WO2022222430A1 - Tin-based bimetallic carbide@carbon nano chain core-shell structure, preparation method therefor and application thereof - Google Patents

Tin-based bimetallic carbide@carbon nano chain core-shell structure, preparation method therefor and application thereof Download PDF

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WO2022222430A1
WO2022222430A1 PCT/CN2021/129367 CN2021129367W WO2022222430A1 WO 2022222430 A1 WO2022222430 A1 WO 2022222430A1 CN 2021129367 W CN2021129367 W CN 2021129367W WO 2022222430 A1 WO2022222430 A1 WO 2022222430A1
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tin
nanochain
core
carbon
bimetallic carbide
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李泽胜
林松威
鲍琳
余长林
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广东石油化工学院
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • 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
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/06—Making microcapsules or microballoons by phase separation
    • B01J13/12—Making microcapsules or microballoons by phase separation removing solvent from the wall-forming material solution
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

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  • the invention relates to the field of electrochemical catalytic water splitting, in particular to a tin-based bimetallic carbide@carbon nano-chain core-shell structure and a preparation method and application thereof.
  • the combustion product of hydrogen is water, which does not produce carbon dioxide and other pollutants, and is a clean and efficient energy source.
  • Hydrogen production by electrolysis of water is a relatively convenient method for producing hydrogen. In the process of water electrolysis, water is decomposed into hydrogen and oxygen under the action of electric current.
  • the low efficiency, high cost, and large power consumption of oxygen-generating electrodes are one of the main technical difficulties in the industrialization of hydrogen production by electrolysis of water.
  • Catalysts can usually greatly reduce the activation energy of electrolyzed water, thereby reducing the overpotential of electrolyzed water and improving electrolysis efficiency.
  • Research on new catalysts to increase energy conversion efficiency is the focus of great attention in the energy field.
  • Both platinum and yttrium oxide are ideal catalysts for water electrolysis, but due to the scarcity of precious metals such as platinum and yttrium, scientists are looking for some cheap catalysts, such as transition metal carbides.
  • bimetallic carbide materials contain binary metal components, the catalytic performance can be significantly optimized, and bimetallic carbide materials have become a new research direction at present (eg CN107185570A).
  • the lack of electrical conductivity of carbide materials itself greatly inhibits the electrochemical application of bimetallic carbide materials.
  • the development of bimetallic carbide/carbon composites can further improve the conductivity and stability of catalytic materials, so it has good development prospects and application value.
  • the purpose of the present invention is to overcome the defects and deficiencies of the high price of the existing catalysts for hydrogen production by electrolysis of water, and to provide a tin-based bimetallic carbide@carbon nano-chain core-shell structure.
  • the second metal is introduced into the tin base, and the catalytic performance is obviously optimized; in addition, the carbon nano-chain is used for coating, which can greatly improve the electrical conductivity and stability of the material.
  • the tin-based bimetallic carbide@carbon nano-chain core-shell structure provided by the invention not only has good electrical conductivity and stability, but also has good catalytic performance.
  • Another object of the present invention is to provide a method for preparing the above-mentioned tin-based bimetallic carbide@carbon nanochain core-shell structure.
  • Another object of the present invention is to provide the application of the above-mentioned tin-based bimetallic carbide@carbon nanochain core-shell structure as a catalyst in electrochemical catalytic water splitting.
  • a tin-based bimetallic carbide@carbon nanochain core-shell structure comprising a tin-based bimetallic carbide MnSnCm and a carbon nanochain, the carbon nanochain wrapping the tin-based bimetallic carbide MnSnCm , 1 ⁇ n ⁇ 3, 0.5 ⁇ m ⁇ 2, the diameter of the tin-based bimetallic carbide Mn SnC m is 12-45 nm, and the thickness of the carbon nanochain is 4-25 nm.
  • the second metal is introduced into the tin base, and the catalytic performance is obviously optimized; in addition, the carbon nano-chain is used for coating, which can greatly improve the electrical conductivity and stability of the material.
  • the tin-based bimetallic carbide@carbon nano-chain core-shell structure provided by the invention not only has good electrical conductivity and stability, but also has good catalytic performance.
  • the second metal M of the tin-based bimetallic compound is cobalt, iron, manganese or titanium.
  • the introduction of several second metals such as cobalt, iron, manganese or titanium can further improve the catalytic performance.
  • the tin-based bimetallic carbides are M 3 SnC 0.7 , Fe 3 SnC, CMn 3 Sn, SnTi 2 C.
  • the diameter of the tin-based bimetallic carbide Mn SnC m is 15-35 nm.
  • the thickness of the carbon nanochains is 8-20 nm.
  • the preparation method of the above-mentioned tin-based bimetallic carbide@carbon nano-chain core-shell structure comprises the following steps:
  • the invention uses cheap tin source and polysaccharide as raw materials to prepare SnO 2 @ polysaccharide core-shell nano-chain precursor, which greatly reduces the preparation cost of the material; and then directly introduces the second metal source, utilizes the core
  • the structure conversion can efficiently prepare a variety of bimetallic carbide@carbon nanochain core-shell structures, and the operation is controllable, which fundamentally simplifies the synthesis steps and improves the efficiency of material synthesis.
  • the polysaccharide in S1 is a thermal polycondensation product of one or more of glucose, sucrose or fructose.
  • the tin source in S1 is sodium stannite.
  • the temperature of the hydrothermal reaction in S1 is 120-220° C.; the time of the hydrothermal reaction is 1-6 h.
  • the mass ratio of the tin source and the polysaccharide in S1 is 1:5-25.
  • the second metal source in S2 is a cobalt source, an iron source, a manganese source or a titanium source.
  • Cobalt, iron, manganese and titanium sources conventional in the art can be used in the present invention.
  • the cobalt source is one or more of cobalt acetate, cobalt nitrate, cobalt sulfate or cobalt chloride.
  • the iron source is one or both of ferric chloride or ferrocene.
  • the manganese source is one or both of manganese acetate or manganese nitrate.
  • the titanium source is one or both of titanate or titanium tetrachloride.
  • the high-temperature sintering temperature in S2 is 400-800° C.; the high-temperature sintering time is 0.5-4 h.
  • the mass ratio of the SnO 2 @polysaccharide core-shell nanochain precursor and the second metal source in S2 is 1:0.2-1.5.
  • the present invention has the following beneficial effects:
  • the tin-based bimetallic carbide@carbon nano-chain core-shell structure provided by the invention has the advantages of low price, good electrical conductivity and stability, and excellent catalytic performance, and can be widely used for electrolysis of water to produce hydrogen; the raw material selected by the preparation method of the invention has low cost. , the steps are simple and the synthesis efficiency is high.
  • Fig. 1 is the general process schematic diagram of the present invention to prepare bimetallic carbide@carbon nano-chain core-shell structure material
  • Fig. 2 is the X-ray diffraction pattern of the bimetallic carbide@carbon nanochain core-shell structure material prepared in Example 1;
  • Fig. 3 is the transmission electron microscope picture of bimetallic carbide@carbon nanochain core-shell structure material prepared in Example 1;
  • Fig. 4 is the polarization curve of the oxygen evolution of electrolyzed water of bimetallic carbide@carbon nanochain core-shell structure material prepared in Example 1;
  • FIG. 5 is the AC impedance curve of the electrolyzed water for oxygen evolution of the bimetallic carbide@carbon nanochain core-shell structure material prepared in Example 1.
