WO2021232751A1 - Porous coo/cop nanotubes, preparation method therefor and use thereof - Google Patents

Porous coo/cop nanotubes, preparation method therefor and use thereof Download PDF

Info

Publication number
WO2021232751A1
WO2021232751A1 PCT/CN2020/134252 CN2020134252W WO2021232751A1 WO 2021232751 A1 WO2021232751 A1 WO 2021232751A1 CN 2020134252 W CN2020134252 W CN 2020134252W WO 2021232751 A1 WO2021232751 A1 WO 2021232751A1
Authority
WO
WIPO (PCT)
Prior art keywords
cop
nanotubes
aspartic acid
coo
porous coo
Prior art date
Application number
PCT/CN2020/134252
Other languages
French (fr)
Chinese (zh)
Inventor
徐林
顾敏怡
贾清扬
朱彦博
唐亚文
Original Assignee
南京师范大学
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 南京师范大学 filed Critical 南京师范大学
Publication of WO2021232751A1 publication Critical patent/WO2021232751A1/en

Links

Images

Classifications

    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
    • B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
    • B01J35/61—
    • 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
    • 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
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
    • 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

Definitions

  • the invention relates to a porous CoO/CoP nanotube, a preparation method thereof and its application as a hydrogen evolution reaction catalyst, and belongs to the technical field of Co-based nanotube materials.
  • Non-precious metal catalysts include heteroatom-doped nano-carbon, transition metal chalcogenides, carbides, nitrides, oxides, phosphates, etc., among which transition metal phosphides (TMPs) are typical representatives of high-activity and low-cost catalysts. It is expected to replace precious metals for electrolysis of water. However, transition metal phosphides have low conductivity, low intrinsic activity, and poor performance. Strategies to further improve their catalytic performance are needed, including hybrid compounding, electronic control, and nanostructure design. The development of high-efficiency and low-cost electrocatalysts is the core of water electrolysis.
  • the present invention provides a porous CoO/CoP nanotube and a preparation method thereof, and the application of the porous CoO/CoP nanotube prepared by the method as an electrode catalytic material in the hydrogen evolution reaction.
  • the present invention prepares the cobalt-aspartic acid complex precursor by a simple and universal self-sacrificing template method, and generates porous CoO/CoP nanotubes after first oxidation and then phosphating, showing excellent HER (hydrogen evolution reaction) performance and stability.
  • a method for preparing porous CoO/CoP nanotubes includes using cobalt salt as a metal source and aspartic acid as a complexing agent, preparing a cobalt-aspartic acid complex in advance through a solvothermal reaction, and then removing the cobalt -The aspartic acid complex is calcined and oxidized, and then phosphatized to obtain the porous CoO/CoP nanotubes.
  • the cobalt salt is selected from one or two of Co(NO 3 ) 2 and CoCl 2.
  • the solvothermal reaction is to add aspartic acid, cobalt salt and sodium hydroxide into a mixed solution of water and ethylene glycol, and after mixing, perform a solvothermal reaction at 140-200°C, the reaction time is 4 ⁇ 10h.
  • the volume ratio of water to ethylene glycol is (0.1-99):1; the molar ratio of aspartic acid, cobalt salt and sodium hydroxide is ( 0.01-1): (0.01-1): (0.01-1).
  • the calcining and oxidation is to heat the cobalt-aspartic acid complex in an oxygen atmosphere to 300-400°C for calcining and oxidizing in a temperature-programmed manner, and keeping it for 3-8h, and more preferably 300°C for calcining and oxidizing.
  • the rate of the programmed temperature rise is 0.5-10°C/min.
  • the calcined and oxidized product and sodium hypophosphite are heated to 300-350° C. in an inert atmosphere in a temperature-programmed manner, and maintained for 20-80 minutes to perform phosphating.
  • the inert atmosphere includes at least one of Ar, Ar/H 2 and N 2 ; the rate of the programmed temperature rise is 1-20° C./min.
  • the present invention also provides porous CoO/CoP nanotubes prepared by the preparation method described in the above scheme.
  • the present invention also provides the application of the porous CoO/CoP nanotube as a hydrogen evolution reaction catalyst.
  • Co(NO 3 ) 2 or CoCl 2 is used as a metal source
  • aspartic acid C 4 H 7 NO 4
  • a pink cobalt-aspartic acid complex is prepared in advance
  • the material is first oxidized and then phosphatized by the self-sacrificial template method to obtain porous CoO/CoP nanotubes.
  • the porous CoO/CoP nanotube has a hollow tubular structure, the rough pipe surface has abundant pores, and the CoO and CoP heterostructure interface permeates each other.
  • the porous CoO/CoP nanotube prepared by the present invention has the following advantages: 1
  • the hollow tubular structure has abundant exposed and accessible active sites, which can promote mass transfer in the plane.
  • 2 The organic components are effectively introduced into the pores when cracking, while retaining its unique morphology, exposing a large specific surface area and abundant active sites, which is helpful for the transmission and diffusion of gas and electrolyte.
  • 3CoO and CoP are uniformly distributed, and the heterostructure interface penetrates each other, which has a strong synergistic effect, enhances the conductivity and electron transfer, and promotes the hydrogen evolution reaction.
  • the present invention is a novel method for preparing porous CoO/CoP nanotubes.
  • the porous CoO/CoP nanotubes are prepared by a simple, self-sacrificing template method that can realize large-scale production.
  • the method has simple process, simple operation, and can be realized.
  • Large-scale production; the prepared product has regular morphology, abundant pores, and features many active sites, good cycle stability, and flower-like structure.
  • the prepared CoO/CoP nanotubes have a strong synergistic effect, have more excellent structural characteristics and component advantages, and are a very potential electrolytic water catalytic material, which will be an energy source in the future.
  • the industry application prospect is broad.
