area and porosity of the molybdenum-loaded biomass-derived carbon-based hydrogen evolution electrocatalyst, thereby promoting the electron transmission of the material and improving the catalytic performance.
本发明采用含锌化合物作为模板剂和致孔剂，能避免碳组分大量流失，防止形成较多的金属碳化物，提高了产物的生成率和质量。The present invention uses zinc-containing compounds as template agents and porogens, which can avoid a large loss of carbon components, prevent the formation of more metal carbides, and improve the production rate and quality of the product.
本发明的其它特征和优点将在随后的说明书中阐述，并且，部分地从说明书中变得显而易见，或者通过实施本发明而了解。Additional features and advantages of the invention will be set forth in the description which follows, and in part will be apparent from the description, or may be learned by practice of the invention.
附图说明Description of the drawings
图1为本发明实施例1制备所得的析氢电催化剂A的晶体结构图。Figure 1 is a crystal structure diagram of hydrogen evolution electrocatalyst A prepared in Example 1 of the present invention.
具体实施方式Detailed ways
以下结合附图说明本发明的具体实施方式。Specific embodiments of the present invention will be described below with reference to the accompanying drawings.
本申请的一种钼负载生物质衍生碳基析氢电催化剂的制备方法，包括：The preparation method of a molybdenum-loaded biomass-derived carbon-based hydrogen evolution electrocatalyst of the present application includes:
步骤一：将破碎的富含氮、硫有机质的生物质原料粉末与含钼化合物混合，在惰性气氛中进行球磨；Step 1: Mix the crushed biomass raw material powder rich in nitrogen and sulfur organic matter with the molybdenum-containing compound, and perform ball milling in an inert atmosphere;
步骤二：向充分球磨后的混合物中加入模板剂和致孔剂，进一步在惰性气氛中混合球磨；Step 2: Add template agent and porogen to the fully ball-milled mixture, and further mix and ball-mill in an inert atmosphere;
步骤三：将步骤二球磨获得的混合物，在惰性气氛下高温煅烧，冷却后获得所述析氢电催化剂。Step 3: The mixture obtained by ball milling in Step 2 is calcined at high temperature under an inert atmosphere and cooled to obtain the hydrogen evolution electrocatalyst.
本申请的钼负载生物质衍生碳基析氢电催化剂的制备方法，采用球磨结合高温煅烧的方法，将钼负载于废弃生物质衍生的碳基材料上，高温煅烧过程中，钼与生物质发生反应并负载于碳基材料上，生物质的部分有机质分解促进了催化剂孔隙的形成，促进了催化活性的提升。The preparation method of the molybdenum-loaded biomass-derived carbon-based hydrogen evolution electrocatalyst of the present application uses ball milling combined with high-temperature calcination to load molybdenum on carbon-based materials derived from waste biomass. During the high-temperature calcination process, molybdenum reacts with the biomass. And loaded on carbon-based materials, the decomposition of part of the organic matter in the biomass promotes the formation of catalyst pores and promotes the improvement of catalytic activity.
本申请的制备方法引入致孔剂和模板剂，丰富材料的孔隙结构，可有效增加钼负载生物质衍生碳基析氢电催化剂的比表面积和孔隙率。制备获得的催化剂可有效促进材料的电子传输，催化性能大大提高。The preparation method of the present application introduces porogens and template agents to enrich the pore structure of the material, which can effectively increase the specific surface area and porosity of the molybdenum-loaded biomass-derived carbon-based hydrogen evolution electrocatalyst. The prepared catalyst can effectively promote the electron transmission of the material, and the catalytic performance is greatly improved.
具体的，所述模板剂和致孔剂为同种含锌化合物。Specifically, the template agent and porogen are the same zinc-containing compound.
优选的，所述含锌化合物为ZnCl2、ZnO、ZnCO3中的一种或几种。Preferably, the zinc-containing compound is one or more of ZnCl 2 , ZnO, and ZnCO 3 .
具体的，所述高温煅烧采用两段式加热过程：Specifically, the high-temperature calcination adopts a two-stage heating process:
第一段加热过程由室温加热至800～900℃，第二段加热过程由800～900℃加热至950～1100℃。The first heating process is from room temperature to 800~900℃, and the second heating process is from 800~900℃ to 950~1100℃.
具体的，第一段加热过程，升温速率1～3℃/min，维持2～5h；第二段加热过程，升温速率5～8℃/min，维持1～2h。Specifically, in the first heating process, the heating rate is 1 to 3°C/min and maintained for 2 to 5 hours; in the second heating process, the heating rate is 5 to 8°C/min and maintained for 1 to 2 hours.