  • This embodiment provides a bimetallic carbide (Co 3 SnC 0.7 )@carbon nanochain core-shell structure, which is prepared through the following process (as shown in FIG. 1 ).
  • the obtained “Co 3 SnC 0.7 @carbon nanochain core-shell structure” material was measured, wherein the thickness of the carbon layer was about 15 nm, and the diameter of Co 3 SnC 0.7 was about 20 nm.
  • This embodiment provides a bimetallic carbide (Co 3 SnC 0.7 )@carbon nanochain core-shell structure, which is prepared through the following process.
  • the obtained “Co 3 SnC 0.7 @carbon nanochain core-shell structure” material is measured, wherein the thickness of the carbon layer is about 8 nm, and the size of Co 3 SnC 0.7 is about 25 nm.
  • This embodiment provides a bimetallic carbide (Co 3 SnC 0.7 )@carbon nanochain core-shell structure, which is prepared through the following process.
  • the obtained “Co 3 SnC 0.7 @carbon nanochain core-shell structure” material was measured, wherein the thickness of the carbon layer was about 20 nm, and the size of Co 3 SnC 0.7 was about 30 nm.
  • This embodiment provides a bimetallic carbide (Co 3 SnC 0.7 )@carbon nanochain core-shell structure, which is prepared through the following process.
  • the obtained “Co 3 SnC 0.7 @carbon nanochain core-shell structure” material was measured, wherein the thickness of the carbon layer was about 15 nm, and the size of Co 3 SnC 0.7 was about 25 nm;
  • This embodiment provides a bimetallic carbide (Co 3 SnC 0.7 )@carbon nanochain core-shell structure, which is prepared through the following process.
  • the obtained "Co 3 SnC 0.7 @carbon nanochain core-shell structure” material is measured, wherein the thickness of the carbon layer is about 15 nm, and the size of Co 3 SnC 0.7 is about 35 nm.
  • This embodiment provides a bimetallic carbide (Co 3 SnC 0.7 )@carbon nanochain core-shell structure, which is prepared through the following process.
  • the obtained “Co 3 SnC 0.7 @carbon nanochain core-shell structure” material was measured, wherein the thickness of the carbon layer was about 18 nm, and the size of Co 3 SnC 0.7 was about 16 nm.
  • This embodiment provides a bimetallic carbide (Co 3 SnC 0.7 )@carbon nanochain core-shell structure, which is prepared through the following process.
  • the obtained “Co 3 SnC 0.7 @carbon nanochain core-shell structure” material was measured, wherein the thickness of the carbon layer was about 25 nm, and the size of Co 3 SnC 0.7 was about 35 nm.
  • This embodiment provides a bimetallic carbide (Fe 3 SnC)@carbon nanochain core-shell structure, which is prepared through the following process.
  • the obtained “Fe 3 SnC@carbon nanochain core-shell structure” material is measured, the thickness of the carbon layer is about 15nm, and the size of Fe 3 SnC is about 30nm.
  • This embodiment provides a bimetallic carbide (CMn 3 Sn)@carbon nanochain core-shell structure, which is prepared through the following process.
  • CMn 3 Sn@carbon nanochain core-shell structure material was measured, wherein the thickness of the carbon layer was about 15 nm, and the size of CMn 3 Sn was about 15 nm.
  • This embodiment provides a bimetallic carbide (SnTi 2 C)@carbon nanochain core-shell structure, which is prepared through the following process.
  • the thickness of the carbon layer is about 15 nm, and the size of SnTi 2 C is about 12 nm.
  • This embodiment provides a bimetallic carbide (Co 3 SnC 0.7 )@carbon nanochain core-shell structure, which is prepared through the following process.
  • the obtained “Co 3 SnC 0.7 @carbon nanochain core-shell structure” material was measured, wherein the thickness of the carbon layer was about 4 nm, and the size of Co 3 SnC 0.7 was about 45 nm.
  • This embodiment provides a bimetallic carbide (Co 3 SnC 0.7 )@carbon nanochain core-shell structure, which is prepared through the following process.
  • the obtained “Co 3 SnC 0.7 @carbon nanochain core-shell structure” material was measured, wherein the thickness of the carbon layer was about 25 nm, and the size of Co 3 SnC 0.7 was about 35 nm.
  • This comparative example provides a bimetallic carbide Co 3 SnC 0.7 , which is prepared through the following process.
  • the obtained “Co 3 SnC 0.7” material was measured, and the size of Co 3 SnC 0.7 was about 75 nm.
  • the present invention takes the bimetallic carbide (Co 3 SnC 0.7 )@carbon nanochain core-shell structure prepared in Example 1 as an example to characterize it.
  • Figure 2 is an X-ray diffraction pattern. It can be seen from FIG. 2 that the product is Co 3 SnC 0.7 of the PDF#29-0513 model, with high diffraction peak intensity and good crystal structure.
  • FIG. 3 is a transmission electron microscope picture, and it can be seen from FIG. 3 that the product is a Co 3 SnC 0.7 nanoparticle structure covered by carbon nanochains.
  • Fig. 4 is the polarization curve of the oxygen evolution of electrolyzed water of the bimetallic carbide@carbon nanochain core-shell structure material prepared in Example 1
  • Fig. 5 is the bimetallic carbide@carbon nanochain core prepared in Example 1 AC impedance curves of electrolyzed water for oxygen evolution of shell-structured materials.
  • Example 1 Test items Characteristic current density (A/g) Resistance ( ⁇ ) Example 1 27.8 20 Example 2 22.3 26 Example 3 20.9 18 Example 4 25.2 twenty two Example 5 19.8 25 Example 6 24.3 38 Example 7 20.6 twenty three Example 8 25.1 20 Example 9 23.2 twenty three Example 10 24.5 20 Example 11 17.6 35 Example 12 20.2 28 Comparative Example 1 14.2 42 Ruthenium dioxide 32.8 39
  • the bimetallic carbide@carbon nanochain core-shell structure materials provided by various embodiments of the present invention have higher characteristic current density, lower resistance, better catalytic performance, and are similar to ruthenium dioxide.
  • the specific performance is already very considerable; the bimetallic carbide in Comparative Example 1 has a slightly poor catalytic performance because it is a non-precious metal material.

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Abstract

The present invention relates to a tin-based bimetallic carbide@carbon nano chain core-shell structure, a preparation method therefor and the application thereof. The tin-based bimetallic carbide@carbon nano chain core-shell structure comprises a tin-based bimetallic carbide of MnSnCm and a carbon nano chain coated on the tin-based bimetallic carbide of MnSnCm, wherein 1≤n≤3 and 0.5≤m≤2, the tin-based bimetallic carbide of MnSnCm has a diameter of 12 to 45 nm, and the carbon nano chain has a thickness of 4 to 25 nm. In the present invention, a second metal is introduced into a tin base, such that the catalytic property is obviously optimized; in addition, coating same with the carbon nano chain can significantly improve the conductivity and stability of the material. The tin-based bimetallic carbide@carbon nano chain core-shell structure provided by the present invention not only has a better conductivity and stability, but also has superior catalytic properties.