  • Figure 1 is a TEM chart of the linear cobalt-aspartic acid complex precursor prepared according to the method of the present invention
  • Figure 2 is a SEM chart of the linear cobalt-aspartic acid complex precursor prepared according to the method of the present invention
  • Figure 3 is the TEM and SEM spectra of porous Co 3 O 4 nanotubes prepared according to the method of the present invention.
  • Figure 4 is an XRD pattern of porous Co 3 O 4 nanotubes prepared according to the method of the present invention.
  • Figure 5 is a TEM chart of porous CoO/CoP nanotubes prepared according to the method of the present invention.
  • Figure 6 is an XRD pattern of porous CoO/CoP nanotubes prepared according to the method of the present invention.
  • Fig. 7 is a HER LSV spectrum of porous CoO/CoP nanotubes and pure CoP prepared according to the method of the present invention.
  • Fig. 8 is a comparison chart of HER before and after 1000 cycles of porous CoO/CoP nanotubes prepared according to the method of the present invention.
  • a method for preparing porous CoO/CoP nanotubes includes the following steps:
  • Step 2) Place the obtained black powder Co 3 O 4 and sodium hypophosphite ( 20 times the mass of Co 3 O 4 ) on the two ends of the porcelain boat at a distance of 5 cm. Heat up to 350°C for heat treatment, keep it at this temperature for 30 minutes, and then cool down to obtain the final product.
  • a method for preparing porous CoO/CoP nanotubes includes the following steps:
  • Step 2) Place the obtained black powder Co 3 O 4 and sodium hypophosphite ( 20 times the mass of Co 3 O 4 ) on the two ends of the porcelain boat at a distance of 5 cm. Heat up to 350°C for heat treatment, keep it at this temperature for 30 minutes, and then cool down to obtain the final product.
  • a method for preparing porous CoO/CoP nanotubes includes the following steps:
  • Step 2) Place the obtained black powder Co 3 O 4 and sodium hypophosphite ( 20 times the mass of Co 3 O 4 ) on the two ends of the porcelain boat at a distance of 5 cm. Heat up to 350°C for heat treatment, keep it at this temperature for 30 minutes, and then cool down to obtain the final product.
  • a method for preparing porous CoO/CoP nanotubes includes the following steps:
  • Step 2) Place the obtained black powder Co 3 O 4 and sodium hypophosphite ( 20 times the mass of Co 3 O 4 ) on the two ends of the porcelain boat at a distance of 5 cm. Heat up to 350°C for heat treatment, keep it at this temperature for 30 minutes, and then cool down to obtain the final product.
  • a method for preparing porous CoO/CoP nanotubes includes the following steps:
  • Step 2) Place the obtained black powder Co 3 O 4 and sodium hypophosphite ( 20 times the mass of Co 3 O 4 ) on the two ends of the porcelain boat at a distance of 5 cm. Heat up to 350°C for heat treatment, keep it at this temperature for 30 minutes, and then cool down to obtain the final product.
  • a method for preparing porous CoO/CoP nanotubes includes the following steps:
  • Step 2) Place the obtained black powder Co 3 O 4 and sodium hypophosphite ( 20 times the mass of Co 3 O 4 ) on the two ends of the porcelain boat at a distance of 5 cm. Heat up to 350°C for heat treatment, keep it at this temperature for 30 minutes, and then cool down to obtain the final product.
  • a method for preparing porous CoO/CoP nanotubes includes the following steps:
  • Step 2) Place the obtained black powder Co 3 O 4 and sodium hypophosphite ( 20 times the mass of Co 3 O 4 ) on the two ends of the porcelain boat at a distance of 5 cm. Heat up to 350°C for heat treatment, keep it at this temperature for 30 minutes, and then cool down to obtain the final product.
  • a method for preparing porous CoO/CoP nanotubes includes the following steps:
  • Step 2) Place the obtained black powder Co 3 O 4 and sodium hypophosphite ( 20 times the mass of Co 3 O 4 ) on the two ends of the porcelain boat at a distance of 5 cm. Heat up to 350°C for heat treatment, keep it at this temperature for 30 minutes, and then cool down to obtain the final product.
  • a method for preparing porous CoO/CoP nanotubes includes the following steps:
  • Step 2) Place the obtained black powder Co 3 O 4 and sodium hypophosphite ( 20 times the mass of Co 3 O 4 ) on the two ends of the porcelain boat at a distance of 5 cm. Heat up to 300°C for heat treatment, keep it at this temperature for 30 minutes, and then cool down to obtain the final product.
  • a method for preparing porous CoO/CoP nanotubes includes the following steps:
  • Step 2) The obtained black powder and Co 3 O 4 hypophosphite (mass of Co 3 O 20 4 times) porcelain boat was placed at both ends spaced 5cm, under an atmosphere of Ar / H 2, at 5 °C /min program the temperature to 350°C for heat treatment, and keep it at this temperature for 30 minutes, and then cool down to obtain the final product.
  • a method for preparing porous CoO/CoP nanotubes includes the following steps:
  • Step 2) Place the obtained black powder Co 3 O 4 and sodium hypophosphite ( 20 times the mass of Co 3 O 4 ) on the two ends of the porcelain boat at a distance of 5 cm. Heat up to 350°C for heat treatment, keep it at this temperature for 120 minutes, and then cool down to obtain the final product.
  • a method for preparing porous CoO/CoP nanotubes includes the following steps:
  • Step 2) Put the obtained black powder Co 3 O 4 and sodium hypophosphite ( 20 times the mass of Co 3 O 4 ) on the two ends of the porcelain boat at a distance of 5 cm, in an Ar atmosphere, with a program of 2°C/min Heat up to 350°C for heat treatment, keep it at this temperature for 30 minutes, and then cool down to obtain the final product.
  • the porous CoO/CoP nanotubes prepared in the above examples were physically characterized by TEM, SEM and XRD. From the TEM and SEM spectra ( Figure 1 and Figure 2), the linear structure of the prepared precursor can be seen.