本申请的制备方法通过两段式加热的调控温度，能充分发挥含锌化合物的效用。含锌化合物在热解过程中会形成Zn，Zn可作为碳生长的模板，即发挥模板剂的效用，而当温度超过950℃时，Zn挥发逸出，产生孔隙，即发挥致孔剂的效用。The preparation method of the present application can fully utilize the effectiveness of the zinc-containing compound by regulating the temperature through two-stage heating. Zinc-containing compounds will form Zn during the pyrolysis process. Zn can serve as a template for carbon growth, that is, it plays the role of a template agent. When the temperature exceeds 950°C, Zn volatilizes and escapes, creating pores, that is, it plays the role of a porogen. .
本申请的含锌化合物在热解过程中充当模板剂和致孔剂两种不同的角色，实现两种不同的作用。含锌化合物在热解过程中不会造成对生物质的刻蚀，能避免造成碳组分大量流失，防止形成较多的金属碳化物，确保最后产物的质量。The zinc-containing compound of the present application plays two different roles as a template agent and a porogen during the pyrolysis process, achieving two different functions. Zinc-containing compounds will not cause etching of biomass during the pyrolysis process, and can avoid a large loss of carbon components, prevent the formation of more metal carbides, and ensure the quality of the final product.
具体的，生物质原料与模板剂加致孔剂的质量比为1∶1～1∶3。Specifically, the mass ratio of biomass raw material to template agent plus porogen is 1:1 to 1:3.
具体的，生物质原料与含钼化合物的质量比为1∶0.5～1∶2。Specifically, the mass ratio of biomass raw materials to molybdenum-containing compounds is 1:0.5 to 1:2.
具体的，所述含钼化合物为钼酸铵、钼酸钠、磷钼酸中的一种或几种。Specifically, the molybdenum-containing compound is one or more of ammonium molybdate, sodium molybdate, and phosphomolybdic acid.
具体的，生物质原料为银杏叶、花生壳、豆类植物根茎中的一种或几种。Specifically, the biomass raw material is one or more of ginkgo leaves, peanut shells, and legume rhizomes.
实施例1：Example 1:
步骤一：采用银杏叶为生物质原料，将银杏叶破碎至300目，采用钼酸铵为含钼化合物，将银杏叶与钼酸铵按质量比1∶0.5混合，在氮气氛围中球磨，球磨机转速为600r/min，运行时间为3h；Step 1: Use ginkgo leaves as the biomass raw material, crush the ginkgo leaves to 300 mesh, use ammonium molybdate as the molybdenum-containing compound, mix the ginkgo leaves and ammonium molybdate at a mass ratio of 1:0.5, and ball-mill in a nitrogen atmosphere. The ball mill speed is 600r/min, running time is 3h;
步骤二：采用ZnCl2作为模板剂和致孔剂，加入步骤一的混合物中，继续在氮气氛围中进行球磨获得混合物前驱体，其中银杏叶与ZnCl2质量比为1∶1，球磨机转速为1200r/min，运行8h；Step 2: Use ZnCl 2 as a template agent and porogen, add it to the mixture in step 1, and continue ball milling in a nitrogen atmosphere to obtain a mixture precursor. The mass ratio of Ginkgo leaves to ZnCl 2 is 1:1, and the ball mill speed is 1200r. /min, run for 8 hours;
步骤三：将步骤二获得的混合物前驱体放入管式炉中，在氮气中首先加热至800℃，升温速率1℃/min，维持5h，随后继续升温至950℃，升温速率5℃/min，维持1h，冷却后收集产物获得析氢电催化剂A，析氢电催化剂A的晶体结构如图1所示。Step 3: Put the mixture precursor obtained in Step 2 into a tube furnace, first heat it to 800°C in nitrogen at a heating rate of 1°C/min, maintain it for 5 hours, and then continue to heat it to 950°C at a heating rate of 5°C/min. , maintain for 1 hour, and collect the product after cooling to obtain hydrogen evolution electrocatalyst A. The crystal structure of hydrogen evolution electrocatalyst A is shown in Figure 1.
由图1可知催化剂A中的晶体结构组成为Mo2C及MoS2，钼酸铵不仅与碳结合形成了Mo2C晶相，且与银杏叶中的含硫组分结合形成了MoS2。It can be seen from Figure 1 that the crystal structure of catalyst A is composed of Mo 2 C and MoS 2. Ammonium molybdate not only combines with carbon to form the Mo 2 C crystal phase, but also combines with the sulfur-containing components in Ginkgo leaves to form MoS 2 .