Description

一种锡基双金属碳化物@碳纳米链核壳结构及其制备方法和应用A tin-based bimetallic carbide@carbon nanochain core-shell structure and its preparation method and application 技术领域technical field
本发明涉及电化学催化分解水领域，特别涉及一种锡基双金属碳化物@碳纳米链核壳结构及其制备方法和应用。The invention relates to the field of electrochemical catalytic water splitting, in particular to a tin-based bimetallic carbide@carbon nano-chain core-shell structure and a preparation method and application thereof.
背景技术Background technique
氢气的燃烧产物是水，不会产生二氧化碳和其他污染物，是一种清洁高效的能源。电解水制氢是一种较为方便的制取氢气的方法。在电解水的过程中，水在电流作用下被分解成氢气和氧气。然而，产氧电极的效率低、成本高、需要消耗大量电力，是电解水制氢产业化的主要技术难题之一。The combustion product of hydrogen is water, which does not produce carbon dioxide and other pollutants, and is a clean and efficient energy source. Hydrogen production by electrolysis of water is a relatively convenient method for producing hydrogen. In the process of water electrolysis, water is decomposed into hydrogen and oxygen under the action of electric current. However, the low efficiency, high cost, and large power consumption of oxygen-generating electrodes are one of the main technical difficulties in the industrialization of hydrogen production by electrolysis of water.
催化剂通常能使电解水的活化能大大降低，从而降低电解水的过电势，提高电解效率。研究新型的催化剂来增加能量转换效率是能源领域十分受关注的焦点。铂金和氧化钇都是比较理想化的电解水催化剂，但是由于铂和钇贵金属资源稀缺，科学家正在寻找一些廉价催化剂，例如过渡金属碳化物。Catalysts can usually greatly reduce the activation energy of electrolyzed water, thereby reducing the overpotential of electrolyzed water and improving electrolysis efficiency. Research on new catalysts to increase energy conversion efficiency is the focus of great attention in the energy field. Both platinum and yttrium oxide are ideal catalysts for water electrolysis, but due to the scarcity of precious metals such as platinum and yttrium, scientists are looking for some cheap catalysts, such as transition metal carbides.
由于双金属碳化材料含有二元金属成分，催化性能可以得到明显优化，双金属碳化材料成为了目前的研究新方向(例如CN107185570A)。然而，碳化物材料本身的导电能力欠缺，大大抑制了双金属碳化材料的电化学应用。发展双金属碳化/碳复合材料可以进一步提升催化材料的导电性和稳定性，因此具有良好的发展前景和应用价值。Since bimetallic carbide materials contain binary metal components, the catalytic performance can be significantly optimized, and bimetallic carbide materials have become a new research direction at present (eg CN107185570A). However, the lack of electrical conductivity of carbide materials itself greatly inhibits the electrochemical application of bimetallic carbide materials. The development of bimetallic carbide/carbon composites can further improve the conductivity and stability of catalytic materials, so it has good development prospects and application value.
发明内容SUMMARY OF THE INVENTION
本发明的目的在于克服现有电解水制氢的催化剂价格高的缺陷和不足，提供一种锡基双金属碳化物@碳纳米链核壳结构。本发明向锡基中引入第二金属，催化性能得到明显优化；另外利用碳纳米链来包覆，可大大提高材料的导电性和稳定性。本发明提供的锡基双金属碳化物@碳纳米链核壳结构不仅具有较好的导电性和稳定性，而且催化性能较佳。The purpose of the present invention is to overcome the defects and deficiencies of the high price of the existing catalysts for hydrogen production by electrolysis of water, and to provide a tin-based bimetallic carbide@carbon nano-chain core-shell structure. In the present invention, the second metal is introduced into the tin base, and the catalytic performance is obviously optimized; in addition, the carbon nano-chain is used for coating, which can greatly improve the electrical conductivity and stability of the material. The tin-based bimetallic carbide@carbon nano-chain core-shell structure provided by the invention not only has good electrical conductivity and stability, but also has good catalytic performance.
本发明的另一目的在于提供上述锡基双金属碳化物@碳纳米链核壳结构的制备方法。Another object of the present invention is to provide a method for preparing the above-mentioned tin-based bimetallic carbide@carbon nanochain core-shell structure.
本发明的另一目的在于提供上述锡基双金属碳化物@碳纳米链核壳结构作为催化剂在电化学催化分解水方面的应用。Another object of the present invention is to provide the application of the above-mentioned tin-based bimetallic carbide@carbon nanochain core-shell structure as a catalyst in electrochemical catalytic water splitting.
为实现上述发明目的，本发明采用如下技术方案：For realizing the above-mentioned purpose of the invention, the present invention adopts following technical scheme:
一种锡基双金属碳化物@碳纳米链核壳结构，包括锡基双金属碳化物M nSnC m和碳纳米链，碳纳米链包覆锡基双金属碳化物M nSnC m，1≤n≤3，0.5≤m≤2，锡基双金属碳化物M nSnC m的直径为12～45nm，碳纳米链的厚度为4～25nm。 A tin-based bimetallic carbide@carbon nanochain core-shell structure, comprising a tin-based bimetallic carbide MnSnCm and a carbon nanochain, the carbon nanochain wrapping the tin-based bimetallic carbide MnSnCm , 1≤ n≤3, 0.5≤m≤2, the diameter of the tin-based bimetallic carbide Mn SnC m is 12-45 nm, and the thickness of the carbon nanochain is 4-25 nm.
本发明向锡基中引入第二金属，催化性能得到明显优化；另外利用碳纳米链来包覆，可大大提高材料的导电性和稳定性。本发明提供的锡基双金属碳化物@碳纳米链核壳结构不仅具有较好的导电性和稳定性，而且催化性能较佳。In the present invention, the second metal is introduced into the tin base, and the catalytic performance is obviously optimized; in addition, the carbon nano-chain is used for coating, which can greatly improve the electrical conductivity and stability of the material. The tin-based bimetallic carbide@carbon nano-chain core-shell structure provided by the invention not only has good electrical conductivity and stability, but also has good catalytic performance.
优选地，所述锡基双金属化合物的第二金属M为钴、铁、锰或钛。Preferably, the second metal M of the tin-based bimetallic compound is cobalt, iron, manganese or titanium.
钴、铁、锰或钛这几种第二金属的引入，可进一步提高催化性能。The introduction of several second metals such as cobalt, iron, manganese or titanium can further improve the catalytic performance.
优选地，所述锡基双金属碳化物为M 3SnC 0.7、Fe 3SnC、CMn 3Sn、SnTi 2C。 Preferably, the tin-based bimetallic carbides are M 3 SnC 0.7 , Fe 3 SnC, CMn 3 Sn, SnTi 2 C.
优选地，所述锡基双金属碳化物M nSnC m的直径为15～35nm。 Preferably, the diameter of the tin-based bimetallic carbide Mn SnC m is 15-35 nm.
优选地，所述碳纳米链的厚度为8～20nm。Preferably, the thickness of the carbon nanochains is 8-20 nm.