  • Fig. 3 is the TEM and SEM spectra of the porous Co 3 O 4 nanotubes prepared according to the method of the present invention. From Fig. 3, the hollow tubular structure of Co 3 O 4 can be seen.
  • Figure 4 is the XRD pattern of the porous Co 3 O 4 nanotubes prepared according to the method of the present invention. It can be seen from Figure 4 that the diffraction peak of the catalyst can be consistent with the standard card of Co 3 O 4.
  • FIG. 5 is a TEM chart of the porous CoO/CoP nanotubes prepared according to the method of the present invention. From Fig. 5, the hollow tubular structure of the catalyst after phosphating can be seen, showing that CoO and CoP are uniformly distributed and the heterostructure interface permeates each other.
  • Figure 6 is the XRD pattern of the porous CoO/CoP nanotubes prepared according to the method of the present invention. It can be seen from Figure 6 that the diffraction peaks of the catalyst can be consistent with the standard cards of CoO and CoP.
  • the prepared porous CoO/CoP nanotubes were applied to the HER reaction, and the HER performance of pure-phase CoP was compared.
  • Figure 7 is the LSV spectrum of the HER of the porous CoO/CoP nanotubes and pure CoP prepared according to the method of the present invention. It can be seen from Figure 7 that at 10mA ⁇ cm -2 , the overpotential of the porous CoO/CoP nanotubes is 65mV, which is excellent The overpotential of pure phase CoP is 92mV.
  • Fig. 8 is a comparison chart of HER before and after 1000 cycles of the porous CoO/CoP nanotubes prepared according to the method of the present invention. Fig. 8 shows that the overpotential changes only slightly after the 1000 cycles of accelerated endurance stability test.

Abstract

Porous CoO/CoP nanotubes, a preparation method therefor, and the use thereof as a hydrogen evolution reaction catalyst. The present invention belongs to the technical field of Co-based nanotube materials. A cobalt salt as a metal source and aspartic acid as a complexing agent are subjected to a solvothermal reaction to prepare a cobalt-aspartic acid complex in advance, and same is then first subjected to calcination oxidation and then to a phosphorization treatment to obtain the porous CoO/CoP nanotubes. The porous CoO/CoP nanotubes are prepared by means of a self-sacrificing template process which is simple and can achieve large scale production, and the method has a simple and easily practicable process, is simple in operation and can achieve large scale production.

Description

一种多孔CoO/CoP纳米管及其制备方法和应用Porous CoO/CoP nanotube and preparation method and application thereof
本申请要求于2020年05月21日提交中国专利局、申请号为202010434540.6、发明名称为“一种多孔CoO/CoP纳米管及其制备方法和应用”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。This application claims the priority of a Chinese patent application filed with the Chinese Patent Office on May 21, 2020, the application number is 202010434540.6, and the invention title is "a porous CoO/CoP nanotube and its preparation method and application", and its entire content Incorporated in this application by reference.
技术领域Technical field
本发明涉及一种多孔CoO/CoP纳米管及其制备方法和其作为析氢反应催化剂的应用，属于Co基纳米管材料技术领域。The invention relates to a porous CoO/CoP nanotube, a preparation method thereof and its application as a hydrogen evolution reaction catalyst, and belongs to the technical field of Co-based nanotube materials.
背景技术Background technique
能源危机和环境污染是目前人类所必须面对的两大难题，开发新技术、新能源是解决这两个问题的关键，也是科研领域的研究热点，诸如太阳能、风能、生物质能等一系列新能源应运而生，其中氢能作为一种高效清洁的可再生能源，被认为是未来最具发展前景的新型能源载体。在众多制氢的方法中，电解水制氢因其高效、绿色、环保、原料丰富等优点脱颖而出，电解所需要的电能可由太阳能、风能等供给，因此，电解水制氢也是一种重要的能源转换与存储的手段。虽然贵金属铂族金属(PGMs)是最先进的电催化剂，但其稀缺性和高成本严重阻碍了其广泛的商业应用。目前，非贵金属催化剂的发展是当今重要的科学问题之一。非贵金属催化剂包括杂原子掺杂纳米碳、过渡金属硫族化合物、碳化物、氮化物、氧化物、磷酸盐等，其中过渡金属磷化物(TMPs)是高活性、低成本的催化剂的典型代表，有望替代贵金属用于电解水。但过渡金属磷化物电导率低，本征活性低，性能差，需要进一步提高其催化性能的策略，包括杂化复合，电子调控，设计纳米结构。开发高效、低成本的电催化剂是电解水的核心。Energy crisis and environmental pollution are two major problems that humans must face at present. The development of new technologies and new energy is the key to solving these two problems, and it is also a research hotspot in the field of scientific research, such as solar energy, wind energy, biomass energy, etc. New energy came into being, among which hydrogen energy, as a highly efficient and clean renewable energy, is considered to be the most promising new energy carrier in the future. Among the many methods of hydrogen production, hydrogen production by electrolysis of water stands out due to its high efficiency, green, environmental protection, and abundant raw materials. The electric energy required for electrolysis can be supplied by solar energy, wind energy, etc. Therefore, hydrogen production by electrolysis is also an important energy source. Means of conversion and storage. Although the precious metals platinum group metals (PGMs) are the most advanced electrocatalysts, their scarcity and high cost have severely hindered their widespread commercial applications. At present, the development of non-precious metal catalysts is one of the important scientific issues today. Non-precious metal catalysts include heteroatom-doped nano-carbon, transition metal chalcogenides, carbides, nitrides, oxides, phosphates, etc., among which transition metal phosphides (TMPs) are typical representatives of high-activity and low-cost catalysts. It is expected to replace precious metals for electrolysis of water. However, transition metal phosphides have low conductivity, low intrinsic activity, and poor performance. Strategies to further improve their catalytic performance are needed, including hybrid compounding, electronic control, and nanostructure design. The development of high-efficiency and low-cost electrocatalysts is the core of water electrolysis.