实施例2：Example 2:
步骤一：采用花生壳为生物质原料，将花生壳破碎至500目，采用钼酸钠为含钼化合物，将花生壳与钼酸钠按质量比1∶1混合，在氮气氛围中球磨，球磨机转速为800r/min，运行时间为4h；Step 1: Use peanut shells as the biomass raw material, crush the peanut shells to 500 mesh, use sodium molybdate as the molybdenum-containing compound, mix the peanut shells and sodium molybdate at a mass ratio of 1:1, ball mill in a nitrogen atmosphere, ball mill The rotation speed is 800r/min and the running time is 4h;
步骤二：采用ZnO作为模板剂和致孔剂，加入步骤一的混合物中，继续在氮气氛围中进行球磨获得混合物前驱体，其中花生壳与ZnO质量比为1∶2，球磨机转速为2400r/min，运行16h；Step 2: Use ZnO as the template agent and porogen, add it to the mixture in step 1, and continue ball milling in a nitrogen atmosphere to obtain the mixture precursor. The mass ratio of peanut shells to ZnO is 1:2, and the ball mill speed is 2400r/min. , run for 16h;
步骤三：将步骤二获得的混合物前驱体放入管式炉中，在氮气中首先加热至850℃，升温速率2℃/min，维持4h，随后继续升温至1000℃，升温速率6℃/min，维持1.5h，冷却后收集产物获得析氢电催化剂B。Step 3: Put the mixture precursor obtained in Step 2 into a tube furnace, first heat it to 850°C in nitrogen at a heating rate of 2°C/min, maintain it for 4 hours, and then continue to heat it to 1000°C at a heating rate of 6°C/min. , maintained for 1.5 h, and collected the product after cooling to obtain hydrogen evolution electrocatalyst B.
实施例3：Example 3:
步骤一：采用黄豆根茎为生物质原料，将黄豆根茎破碎至600目，采用钼酸钠为含钼化合物，将黄豆根茎与钼酸钠按质量比1∶2混合，在氮气氛围中球磨，球磨机转速为1000r/min，运行时间为6h；Step 1: Use soybean rhizome as the biomass raw material, crush the soybean rhizome to 600 mesh, use sodium molybdate as the molybdenum-containing compound, mix the soybean rhizome and sodium molybdate at a mass ratio of 1:2, ball mill in a nitrogen atmosphere, ball mill The rotation speed is 1000r/min and the running time is 6h;
步骤二：采用ZnCO3作为模板剂和致孔剂，加入步骤一的混合物中，继续在氮气氛围中进行球磨获得混合物前驱体，其中黄豆根茎与ZnCO2质量比为1∶3，球磨机转速为3600r/min，运行24h；Step 2: Use ZnCO 3 as the template agent and porogen, add it to the mixture in step 1, and continue ball milling in a nitrogen atmosphere to obtain the mixture precursor. The mass ratio of soybean rhizome to ZnCO 2 is 1:3, and the ball mill speed is 3600r. /min, run for 24 hours;
步骤三：将步骤二获得的混合物前驱体放入管式炉中，在氮气中首先加热至900℃，升温速率3℃/min，维持2h，随后继续升温至1100℃，升温速率8℃/min，维持2h，，冷却后收集产物获得析氢电催化剂C。Step 3: Put the mixture precursor obtained in Step 2 into a tube furnace, first heat it to 900°C in nitrogen at a heating rate of 3°C/min, maintain it for 2 hours, and then continue to heat it to 1100°C at a heating rate of 8°C/min. , maintained for 2 h, and collected the product after cooling to obtain hydrogen evolution electrocatalyst C.
经过电化学测试测定，上述的析氢电催化剂A、析氢电催化剂B、析氢电催化剂C驱动析氢电流密度达到10mAcm-2时的过电势为198mV，210mV和206mV，因此具有良好的催化活性。After electrochemical testing, the overpotentials of the above-mentioned hydrogen evolution electrocatalyst A, hydrogen evolution electrocatalyst B, and hydrogen evolution electrocatalyst C when driving the hydrogen evolution current density to 10 mAcm -2 are 198 mV, 210 mV, and 206 mV, so they have good catalytic activity.
本领域普通技术人员可以理解：以上所述仅为本发明的优选实施例而已，并不用于限制本发明，尽管参照前述实施例对本发明进行了详细的说明，对于本领域的技术人员来说，其依然可以对前述各实施例记载的技术方案进行修改，或者对其中部分技术特征进行等同替换。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。Those of ordinary skill in the art can understand that the above are only preferred embodiments of the present invention and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, for those skilled in the art, It is still possible to modify the technical solutions recorded in the foregoing embodiments, or to make equivalent replacements for some of the technical features. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention shall be included in the protection scope of the present invention.