上述锡基双金属碳化物@碳纳米链核壳结构的制备方法，包括如下步骤：The preparation method of the above-mentioned tin-based bimetallic carbide@carbon nano-chain core-shell structure comprises the following steps:
S1：以多聚糖作为碳源和锡源混合后进行水热反应得SnO 2@多聚糖核壳纳米链前驱体； S1: Using polysaccharide as a carbon source and a tin source to mix and perform a hydrothermal reaction to obtain SnO 2 @polysaccharide core-shell nanochain precursor;
S2：将SnO 2@多聚糖核壳纳米链前驱体和第二金属源混合，在惰性气氛下高温烧结，即得所述锡基双金属碳化物@碳纳米链核壳结构。 S2: Mixing the SnO 2 @polysaccharide core-shell nanochain precursor and the second metal source, and sintering at high temperature in an inert atmosphere, the tin-based bimetallic carbide@carbon nanochain core-shell structure is obtained.
本发明以廉价的锡源和多聚糖作为原料来制备SnO 2@多聚糖核壳纳米链前驱体，很大程度上降低了材料的制备成本；然后通过直接引入第二金属源，利用核结构转换，可高效制备出多样化的双金属碳化物@碳纳米链核壳结构，操作可控，从根本上简化了合成步骤，提高了材料合成的效率。 The invention uses cheap tin source and polysaccharide as raw materials to prepare SnO 2 @ polysaccharide core-shell nano-chain precursor, which greatly reduces the preparation cost of the material; and then directly introduces the second metal source, utilizes the core The structure conversion can efficiently prepare a variety of bimetallic carbide@carbon nanochain core-shell structures, and the operation is controllable, which fundamentally simplifies the synthesis steps and improves the efficiency of material synthesis.
本领域常规的多聚糖、锡源均可用于本发明中。Conventional polysaccharides and tin sources in the art can be used in the present invention.
优选地，S1中所述多聚糖为葡萄糖、蔗糖或果糖中的一种或几种的热缩聚产物。Preferably, the polysaccharide in S1 is a thermal polycondensation product of one or more of glucose, sucrose or fructose.
优选地，S1中所述锡源为亚锡酸钠。Preferably, the tin source in S1 is sodium stannite.
优选地，S1中所述水热反应的温度为120～220℃；水热反应的时间为1～6h。Preferably, the temperature of the hydrothermal reaction in S1 is 120-220° C.; the time of the hydrothermal reaction is 1-6 h.
优选地，S1中所述锡源和多聚糖的质量比为1:5～25。Preferably, the mass ratio of the tin source and the polysaccharide in S1 is 1:5-25.
优选地，S2中所述第二金属源为钴源、铁源、锰源或钛源。Preferably, the second metal source in S2 is a cobalt source, an iron source, a manganese source or a titanium source.
本领域常规的钴源、铁源、锰源和钛源均可用于本发明中。Cobalt, iron, manganese and titanium sources conventional in the art can be used in the present invention.
更为优选地，所述钴源为醋酸钴、硝酸钴、硫酸钴或氯化钴中的一种或几种。More preferably, the cobalt source is one or more of cobalt acetate, cobalt nitrate, cobalt sulfate or cobalt chloride.
更为优选地，所述铁源为氯化铁或二茂铁中的一种或两种。More preferably, the iron source is one or both of ferric chloride or ferrocene.
更为优选地，所述锰源为醋酸锰或硝酸锰中的一种或两种。More preferably, the manganese source is one or both of manganese acetate or manganese nitrate.
更为优选地，所述钛源为钛酸酯或四氯化钛中的一种或两种。More preferably, the titanium source is one or both of titanate or titanium tetrachloride.
优选地，S2中所述高温烧结的温度为400～800℃；高温烧结的时间为0.5～4h。Preferably, the high-temperature sintering temperature in S2 is 400-800° C.; the high-temperature sintering time is 0.5-4 h.
优选地，S2中所述SnO 2@多聚糖核壳纳米链前驱体和第二金属源的质量比为1:0.2～1.5。 Preferably, the mass ratio of the SnO 2 @polysaccharide core-shell nanochain precursor and the second metal source in S2 is 1:0.2-1.5.
上述锡基双金属碳化物@碳纳米链核壳结构作为催化剂在电化学催化分解水方面的应用也在本发明的保护范围内。The application of the above-mentioned tin-based bimetallic carbide@carbon nanochain core-shell structure as a catalyst in electrochemical catalytic water splitting is also within the protection scope of the present invention.
与现有技术相比，本发明具有如下有益效果：Compared with the prior art, the present invention has the following beneficial effects:
本发明提供的锡基双金属碳化物@碳纳米链核壳结构价格低廉，导电性和稳定性好，催化性能优异，可推广用于电解水制氢；本发明的制备方法选用的原料成本低，步骤简单，合成效率高。The tin-based bimetallic carbide@carbon nano-chain core-shell structure provided by the invention has the advantages of low price, good electrical conductivity and stability, and excellent catalytic performance, and can be widely used for electrolysis of water to produce hydrogen; the raw material selected by the preparation method of the invention has low cost. , the steps are simple and the synthesis efficiency is high.
附图说明Description of drawings
图1是本发明制备双金属碳化物@碳纳米链核壳结构材料的通用过程示意图；Fig. 1 is the general process schematic diagram of the present invention to prepare bimetallic carbide@carbon nano-chain core-shell structure material;
图2是实施例1制备的双金属碳化物@碳纳米链核壳结构材料的X射线衍射图谱；Fig. 2 is the X-ray diffraction pattern of the bimetallic carbide@carbon nanochain core-shell structure material prepared in Example 1;
图3是实施例1制备的双金属碳化物@碳纳米链核壳结构材料的透射电子显微镜图片；Fig. 3 is the transmission electron microscope picture of bimetallic carbide@carbon nanochain core-shell structure material prepared in Example 1;
图4是实施例1制备的双金属碳化物@碳纳米链核壳结构材料的电解水析氧的极化曲线；Fig. 4 is the polarization curve of the oxygen evolution of electrolyzed water of bimetallic carbide@carbon nanochain core-shell structure material prepared in Example 1;
图5是实施例1所制备的双金属碳化物@碳纳米链核壳结构材料的电解水析氧的交流阻抗曲线。FIG. 5 is the AC impedance curve of the electrolyzed water for oxygen evolution of the bimetallic carbide@carbon nanochain core-shell structure material prepared in Example 1. FIG.
具体实施方式Detailed ways
下面结合实施例进一步阐述本发明。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。下例实施例中未注明具体条件的实验方法，通常按照本领域常规条件或按照制造厂商建议的条件；所使用的原料、试剂等，如无特殊说明，均为可从常规市场等商业途径得到的原料和试剂。本领域的技术人员在本发明的基础上所做的任何非实质性的变化及替换均属于本发明所要求保护的范围。The present invention is further described below in conjunction with the examples. These examples are only intended to illustrate the present invention and are not intended to limit the scope of the present invention. The experimental methods that do not specify specific conditions in the following examples are usually in accordance with the conventional conditions in the field or the conditions suggested by the manufacturer; the raw materials, reagents, etc. used, unless otherwise specified, are available from commercial channels such as conventional markets. The obtained raw materials and reagents. Any insubstantial changes and substitutions made by those skilled in the art on the basis of the present invention fall within the scope of protection claimed by the present invention.
实施例1Example 1
本实施例提供一种双金属碳化物(Co 3SnC 0.7)@碳纳米链核壳结构，通过如下过程制备得到(如图1)。 This embodiment provides a bimetallic carbide (Co 3 SnC 0.7 )@carbon nanochain core-shell structure, which is prepared through the following process (as shown in FIG. 1 ).