发明内容Summary of the invention
为解决上述技术问题，本发明提供了一种多孔CoO/CoP纳米管及其制备方法，以及该方法制得的多孔CoO/CoP纳米管作为电极催化材料在析氢反应方面的应用。本发明通过一种简易通用的自牺牲模板法制备钴- 天冬氨酸配合物前驱体，经过先氧化后磷化生成多孔CoO/CoP纳米管，表现出优异的HER(氢气析出反应)性能和稳定性。In order to solve the above technical problems, the present invention provides a porous CoO/CoP nanotube and a preparation method thereof, and the application of the porous CoO/CoP nanotube prepared by the method as an electrode catalytic material in the hydrogen evolution reaction. The present invention prepares the cobalt-aspartic acid complex precursor by a simple and universal self-sacrificing template method, and generates porous CoO/CoP nanotubes after first oxidation and then phosphating, showing excellent HER (hydrogen evolution reaction) performance and stability.
技术方案：为了达到上述发明目的，本发明所采用的技术方案如下：Technical solution: In order to achieve the above-mentioned purpose of the invention, the technical solution adopted by the present invention is as follows:
一种多孔CoO/CoP纳米管的制备方法，包括以钴盐为金属源，天冬氨酸为配位剂，通过溶剂热反应预先制备钴-天冬氨酸配合物，然后先将所述钴-天冬氨酸配合物煅烧氧化，再磷化处理，得到所述多孔CoO/CoP纳米管。A method for preparing porous CoO/CoP nanotubes includes using cobalt salt as a metal source and aspartic acid as a complexing agent, preparing a cobalt-aspartic acid complex in advance through a solvothermal reaction, and then removing the cobalt -The aspartic acid complex is calcined and oxidized, and then phosphatized to obtain the porous CoO/CoP nanotubes.
作为优选：As a preference:
所述钴盐选自Co(NO 3) 2和CoCl 2中的一种或两种。 The cobalt salt is selected from one or two of Co(NO 3 ) 2 and CoCl 2.
所述溶剂热反应，是将天冬氨酸、钴盐和氢氧化钠加入水和乙二醇的混合溶液中，混匀后，在140～200℃条件下进行溶剂热反应，反应时间4～10h。The solvothermal reaction is to add aspartic acid, cobalt salt and sodium hydroxide into a mixed solution of water and ethylene glycol, and after mixing, perform a solvothermal reaction at 140-200°C, the reaction time is 4~ 10h.
进一步优选，所述水和乙二醇的混合溶液中，水和乙二醇的体积比为(0.1～99)：1；所述天冬氨酸、钴盐和氢氧化钠的摩尔比为(0.01～1)：(0.01～1)：(0.01～1)。Further preferably, in the mixed solution of water and ethylene glycol, the volume ratio of water to ethylene glycol is (0.1-99):1; the molar ratio of aspartic acid, cobalt salt and sodium hydroxide is ( 0.01-1): (0.01-1): (0.01-1).
所述煅烧氧化，是将所述钴-天冬氨酸配合物在氧气气氛中，以程序升温的方式加热到300～400℃煅烧氧化，保持3～8h，进一步优选300℃煅烧氧化。The calcining and oxidation is to heat the cobalt-aspartic acid complex in an oxygen atmosphere to 300-400°C for calcining and oxidizing in a temperature-programmed manner, and keeping it for 3-8h, and more preferably 300°C for calcining and oxidizing.
进一步优选，所述程序升温的速率为0.5～10℃/min。Further preferably, the rate of the programmed temperature rise is 0.5-10°C/min.
所述磷化处理，是将煅烧氧化后产品与次亚磷酸钠在惰性气氛中，以程序升温的方式加热至300～350℃，保持20～80min，进行磷化。In the phosphating treatment, the calcined and oxidized product and sodium hypophosphite are heated to 300-350° C. in an inert atmosphere in a temperature-programmed manner, and maintained for 20-80 minutes to perform phosphating.
进一步优选，所述惰性气氛包括Ar、Ar/H 2和N 2中的至少一种；所述程序升温的速率为1～20℃/min。 Further preferably, the inert atmosphere includes at least one of Ar, Ar/H 2 and N 2 ; the rate of the programmed temperature rise is 1-20° C./min.
本发明还提供了上述方案所述制备方法制备的多孔CoO/CoP纳米管。The present invention also provides porous CoO/CoP nanotubes prepared by the preparation method described in the above scheme.
本发明另提供了所述的多孔CoO/CoP纳米管作为析氢反应催化剂的应用。The present invention also provides the application of the porous CoO/CoP nanotube as a hydrogen evolution reaction catalyst.
本发明所述制备方法中，以Co(NO 3) 2或CoCl 2为金属源，天冬氨酸(C 4H 7NO 4)为配位剂，预先制备粉色的钴-天冬氨酸配合物，在通过自牺牲模板法先氧化后磷化处理得到多孔CoO/CoP纳米管。所述多孔CoO/CoP 纳米管具有空心的管状结构，粗糙的管道表面具有丰富的孔道，CoO与CoP异质结构界面相互渗透。 In the preparation method of the present invention, Co(NO 3 ) 2 or CoCl 2 is used as a metal source, aspartic acid (C 4 H 7 NO 4 ) is used as a complexing agent, and a pink cobalt-aspartic acid complex is prepared in advance The material is first oxidized and then phosphatized by the self-sacrificial template method to obtain porous CoO/CoP nanotubes. The porous CoO/CoP nanotube has a hollow tubular structure, the rough pipe surface has abundant pores, and the CoO and CoP heterostructure interface permeates each other.