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106684396A (en) * | 2016-12-21 | 2017-05-17 | 北京化工大学 | Method for preparing bifunctional catalyst from peanut hull |
| CN108970626A (en) * | 2018-07-30 | 2018-12-11 | 苏州科技大学 | A kind of optic catalytic composite material and the preparation method and application thereof |
| CN109046419A (en) * | 2018-07-03 | 2018-12-21 | 桂林电子科技大学 | A kind of ginkgo leaf base porous carbon materials and its preparation method and application loading ruthenium |
| CN109516458A (en) * | 2018-12-05 | 2019-03-26 | 华南师范大学 | A kind of biomass-based graded porous carbon and preparation method thereof |
| CN109835900A (en) * | 2019-03-21 | 2019-06-04 | 哈尔滨工业大学 | A kind of preparation method of the coal base porous carbon based on potassium carbonate cyclic activation and the preparation method of biomass-based porous carbon |
| CN110124699A (en) * | 2019-05-30 | 2019-08-16 | 河北科技大学 | Biomass carbon pipe assists MoS2The preparation method and applications of liberation of hydrogen catalyst |
| KR20210082686A (en) * | 2019-12-26 | 2021-07-06 | 울산과학기술원 | Method for producing hydrogen using a reduction of phosphomolybdic acid and system for producing hydrogen |
| CN113416975A (en) * | 2021-05-28 | 2021-09-21 | 江苏大学 | Method for preparing biomass carbon-loaded molybdenum carbide electrode material by one-step calcination method |
| CN113463111A (en) * | 2021-06-28 | 2021-10-01 | 江苏大学 | Method for preparing biomass carbon-loaded molybdenum sulfide electrode material by one-step method |
| CN113611878A (en) * | 2021-06-16 | 2021-11-05 | 东南大学 | Nitrogen-rich bio-oil-based porous carbon and preparation method and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014055533A1 (en) * | 2012-10-01 | 2014-04-10 | Brookhaven Science Associates / Brookhaven National Laboratory | Biomass transition metal hydrogen-evolution electrocatalysts and electrodes |
-
2022
- 2022-04-27 CN CN202210462886.6A patent/CN114836787B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106684396A (en) * | 2016-12-21 | 2017-05-17 | 北京化工大学 | Method for preparing bifunctional catalyst from peanut hull |
| CN109046419A (en) * | 2018-07-03 | 2018-12-21 | 桂林电子科技大学 | A kind of ginkgo leaf base porous carbon materials and its preparation method and application loading ruthenium |
| CN108970626A (en) * | 2018-07-30 | 2018-12-11 | 苏州科技大学 | A kind of optic catalytic composite material and the preparation method and application thereof |
| CN109516458A (en) * | 2018-12-05 | 2019-03-26 | 华南师范大学 | A kind of biomass-based graded porous carbon and preparation method thereof |
| CN109835900A (en) * | 2019-03-21 | 2019-06-04 | 哈尔滨工业大学 | A kind of preparation method of the coal base porous carbon based on potassium carbonate cyclic activation and the preparation method of biomass-based porous carbon |
| CN110124699A (en) * | 2019-05-30 | 2019-08-16 | 河北科技大学 | Biomass carbon pipe assists MoS2The preparation method and applications of liberation of hydrogen catalyst |
| KR20210082686A (en) * | 2019-12-26 | 2021-07-06 | 울산과학기술원 | Method for producing hydrogen using a reduction of phosphomolybdic acid and system for producing hydrogen |
| CN113416975A (en) * | 2021-05-28 | 2021-09-21 | 江苏大学 | Method for preparing biomass carbon-loaded molybdenum carbide electrode material by one-step calcination method |
| CN113611878A (en) * | 2021-06-16 | 2021-11-05 | 东南大学 | Nitrogen-rich bio-oil-based porous carbon and preparation method and application thereof |
| CN113463111A (en) * | 2021-06-28 | 2021-10-01 | 江苏大学 | Method for preparing biomass carbon-loaded molybdenum sulfide electrode material by one-step method |
Non-Patent Citations (2)
| Title |
|---|
| Nitrogen and sulfur co-doped porous carbon derived from human hair as highly efficient metal-free electrocatalysts for hydrogen evolution reactions;Xiaojun Liu等;J. Mater. Chem. A;第3卷;第8840-8846页 * |
| One-pot synthesis of Mo2C&MoS2 loaded on N/S co-doped carbon materials as the electrocatalyts for hydrogen evolution reaction;Qichang Wang等;Fuel;第318卷;第123615-1—123615-8页 * |
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