将0.3g亚锡酸钠和4.5g葡萄糖(碳源)，通过水热合成在180℃条件下反应4h，得到SnO 2@多聚糖核壳纳米链前驱体；将0.1gSnO 2@多聚糖核壳纳米链前驱体和0.06g第二金属源(醋酸钴)用蒸馏水混合后，在氮气保护下600℃高温烧结2h，得到“双金属碳化物(Co 3SnC 0.7)@碳纳米链核壳结构”。 0.3g sodium stannite and 4.5g glucose (carbon source) were reacted by hydrothermal synthesis at 180℃ for 4h to obtain SnO 2 @polysaccharide core-shell nanochain precursor; 0.1gSnO 2 @polysaccharide The core-shell nanochain precursor and 0.06 g of the second metal source (cobalt acetate) were mixed with distilled water and sintered at 600 °C for 2 h under nitrogen protection to obtain "bimetallic carbide (Co 3 SnC 0.7 )@carbon nanochain core-shell"structure".
对得到的“Co 3SnC 0.7@碳纳米链核壳结构”材料进行测定，其中，碳层厚度约为15nm，Co 3SnC 0.7直径约为20nm。 The obtained "Co 3 SnC 0.7 @carbon nanochain core-shell structure" material was measured, wherein the thickness of the carbon layer was about 15 nm, and the diameter of Co 3 SnC 0.7 was about 20 nm.
实施例2Example 2
本实施例提供一种双金属碳化物(Co 3SnC 0.7)@碳纳米链核壳结构，通过如下过程制备得到。 This embodiment provides a bimetallic carbide (Co 3 SnC 0.7 )@carbon nanochain core-shell structure, which is prepared through the following process.
将0.3g亚锡酸钠和4.5g葡萄糖(碳源)，通过水热合成在180℃条件下反应2h，得到SnO 2@多聚糖核壳纳米链前驱体；将0.1gSnO 2@多聚糖核壳纳米链前驱体和0.06g第二金属源(醋酸钴)用蒸馏水混合后，在氮气保护下600℃高温烧结2h，得到“双金属碳化物(Co 3SnC 0.7)@碳纳米链核壳结构”。 0.3g sodium stannite and 4.5g glucose (carbon source) were reacted by hydrothermal synthesis at 180℃ for 2h to obtain SnO 2 @polysaccharide core-shell nanochain precursor; 0.1gSnO 2 @polysaccharide The core-shell nanochain precursor and 0.06 g of the second metal source (cobalt acetate) were mixed with distilled water and sintered at 600 °C for 2 h under nitrogen protection to obtain "bimetallic carbide (Co 3 SnC 0.7 )@carbon nanochain core-shell"structure".
对得到的“Co 3SnC 0.7@碳纳米链核壳结构”材料进行测定，其中，碳层厚度约为8nm，Co 3SnC 0.7大小约为25nm。 The obtained "Co 3 SnC 0.7 @carbon nanochain core-shell structure" material is measured, wherein the thickness of the carbon layer is about 8 nm, and the size of Co 3 SnC 0.7 is about 25 nm.
实施例3Example 3
本实施例提供一种双金属碳化物(Co 3SnC 0.7)@碳纳米链核壳结构，通过如下过程制备得到。 This embodiment provides a bimetallic carbide (Co 3 SnC 0.7 )@carbon nanochain core-shell structure, which is prepared through the following process.
将0.3g亚锡酸钠和4.5g葡萄糖(碳源)，通过水热合成在180℃条件下反应6h，得到SnO 2@多聚糖核壳纳米链前驱体；将0.1gSnO 2@多聚糖核壳纳米链前驱体和0.06g第二金属源(醋酸钴)用蒸馏水混合后，在氮气保护下600℃高温烧结2h，得到“双金属碳化物(Co 3SnC 0.7)@碳纳米链核壳结构”。 0.3g sodium stannite and 4.5g glucose (carbon source) were reacted by hydrothermal synthesis at 180℃ for 6h to obtain SnO 2 @polysaccharide core-shell nanochain precursor; 0.1gSnO 2 @polysaccharide The core-shell nanochain precursor and 0.06 g of the second metal source (cobalt acetate) were mixed with distilled water and sintered at 600 °C for 2 h under nitrogen protection to obtain "bimetallic carbide (Co 3 SnC 0.7 )@carbon nanochain core-shell"structure".
对得到的“Co 3SnC 0.7@碳纳米链核壳结构”材料进行测定，其中，碳层厚度约为20nm，Co 3SnC 0.7大小约为30nm。 The obtained "Co 3 SnC 0.7 @carbon nanochain core-shell structure" material was measured, wherein the thickness of the carbon layer was about 20 nm, and the size of Co 3 SnC 0.7 was about 30 nm.
实施例4Example 4
本实施例提供一种双金属碳化物(Co 3SnC 0.7)@碳纳米链核壳结构，通过如下过程制备得到。 This embodiment provides a bimetallic carbide (Co 3 SnC 0.7 )@carbon nanochain core-shell structure, which is prepared through the following process.
将0.3g亚锡酸钠和4.5g葡萄糖为碳源，通过水热合成在180℃条件下反应4h，得到SnO 2@多聚糖核壳纳米链前驱体；将0.1gSnO 2@多聚糖核壳纳米链前驱体和0.02g第二金属源(醋酸钴)用蒸馏水混合后，在氮气保护下600℃高温烧结2h，得到“双金属碳化物(Co 3SnC 0.7)@碳纳米链核壳结构”。 Using 0.3g sodium stannite and 4.5g glucose as the carbon source, and reacting at 180℃ for 4h by hydrothermal synthesis, SnO 2 @polysaccharide core-shell nanochain precursor was obtained; 0.1gSnO 2 @polysaccharide core The shell nanochain precursor and 0.02 g of the second metal source (cobalt acetate) were mixed with distilled water and sintered at 600 °C for 2 h under nitrogen protection to obtain a "bimetallic carbide (Co 3 SnC 0.7 )@carbon nanochain core-shell structure". ".
对得到的“Co 3SnC 0.7@碳纳米链核壳结构”材料进行测定，其中，碳层厚度约为15nm，Co 3SnC 0.7大小约为25nm； The obtained "Co 3 SnC 0.7 @carbon nanochain core-shell structure" material was measured, wherein the thickness of the carbon layer was about 15 nm, and the size of Co 3 SnC 0.7 was about 25 nm;
实施例5Example 5
本实施例提供一种双金属碳化物(Co 3SnC 0.7)@碳纳米链核壳结构，通过如下过程制备得到。 This embodiment provides a bimetallic carbide (Co 3 SnC 0.7 )@carbon nanochain core-shell structure, which is prepared through the following process.
将0.3g亚锡酸钠和4.5g葡萄糖为碳源，通过水热合成在180℃条件下反应4h，得到SnO 2@多聚糖核壳纳米链前驱体；将0.1gSnO 2@多聚糖核壳纳米链前驱体和0.1g第二金属源(醋酸钴)用蒸馏水混合后，在氮气保护下600℃高温烧结2h，得到“双金属碳化物(Co 3SnC 0.7)@碳纳米链核壳结构”。 Using 0.3g sodium stannite and 4.5g glucose as the carbon source, and reacting at 180℃ for 4h by hydrothermal synthesis, SnO 2 @polysaccharide core-shell nanochain precursor was obtained; 0.1gSnO 2 @polysaccharide core The shell nanochain precursor and 0.1 g of the second metal source (cobalt acetate) were mixed with distilled water and sintered at 600 °C for 2 h under nitrogen protection to obtain a "bimetallic carbide (Co 3 SnC 0.7 )@carbon nanochain core-shell structure". ".