本发明制备的多孔CoO/CoP纳米管，具有以下几种优势：①空心管状结构具有丰富的暴露的可接近的活性位点，可以促进平面内的传质。②有机组***解时有效引入孔道，同时保留其独特的形貌，暴露出大的比表面积和丰富的活性位点，有助于气体和电解质的传输与扩散。③CoO与CoP分布均匀，异质结构界面相互渗透，具有强烈的协同作用，增强了导电性能和电子转移，促进了析氢反应。The porous CoO/CoP nanotube prepared by the present invention has the following advantages: ① The hollow tubular structure has abundant exposed and accessible active sites, which can promote mass transfer in the plane. ②The organic components are effectively introduced into the pores when cracking, while retaining its unique morphology, exposing a large specific surface area and abundant active sites, which is helpful for the transmission and diffusion of gas and electrolyte. ③CoO and CoP are uniformly distributed, and the heterostructure interface penetrates each other, which has a strong synergistic effect, enhances the conductivity and electron transfer, and promotes the hydrogen evolution reaction.
有益效果：相对于现有技术，本发明的优势在于：Beneficial effects: Compared with the prior art, the advantages of the present invention are:
本发明是一种新型的多孔CoO/CoP纳米管的制备方法，通过简便、可实现规模化生产的自牺牲模板法制备多孔CoO/CoP纳米管，该方法工艺简单易行、操作简单、可实现大规模生产；所制得的产物形貌规整，孔道丰富具有活性位点多、循环稳定性良好和花状结构等特点。与常规CoP材料相比，所制备的CoO/CoP纳米管，有强烈的协同作用，具备更为优异的结构特点和组分优势，是一种极有潜力的电解水催化材料，在未来的能源行业应用前景广阔。The present invention is a novel method for preparing porous CoO/CoP nanotubes. The porous CoO/CoP nanotubes are prepared by a simple, self-sacrificing template method that can realize large-scale production. The method has simple process, simple operation, and can be realized. Large-scale production; the prepared product has regular morphology, abundant pores, and features many active sites, good cycle stability, and flower-like structure. Compared with conventional CoP materials, the prepared CoO/CoP nanotubes have a strong synergistic effect, have more excellent structural characteristics and component advantages, and are a very potential electrolytic water catalytic material, which will be an energy source in the future. The industry application prospect is broad.
附图说明Description of the drawings
图1是根据本发明方法制备的线状钴-天冬氨酸配合物前驱体的TEM图谱；Figure 1 is a TEM chart of the linear cobalt-aspartic acid complex precursor prepared according to the method of the present invention;
图2是根据本发明方法制备的线状钴-天冬氨酸配合物前驱体的SEM图谱；Figure 2 is a SEM chart of the linear cobalt-aspartic acid complex precursor prepared according to the method of the present invention;
图3是根据本发明方法制备的多孔Co 3O 4纳米管的TEM和SEM图谱； Figure 3 is the TEM and SEM spectra of porous Co 3 O 4 nanotubes prepared according to the method of the present invention;
图4是根据本发明方法制备的多孔Co 3O 4纳米管的XRD图谱； Figure 4 is an XRD pattern of porous Co 3 O 4 nanotubes prepared according to the method of the present invention;
图5是根据本发明方法制备的多孔CoO/CoP纳米管的TEM图谱；Figure 5 is a TEM chart of porous CoO/CoP nanotubes prepared according to the method of the present invention;
图6是根据本发明方法制备的多孔CoO/CoP纳米管的XRD图谱；Figure 6 is an XRD pattern of porous CoO/CoP nanotubes prepared according to the method of the present invention;
图7是根据本发明方法制备的多孔CoO/CoP纳米管与纯相CoP的HER的LSV图谱；Fig. 7 is a HER LSV spectrum of porous CoO/CoP nanotubes and pure CoP prepared according to the method of the present invention;
图8是根据本发明方法制备的多孔CoO/CoP纳米管的循环1000圈前 后的HER对比图谱。Fig. 8 is a comparison chart of HER before and after 1000 cycles of porous CoO/CoP nanotubes prepared according to the method of the present invention.
具体实施方式Detailed ways
下面通过具体实施例对本发明所述的技术方案给予进一步详细的说明。The technical solutions of the present invention will be further described in detail below through specific embodiments.
实施例1Example 1
一种多孔CoO/CoP纳米管的制备方法，包括以下步骤:A method for preparing porous CoO/CoP nanotubes includes the following steps:
1)合成线状钴-天冬氨酸配合物：配制混合溶液(水：乙二醇体积比＝1:1)，3mmol天冬氨酸、3mmol Co(NO 3) 2和3mmolNaOH加入至溶于36mL混合溶液，搅拌至粉色，转移至反应釜，180℃反应5h。离心真空干燥得到粉色粉末，即线状钴-天冬氨酸配合物； 1) Synthesis of linear cobalt-aspartic acid complex: prepare a mixed solution (water: ethylene glycol volume ratio = 1:1), 3mmol aspartic acid, 3mmol Co(NO 3 ) 2 and 3mmol NaOH are added to the solution 36mL of the mixed solution, stirred to pink, transferred to the reactor, and reacted at 180°C for 5h. Centrifugal vacuum drying to obtain pink powder, namely linear cobalt-aspartic acid complex;
2)制备多孔CoO/CoP纳米管：将步骤1)制得的粉色粉末，在氧气气氛下，以0.5℃/min程序升温至300℃进行热处理，并在该温度下保持4h；2) Preparation of porous CoO/CoP nanotubes: heat the pink powder prepared in step 1) at a program temperature of 0.5°C/min to 300°C in an oxygen atmosphere, and keep it at this temperature for 4h;
3)步骤2)将得到的黑色粉末Co 3O 4与次亚磷酸钠(质量为Co 3O 4的20倍)置于瓷舟两端相隔5cm，在Ar气氛下，以5℃/min程序升温至350℃进行热处理，并在该温度下保持30min，然后冷却，即可得到最终产物。 3) Step 2) Place the obtained black powder Co 3 O 4 and sodium hypophosphite ( 20 times the mass of Co 3 O 4 ) on the two ends of the porcelain boat at a distance of 5 cm. Heat up to 350°C for heat treatment, keep it at this temperature for 30 minutes, and then cool down to obtain the final product.