对得到的“Co 3SnC 0.7@碳纳米链核壳结构”材料进行测定，其中，碳层厚度约为15nm，Co 3SnC 0.7大小约为35nm。 The obtained "Co 3 SnC 0.7 @carbon nanochain core-shell structure" material is measured, wherein the thickness of the carbon layer is about 15 nm, and the size of Co 3 SnC 0.7 is about 35 nm.
实施例6Example 6
本实施例提供一种双金属碳化物(Co 3SnC 0.7)@碳纳米链核壳结构，通过如下过程制备得到。 This embodiment provides a bimetallic carbide (Co 3 SnC 0.7 )@carbon nanochain core-shell structure, which is prepared through the following process.
将0.3g亚锡酸钠和4.5g葡萄糖(碳源)，通过水热合成在180℃条件下反应4h，得到SnO 2@多聚糖核壳纳米链前驱体；将0.1gSnO 2@多聚糖核壳纳米链前驱体和0.06g第二金属源(醋酸钴)用蒸馏水混合后，在氮气保护下400℃高温烧结2h，得到“双金属碳化物(Co 3SnC 0.7)@碳纳米链核壳结构”。 0.3g sodium stannite and 4.5g glucose (carbon source) were reacted by hydrothermal synthesis at 180℃ for 4h to obtain SnO 2 @polysaccharide core-shell nanochain precursor; 0.1gSnO 2 @polysaccharide The core-shell nanochain precursor and 0.06 g of the second metal source (cobalt acetate) were mixed with distilled water, and then sintered at 400 °C for 2 h under nitrogen protection to obtain "bimetallic carbide (Co 3 SnC 0.7 )@carbon nanochain core-shell"structure".
对得到的“Co 3SnC 0.7@碳纳米链核壳结构”材料进行测定，其中，碳层厚度约为18nm，Co 3SnC 0.7大小约为16nm。 The obtained "Co 3 SnC 0.7 @carbon nanochain core-shell structure" material was measured, wherein the thickness of the carbon layer was about 18 nm, and the size of Co 3 SnC 0.7 was about 16 nm.
实施例7Example 7
本实施例提供一种双金属碳化物(Co 3SnC 0.7)@碳纳米链核壳结构，通过如下过程制备得到。 This embodiment provides a bimetallic carbide (Co 3 SnC 0.7 )@carbon nanochain core-shell structure, which is prepared through the following process.
将0.3g亚锡酸钠和4.5g葡萄糖(碳源)，通过水热合成在180℃条件下反应4h，得到SnO 2@多聚糖核壳纳米链前驱体；将0.1gSnO 2@多聚糖核壳纳米链前驱体和0.06g第二金属源(醋酸钴)用蒸馏水混合后，在氮气保护下800℃高温烧结2h，得到“双金属碳化物(Co 3SnC 0.7)@碳纳米链核壳结构”。 0.3g sodium stannite and 4.5g glucose (carbon source) were reacted by hydrothermal synthesis at 180℃ for 4h to obtain SnO 2 @polysaccharide core-shell nanochain precursor; 0.1gSnO 2 @polysaccharide The core-shell nanochain precursor and 0.06 g of the second metal source (cobalt acetate) were mixed with distilled water and sintered at 800 °C for 2 h under nitrogen protection to obtain "bimetallic carbide (Co 3 SnC 0.7 )@carbon nanochain core-shell"structure".
对得到的“Co 3SnC 0.7@碳纳米链核壳结构”材料进行测定，其中，碳层厚度约为25nm，Co 3SnC 0.7大小约为35nm。 The obtained "Co 3 SnC 0.7 @carbon nanochain core-shell structure" material was measured, wherein the thickness of the carbon layer was about 25 nm, and the size of Co 3 SnC 0.7 was about 35 nm.
实施例8Example 8
本实施例提供一种双金属碳化物(Fe 3SnC)@碳纳米链核壳结构，通过如下过程制备得到。 This embodiment provides a bimetallic carbide (Fe 3 SnC)@carbon nanochain core-shell structure, which is prepared through the following process.
将0.3g亚锡酸钠和4.5g葡萄糖为碳源，通过水热合成在180℃条件下反应4h，得到SnO 2@多聚糖核壳纳米链前驱体；将0.1gSnO 2@多聚糖核壳纳米链前驱体和0.06g第二金属源(氯化铁)用蒸馏水混合后，在氮气保护下600℃高温烧结2h，得到“双金属碳化物(Fe 3SnC)@碳纳米链核壳结构”。 Using 0.3g sodium stannite and 4.5g glucose as the carbon source, and reacting at 180℃ for 4h by hydrothermal synthesis, SnO 2 @polysaccharide core-shell nanochain precursor was obtained; 0.1gSnO 2 @polysaccharide core The shell nanochain precursor and 0.06 g of the second metal source (ferric chloride) were mixed with distilled water, and then sintered at 600 °C for 2 h under nitrogen protection to obtain a "bimetallic carbide ( Fe3SnC )@carbon nanochain core-shell structure. ".
对得到的“Fe 3SnC@碳纳米链核壳结构”材料进行测定，碳层厚度约为15nm，Fe 3SnC大小约为30nm。 The obtained "Fe 3 SnC@carbon nanochain core-shell structure" material is measured, the thickness of the carbon layer is about 15nm, and the size of Fe 3 SnC is about 30nm.
实施例9Example 9
本实施例提供一种双金属碳化物(CMn 3Sn)@碳纳米链核壳结构，通过如下过程制备得到。 This embodiment provides a bimetallic carbide (CMn 3 Sn)@carbon nanochain core-shell structure, which is prepared through the following process.
将0.3g亚锡酸钠和4.5g葡萄糖为碳源，通过水热合成在180℃条件下反应4h，得到SnO 2@多聚糖核壳纳米链前驱体；将0.1gSnO 2@多聚糖核壳纳米链前驱体和0.06g第二金属源(醋酸锰)用蒸馏水混合后，在氮气保护下600℃高温烧结2h，得到“双金属碳化物(CMn 3Sn)@碳纳米链核壳结构”。 Using 0.3g sodium stannite and 4.5g glucose as the carbon source, and reacting at 180℃ for 4h by hydrothermal synthesis, SnO 2 @polysaccharide core-shell nanochain precursor was obtained; 0.1gSnO 2 @polysaccharide core The shell nanochain precursor and 0.06g of the second metal source (manganese acetate) were mixed with distilled water, and then sintered at 600 °C for 2 h under nitrogen protection to obtain a "bimetallic carbide (CMn 3 Sn)@carbon nanochain core-shell structure" .
对得到的“CMn 3Sn@碳纳米链核壳结构”材料进行测定，其中，碳层厚度约为15nm，CMn 3Sn大小约为15nm。 The obtained "CMn 3 Sn@carbon nanochain core-shell structure" material was measured, wherein the thickness of the carbon layer was about 15 nm, and the size of CMn 3 Sn was about 15 nm.
实施例10Example 10
本实施例提供一种双金属碳化物(SnTi 2C)@碳纳米链核壳结构，通过如下 过程制备得到。 This embodiment provides a bimetallic carbide (SnTi 2 C)@carbon nanochain core-shell structure, which is prepared through the following process.
将0.3g亚锡酸钠和4.5g葡萄糖为碳源，通过水热合成在180℃条件下反应4h，得到SnO 2@多聚糖核壳纳米链前驱体；将0.1gSnO 2@多聚糖核壳纳米链前驱体和0.06g第二金属源(钛酸酯)用蒸馏水混合后，在氮气保护下600℃高温烧结2h，得到“双金属碳化物(SnTi 2C)@碳纳米链核壳结构”。 Using 0.3g sodium stannite and 4.5g glucose as the carbon source, and reacting at 180℃ for 4h by hydrothermal synthesis, SnO 2 @polysaccharide core-shell nanochain precursor was obtained; 0.1gSnO 2 @polysaccharide core The shell nanochain precursor and 0.06 g of the second metal source (titanate) were mixed with distilled water and sintered at 600 °C for 2 h under nitrogen protection to obtain a "bimetallic carbide (SnTi 2 C)@carbon nanochain core-shell structure". ".
对得到的“SnTi 2C@碳纳米链核壳结构”材料，其中碳层厚度约为15nm，SnTi 2C大小约为12nm。 For the obtained "SnTi 2 C@carbon nanochain core-shell structure" material, the thickness of the carbon layer is about 15 nm, and the size of SnTi 2 C is about 12 nm.
实施例11Example 11
本实施例提供一种双金属碳化物(Co 3SnC 0.7)@碳纳米链核壳结构，通过如下过程制备得到。 This embodiment provides a bimetallic carbide (Co 3 SnC 0.7 )@carbon nanochain core-shell structure, which is prepared through the following process.
将0.3g亚锡酸钠和1.5g葡萄糖(碳源)，通过水热合成在180℃条件下反应4h，得到SnO 2@多聚糖核壳纳米链前驱体；将0.1gSnO 2@多聚糖核壳纳米链前驱体和0.06g第二金属源(醋酸钴)用蒸馏水混合后，在氮气保护下600℃高温烧结2h，得到“双金属碳化物(Co 3SnC 0.7)@碳纳米链核壳结构”。 0.3g sodium stannite and 1.5g glucose (carbon source) were reacted by hydrothermal synthesis at 180℃ for 4h to obtain SnO 2 @polysaccharide core-shell nanochain precursor; 0.1gSnO 2 @polysaccharide The core-shell nanochain precursor and 0.06 g of the second metal source (cobalt acetate) were mixed with distilled water and sintered at 600 °C for 2 h under nitrogen protection to obtain "bimetallic carbide (Co 3 SnC 0.7 )@carbon nanochain core-shell"structure".
对得到的“Co 3SnC 0.7@碳纳米链核壳结构”材料进行测定，其中，碳层厚度约为4nm，Co 3SnC 0.7大小约为45nm。 The obtained "Co 3 SnC 0.7 @carbon nanochain core-shell structure" material was measured, wherein the thickness of the carbon layer was about 4 nm, and the size of Co 3 SnC 0.7 was about 45 nm.
实施例12Example 12
本实施例提供一种双金属碳化物(Co 3SnC 0.7)@碳纳米链核壳结构，通过如下过程制备得到。 This embodiment provides a bimetallic carbide (Co 3 SnC 0.7 )@carbon nanochain core-shell structure, which is prepared through the following process.
将0.3g亚锡酸钠和7.5g葡萄糖(碳源)，通过水热合成在180℃条件下反应4h，得到SnO 2@多聚糖核壳纳米链前驱体；将0.1gSnO 2@多聚糖核壳纳米链前驱体和0.06g第二金属源(醋酸钴)用蒸馏水混合后，在氮气保护下600℃高温烧结2h，得到“双金属碳化物(Co 3SnC 0.7)@碳纳米链核壳结构”。 0.3g sodium stannite and 7.5g glucose (carbon source) were reacted by hydrothermal synthesis at 180℃ for 4h to obtain SnO 2 @polysaccharide core-shell nanochain precursor; 0.1gSnO 2 @polysaccharide The core-shell nanochain precursor and 0.06 g of the second metal source (cobalt acetate) were mixed with distilled water and sintered at 600 °C for 2 h under nitrogen protection to obtain "bimetallic carbide (Co 3 SnC 0.7 )@carbon nanochain core-shell"structure".
对得到的“Co 3SnC 0.7@碳纳米链核壳结构”材料进行测定，其中碳层厚度约为25nm，Co 3SnC 0.7大小约为35nm。 The obtained "Co 3 SnC 0.7 @carbon nanochain core-shell structure" material was measured, wherein the thickness of the carbon layer was about 25 nm, and the size of Co 3 SnC 0.7 was about 35 nm.
对比例1Comparative Example 1
本对比例提供一种双金属碳化物Co 3SnC 0.7，通过如下过程制备得到。 This comparative example provides a bimetallic carbide Co 3 SnC 0.7 , which is prepared through the following process.
将0.3g亚锡酸钠，通过水热合成在180℃条件下反应4h，在氮气保护下600℃高温烧结2h，得到“双金属碳化物(Co 3SnC 0.7)”。 0.3 g of sodium stannite was reacted at 180 °C for 4 hours by hydrothermal synthesis, and sintered at a high temperature of 600 °C for 2 hours under nitrogen protection to obtain "bimetallic carbide (Co 3 SnC 0.7 )".
对得到的“Co 3SnC 0.7”材料进行测定，Co 3SnC 0.7大小约为75nm。 The obtained "Co 3 SnC 0.7 " material was measured, and the size of Co 3 SnC 0.7 was about 75 nm.
性能测试Performance Testing
(1)材料表征(1) Material characterization
本发明以实施例1制备得到的双金属碳化物(Co 3SnC 0.7)@碳纳米链核壳结构为例，对其进行表征。 The present invention takes the bimetallic carbide (Co 3 SnC 0.7 )@carbon nanochain core-shell structure prepared in Example 1 as an example to characterize it.
图2为X射线衍射图谱。从图2可知，该产物为PDF#29-0513型号的Co 3SnC 0.7，衍射峰强度高，晶体结构良好。 Figure 2 is an X-ray diffraction pattern. It can be seen from FIG. 2 that the product is Co 3 SnC 0.7 of the PDF#29-0513 model, with high diffraction peak intensity and good crystal structure.
图3为透射电子显微镜图片，从图3可知，该产物为碳纳米链包覆的Co 3SnC 0.7纳米颗粒结构。 FIG. 3 is a transmission electron microscope picture, and it can be seen from FIG. 3 that the product is a Co 3 SnC 0.7 nanoparticle structure covered by carbon nanochains.
(2)电解水析氧性能表征：电解水析氧的极化曲线在10mV/s条件下测试，交流阻抗为100mHz～100kHz。(2) Characterization of oxygen evolution performance of electrolyzed water: The polarization curve of oxygen evolution of electrolyzed water was tested under the condition of 10mV/s, and the AC impedance was 100mHz～100kHz.