实施例2Example 2
一种多孔CoO/CoP纳米管的制备方法，包括以下步骤:A method for preparing porous CoO/CoP nanotubes includes the following steps:
1)合成线状钴-天冬氨酸配合物：配制混合溶液(水：乙二醇体积比＝1:1)，3mmol天冬氨酸、3mmol Co(NO 3) 2和6mmolNaOH加入至溶于36mL混合溶液，搅拌至粉色，转移至反应釜，180℃反应5h。离心真空干燥得到粉色粉末，即线状钴-天冬氨酸配合物； 1) Synthesis of linear cobalt-aspartic acid complex: prepare a mixed solution (water: ethylene glycol volume ratio = 1:1), 3mmol aspartic acid, 3mmol Co(NO 3 ) 2 and 6mmol NaOH are added to the solution 36mL of the mixed solution, stirred to pink, transferred to the reactor, and reacted at 180°C for 5h. Centrifugal vacuum drying to obtain pink powder, namely linear cobalt-aspartic acid complex;
2)制备多孔CoO/CoP纳米管：将步骤1)制得的粉色粉末，在氧气气氛下，以0.5℃/min程序升温至300℃进行热处理，并在该温度下保持4h。2) Preparation of porous CoO/CoP nanotubes: heat the pink powder prepared in step 1) at a program temperature of 0.5°C/min to 300°C in an oxygen atmosphere, and keep the powder at this temperature for 4h.
3)步骤2)将得到的黑色粉末Co 3O 4与次亚磷酸钠(质量为Co 3O 4的20倍)置于瓷舟两端相隔5cm，在Ar气氛下，以5℃/min程序升温至350℃进行热处理，并在该温度下保持30min，然后冷却，即可得到最终产物。 3) Step 2) Place the obtained black powder Co 3 O 4 and sodium hypophosphite ( 20 times the mass of Co 3 O 4 ) on the two ends of the porcelain boat at a distance of 5 cm. Heat up to 350°C for heat treatment, keep it at this temperature for 30 minutes, and then cool down to obtain the final product.
实施例3Example 3
一种多孔CoO/CoP纳米管的制备方法，包括以下步骤:A method for preparing porous CoO/CoP nanotubes includes the following steps:
1)合成线状钴-天冬氨酸配合物：配制混合溶液(水：乙二醇体积比＝ 1:1)，3mmol天冬氨酸、3mmol Co(NO 3) 2和1mmolNaOH加入至溶于36mL混合溶液，搅拌至粉色，转移至反应釜，180℃反应5h。离心真空干燥得到粉色粉末，即线状钴-天冬氨酸配合物； 1) Synthesis of linear cobalt-aspartic acid complex: prepare a mixed solution (water: ethylene glycol volume ratio = 1:1), 3mmol aspartic acid, 3mmol Co(NO 3 ) 2 and 1mmol NaOH are added to the solution 36mL of the mixed solution, stirred to pink, transferred to the reactor, and reacted at 180°C for 5h. Centrifugal vacuum drying to obtain pink powder, namely linear cobalt-aspartic acid complex;
2)制备多孔CoO/CoP纳米管：将步骤1)制得的粉色粉末，在氧气气氛下，以0.5℃/min程序升温至300℃进行热处理，并在该温度下保持4h；2) Preparation of porous CoO/CoP nanotubes: heat the pink powder prepared in step 1) at a program temperature of 0.5°C/min to 300°C in an oxygen atmosphere, and keep it at this temperature for 4h;
3)步骤2)将得到的黑色粉末Co 3O 4与次亚磷酸钠(质量为Co 3O 4的20倍)置于瓷舟两端相隔5cm，在Ar气氛下，以5℃/min程序升温至350℃进行热处理，并在该温度下保持30min，然后冷却，即可得到最终产物。 3) Step 2) Place the obtained black powder Co 3 O 4 and sodium hypophosphite ( 20 times the mass of Co 3 O 4 ) on the two ends of the porcelain boat at a distance of 5 cm. Heat up to 350°C for heat treatment, keep it at this temperature for 30 minutes, and then cool down to obtain the final product.
实施例4Example 4
一种多孔CoO/CoP纳米管的制备方法，包括以下步骤:A method for preparing porous CoO/CoP nanotubes includes the following steps:
1)合成线状钴-天冬氨酸配合物：配制混合溶液(水：乙二醇体积比＝1:1)，3mmol天冬氨酸、3mmol Co(NO 3) 2和3mmolNaOH加入至溶于36mL混合溶液，搅拌至粉色，转移至反应釜，140℃反应5h。离心真空干燥得到粉色粉末，即线状钴-天冬氨酸配合物； 1) Synthesis of linear cobalt-aspartic acid complex: prepare a mixed solution (water: ethylene glycol volume ratio = 1:1), 3mmol aspartic acid, 3mmol Co(NO 3 ) 2 and 3mmol NaOH are added to the solution 36mL of the mixed solution, stirred until it was pink, transferred to the reactor, and reacted at 140°C for 5h. Centrifugal vacuum drying to obtain pink powder, namely linear cobalt-aspartic acid complex;
2)制备多孔CoO/CoP纳米管：将步骤1)制得的粉色粉末，在氧气气氛下，以0.5℃/min程序升温至300℃进行热处理，并在该温度下保持4h；2) Preparation of porous CoO/CoP nanotubes: heat the pink powder prepared in step 1) at a program temperature of 0.5°C/min to 300°C in an oxygen atmosphere, and keep it at this temperature for 4h;
3)步骤2)将得到的黑色粉末Co 3O 4与次亚磷酸钠(质量为Co 3O 4的20倍)置于瓷舟两端相隔5cm，在Ar气氛下，以5℃/min程序升温至350℃进行热处理，并在该温度下保持30min，然后冷却，即可得到最终产物。 3) Step 2) Place the obtained black powder Co 3 O 4 and sodium hypophosphite ( 20 times the mass of Co 3 O 4 ) on the two ends of the porcelain boat at a distance of 5 cm. Heat up to 350°C for heat treatment, keep it at this temperature for 30 minutes, and then cool down to obtain the final product.