测试结果如图4、图5和表1。其中，图4为实施例1制备的双金属碳化物@碳纳米链核壳结构材料的电解水析氧的极化曲线，图5为实施例1所制备的双金属碳化物@碳纳米链核壳结构材料的电解水析氧的交流阻抗曲线。The test results are shown in Figure 4, Figure 5 and Table 1. Wherein, Fig. 4 is the polarization curve of the oxygen evolution of electrolyzed water of the bimetallic carbide@carbon nanochain core-shell structure material prepared in Example 1, and Fig. 5 is the bimetallic carbide@carbon nanochain core prepared in Example 1 AC impedance curves of electrolyzed water for oxygen evolution of shell-structured materials.
表1各实施例和对比例提供的材料的电解水析氧的特征电流密度和电阻Table 1 Characteristic current density and resistance of oxygen evolution in electrolyzed water of the materials provided in each example and comparative example
测试项目Test items 特征电流密度(A/g)Characteristic current density (A/g) 电阻(Ω)Resistance (Ω)
实施例1Example 1 27.827.8 2020
实施例2Example 2 22.322.3 2626
实施例3Example 3 20.920.9 1818
实施例4Example 4 25.225.2 22twenty two
实施例5Example 5 19.819.8 2525
实施例6Example 6 24.324.3 3838
实施例7Example 7 20.620.6 23twenty three
实施例8Example 8 25.125.1 2020
实施例9Example 9 23.223.2 23twenty three
实施例10Example 10 24.524.5 2020
实施例11Example 11 17.617.6 3535
实施例12Example 12 20.220.2 2828
对比例1Comparative Example 1 14.214.2 4242
二氧化钌Ruthenium dioxide 32.832.8 3939
从图4～5和表1可知，本发明各实施例提供的双金属碳化物@碳纳米链核壳结构材料的特征电流密度较高、电阻较低，催化性能较佳，与二氧化钌相比性能 已经非常可观；对比例1中的双金属碳化物由于是非贵金属材质，催化性能略差。It can be seen from FIGS. 4 to 5 and Table 1 that the bimetallic carbide@carbon nanochain core-shell structure materials provided by various embodiments of the present invention have higher characteristic current density, lower resistance, better catalytic performance, and are similar to ruthenium dioxide. The specific performance is already very considerable; the bimetallic carbide in Comparative Example 1 has a slightly poor catalytic performance because it is a non-precious metal material.
以上所述的具体实施方式，对本发明的目的、技术方案和有益效果进行了进一步详细说明，所应理解的是，以上所述仅为本发明的具体实施方式而已，并不用于限定本发明的保护范围，凡在本发明的精神和原则之内，所做的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。The specific embodiments described above further describe the objectives, technical solutions and beneficial effects of the present invention in detail. It should be understood that the above descriptions are only specific embodiments of the present invention, and are not intended to limit the scope of the present invention. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims (10)

  1. 一种锡基双金属碳化物@碳纳米链核壳结构，其特征在于，包括锡基双金属碳化物M nSnC m和碳纳米链，碳纳米链包覆锡基双金属碳化物M nSnC m，1≤n≤3，0.5≤m≤2，锡基双金属碳化物M nSnC m的直径为12～45nm，碳纳米链的厚度为4～25nm。 A tin-based bimetallic carbide@carbon nano-chain core-shell structure, characterized in that it comprises a tin-based bimetallic carbide MnSnCm and a carbon nanochain, and the carbon nanochain coats the tin-based bimetallic carbide MnSnC m , 1≤n≤3, 0.5≤m≤2, the diameter of the tin-based bimetallic carbide Mn SnC m is 12-45 nm, and the thickness of the carbon nanochain is 4-25 nm.
  2. 根据权利要求1所述锡基双金属碳化物@碳纳米链核壳结构，其特征在于，所述锡基双金属碳化物的第二金属M为钴、铁、锰或钛。The tin-based bimetallic carbide@carbon nanochain core-shell structure according to claim 1, wherein the second metal M of the tin-based bimetallic carbide is cobalt, iron, manganese or titanium.
  3. 根据权利要求1所述锡基双金属碳化物@碳纳米链核壳结构，其特征在于，所述锡基双金属碳化物为M 3SnC 0.7、Fe 3SnC、CMn 3Sn或SnTi 2C。 The tin-based bimetallic carbide@carbon nanochain core-shell structure according to claim 1, wherein the tin-based bimetallic carbide is M 3 SnC 0.7 , Fe 3 SnC, CMn 3 Sn or SnTi 2 C.
  4. 权利要求1～3任一所述锡基双金属碳化物@碳纳米链核壳结构的制备方法，其特征在于，包括如下步骤：The preparation method of the tin-based bimetallic carbide@carbon nanochain core-shell structure according to any one of claims 1 to 3, characterized in that, comprising the following steps:
    S1：以多聚糖作为碳源和锡源混合后进行水热反应得SnO 2@多聚糖核壳纳米链前驱体； S1: Using polysaccharide as a carbon source and a tin source to mix and perform a hydrothermal reaction to obtain SnO 2 @polysaccharide core-shell nanochain precursor;
    S2：将SnO 2@多聚糖核壳纳米链前驱体和第二金属源混合，在惰性气氛下高温烧结，即得所述锡基双金属碳化物@碳纳米链核壳结构。 S2: Mixing the SnO 2 @polysaccharide core-shell nanochain precursor and the second metal source, and sintering at high temperature in an inert atmosphere, the tin-based bimetallic carbide@carbon nanochain core-shell structure is obtained.
  5. 根据权利要求4所述制备方法，其特征在于，S1中所述多聚糖为葡萄糖、蔗糖或果糖中的一种或几种的热缩聚产物；S1中所述锡源为亚锡酸钠。The preparation method according to claim 4, wherein the polysaccharide in S1 is one or more thermal polycondensation products of glucose, sucrose or fructose; the tin source in S1 is sodium stannate.
  6. 根据权利要求4所述制备方法，其特征在于，S1中所述水热反应的温度为120～220℃；水热反应的时间为1～6h。The preparation method according to claim 4, wherein the temperature of the hydrothermal reaction in S1 is 120-220° C.; the time of the hydrothermal reaction is 1-6 h.
  7. 根据权利要求4所述制备方法，其特征在于，S1中所述锡源和多聚糖的质量比为1:5～25。The preparation method according to claim 4, wherein the mass ratio of the tin source and the polysaccharide in S1 is 1:5-25.
  8. 根据权利要求4所述制备方法，其特征在于，S2中所述高温烧结的温度为400～800℃；高温烧结的时间为0.5～4h。The preparation method according to claim 4, wherein the temperature of the high-temperature sintering in S2 is 400-800° C.; the high-temperature sintering time is 0.5-4 h.
  9. 据权利要求4所述制备方法，其特征在于，S2中所述SnO 2@多聚糖核壳纳米链前驱体和第二金属源的质量比为1:0.2～1.5。 The preparation method according to claim 4, wherein the mass ratio of the SnO 2 @polysaccharide core-shell nanochain precursor and the second metal source in S2 is 1:0.2-1.5.
  10. 权利要求1～3任一所述锡基双金属碳化物@碳纳米链核壳结构作为催化剂在电化学催化分解水方面的应用。Application of the tin-based bimetallic carbide@carbon nanochain core-shell structure described in any one of claims 1 to 3 as a catalyst in electrochemical catalytic water splitting.
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