实施例5Example 5
一种多孔CoO/CoP纳米管的制备方法，包括以下步骤:A method for preparing porous CoO/CoP nanotubes includes the following steps:
1)合成线状钴-天冬氨酸配合物：配制混合溶液(水：乙二醇体积比＝1:1)，3mmol天冬氨酸、3mmol Co(NO 3) 2和3mmolNaOH加入至溶于36mL混合溶液，搅拌至粉色，转移至反应釜，180℃反应12h。离心真空干燥得到粉色粉末，即线状钴-天冬氨酸配合物； 1) Synthesis of linear cobalt-aspartic acid complex: prepare a mixed solution (water: ethylene glycol volume ratio = 1:1), 3mmol aspartic acid, 3mmol Co(NO 3 ) 2 and 3mmol NaOH are added to the solution 36mL of the mixed solution, stirred to pink, transferred to the reactor, and reacted at 180°C for 12h. Centrifugal vacuum drying to obtain pink powder, namely linear cobalt-aspartic acid complex;
2)制备多孔CoO/CoP纳米管：将步骤1)制得的粉色粉末，在氧气气氛下，以0.5℃/min程序升温至300℃进行热处理，并在该温度下保持4h；2) Preparation of porous CoO/CoP nanotubes: heat the pink powder prepared in step 1) at a program temperature of 0.5°C/min to 300°C in an oxygen atmosphere, and keep it at this temperature for 4h;
3)步骤2)将得到的黑色粉末Co 3O 4与次亚磷酸钠(质量为Co 3O 4的20倍)置于瓷舟两端相隔5cm，在Ar气氛下，以5℃/min程序升温至350℃进行热处理，并在该温度下保持30min，然后冷却，即可得到最终产物。 3) Step 2) Place the obtained black powder Co 3 O 4 and sodium hypophosphite ( 20 times the mass of Co 3 O 4 ) on the two ends of the porcelain boat at a distance of 5 cm. Heat up to 350°C for heat treatment, keep it at this temperature for 30 minutes, and then cool down to obtain the final product.
实施例6Example 6
一种多孔CoO/CoP纳米管的制备方法，包括以下步骤:A method for preparing porous CoO/CoP nanotubes includes the following steps:
1)合成线状钴-天冬氨酸配合物：配制混合溶液(水：乙二醇体积比＝2:1)，3mmol天冬氨酸、3mmol Co(NO 3) 2和3mmolNaOH加入至溶于36mL混合溶液，搅拌至粉色，转移至反应釜，180℃反应5h。离心真空干燥得到粉色粉末，即线状钴-天冬氨酸配合物； 1) Synthesis of linear cobalt-aspartic acid complex: prepare a mixed solution (water: ethylene glycol volume ratio = 2:1), 3mmol aspartic acid, 3mmol Co(NO 3 ) 2 and 3mmol NaOH are added to the solution 36mL of the mixed solution, stirred to pink, transferred to the reactor, and reacted at 180°C for 5h. Centrifugal vacuum drying to obtain pink powder, namely linear cobalt-aspartic acid complex;
2)制备多孔CoO/CoP纳米管：将步骤1)制得的粉色粉末，在氧气气氛下，以0.5℃/min程序升温至300℃进行热处理，并在该温度下保持4h；2) Preparation of porous CoO/CoP nanotubes: heat the pink powder prepared in step 1) at a program temperature of 0.5°C/min to 300°C in an oxygen atmosphere, and keep it at this temperature for 4h;
3)步骤2)将得到的黑色粉末Co 3O 4与次亚磷酸钠(质量为Co 3O 4的20倍)置于瓷舟两端相隔5cm，在Ar气氛下，以5℃/min程序升温至350℃进行热处理，并在该温度下保持30min，然后冷却，即可得到最终产物。 3) Step 2) Place the obtained black powder Co 3 O 4 and sodium hypophosphite ( 20 times the mass of Co 3 O 4 ) on the two ends of the porcelain boat at a distance of 5 cm. Heat up to 350°C for heat treatment, keep it at this temperature for 30 minutes, and then cool down to obtain the final product.
实施例7Example 7
一种多孔CoO/CoP纳米管的制备方法，包括以下步骤:A method for preparing porous CoO/CoP nanotubes includes the following steps:
1)合成线状钴-天冬氨酸配合物：配制混合溶液(水：乙二醇体积比＝2:1)，3mmol天冬氨酸、3mmol Co(NO 3) 2和3mmolNaOH加入至溶于36mL混合溶液，搅拌至粉色，转移至反应釜，180℃反应5h。离心真空干燥得到粉色粉末，即线状钴-天冬氨酸配合物； 1) Synthesis of linear cobalt-aspartic acid complex: prepare a mixed solution (water: ethylene glycol volume ratio = 2:1), 3mmol aspartic acid, 3mmol Co(NO 3 ) 2 and 3mmol NaOH are added to the solution 36mL of the mixed solution, stirred to pink, transferred to the reactor, and reacted at 180°C for 5h. Centrifugal vacuum drying to obtain pink powder, namely linear cobalt-aspartic acid complex;
2)制备多孔CoO/CoP纳米管：将步骤1)制得的粉色粉末，在氧气气氛下，以0.5℃/min程序升温至300℃进行热处理，并在该温度下保持4h；2) Preparation of porous CoO/CoP nanotubes: heat the pink powder prepared in step 1) at a program temperature of 0.5°C/min to 300°C in an oxygen atmosphere, and keep it at this temperature for 4h;
3)步骤2)将得到的黑色粉末Co 3O 4与次亚磷酸钠(质量为Co 3O 4的20倍)置于瓷舟两端相隔5cm，在Ar气氛下，以5℃/min程序升温至350℃进行热处理，并在该温度下保持30min，然后冷却，即可得到最终产物。 3) Step 2) Place the obtained black powder Co 3 O 4 and sodium hypophosphite ( 20 times the mass of Co 3 O 4 ) on the two ends of the porcelain boat at a distance of 5 cm. Heat up to 350°C for heat treatment, keep it at this temperature for 30 minutes, and then cool down to obtain the final product.
实施例8Example 8
一种多孔CoO/CoP纳米管的制备方法，包括以下步骤:A method for preparing porous CoO/CoP nanotubes includes the following steps:
1)合成线状钴-天冬氨酸配合物：配制混合溶液(水：乙二醇体积比＝1:1)，3mmol天冬氨酸、3mmol Co(NO 3) 2和3mmolNaOH加入至溶于36mL混合溶液，搅拌至粉色，转移至反应釜，180℃反应5h。离心真空干燥得到粉色粉末，即线状钴-天冬氨酸配合物； 1) Synthesis of linear cobalt-aspartic acid complex: prepare a mixed solution (water: ethylene glycol volume ratio = 1:1), 3mmol aspartic acid, 3mmol Co(NO 3 ) 2 and 3mmol NaOH are added to the solution 36mL of the mixed solution, stirred to pink, transferred to the reactor, and reacted at 180°C for 5h. Centrifugal vacuum drying to obtain pink powder, namely linear cobalt-aspartic acid complex;
2)制备多孔CoO/CoP纳米管：将步骤1)制得的粉色粉末，在氧气气氛下，以5℃/min程序升温至300℃进行热处理，并在该温度下保持4h；2) Preparation of porous CoO/CoP nanotubes: heat the pink powder prepared in step 1) at a program temperature of 5°C/min to 300°C in an oxygen atmosphere, and keep it at this temperature for 4h;
3)步骤2)将得到的黑色粉末Co 3O 4与次亚磷酸钠(质量为Co 3O 4的20倍)置于瓷舟两端相隔5cm，在Ar气氛下，以5℃/min程序升温至350℃进行热处理，并在该温度下保持30min，然后冷却，即可得到最终产物。 3) Step 2) Place the obtained black powder Co 3 O 4 and sodium hypophosphite ( 20 times the mass of Co 3 O 4 ) on the two ends of the porcelain boat at a distance of 5 cm. Heat up to 350°C for heat treatment, keep it at this temperature for 30 minutes, and then cool down to obtain the final product.
实施例9Example 9
一种多孔CoO/CoP纳米管的制备方法，包括以下步骤:A method for preparing porous CoO/CoP nanotubes includes the following steps:
1)合成线状钴-天冬氨酸配合物：配制混合溶液(水：乙二醇体积比＝1:1)，3mmol天冬氨酸、3mmol Co(NO 3) 2和3mmolNaOH加入至溶于36mL混合溶液，搅拌至粉色，转移至反应釜，180℃反应5h。离心真空干燥得到粉色粉末，即线状钴-天冬氨酸配合物； 1) Synthesis of linear cobalt-aspartic acid complex: prepare a mixed solution (water: ethylene glycol volume ratio = 1:1), 3mmol aspartic acid, 3mmol Co(NO 3 ) 2 and 3mmol NaOH are added to the solution 36mL of the mixed solution, stirred to pink, transferred to the reactor, and reacted at 180°C for 5h. Centrifugal vacuum drying to obtain pink powder, namely linear cobalt-aspartic acid complex;
2)制备多孔CoO/CoP纳米管：将步骤1)制得的粉色粉末，在氧气气氛下，以0.5℃/min程序升温至300℃进行热处理，并在该温度下保持4h；2) Preparation of porous CoO/CoP nanotubes: heat the pink powder prepared in step 1) at a program temperature of 0.5°C/min to 300°C in an oxygen atmosphere, and keep it at this temperature for 4h;
3)步骤2)将得到的黑色粉末Co 3O 4与次亚磷酸钠(质量为Co 3O 4的20倍)置于瓷舟两端相隔5cm，在Ar气氛下，以5℃/min程序升温至300℃进行热处理，并在该温度下保持30min，然后冷却，即可得到最终产物。 3) Step 2) Place the obtained black powder Co 3 O 4 and sodium hypophosphite ( 20 times the mass of Co 3 O 4 ) on the two ends of the porcelain boat at a distance of 5 cm. Heat up to 300°C for heat treatment, keep it at this temperature for 30 minutes, and then cool down to obtain the final product.
实施例10Example 10
一种多孔CoO/CoP纳米管的制备方法，包括以下步骤:A method for preparing porous CoO/CoP nanotubes includes the following steps:
1)合成线状钴-天冬氨酸配合物：配制混合溶液(水：乙二醇体积比＝1:1)，3mmol天冬氨酸、3mmol Co(NO 3) 2和3mmolNaOH加入至溶于36mL混合溶液，搅拌至粉色，转移至反应釜，180℃反应5h。离心真空干燥得到粉色粉末，即线状钴-天冬氨酸配合物； 1) Synthesis of linear cobalt-aspartic acid complex: prepare a mixed solution (water: ethylene glycol volume ratio = 1:1), 3mmol aspartic acid, 3mmol Co(NO 3 ) 2 and 3mmol NaOH are added to the solution 36mL of the mixed solution, stirred to pink, transferred to the reactor, and reacted at 180°C for 5h. Centrifugal vacuum drying to obtain pink powder, namely linear cobalt-aspartic acid complex;
2)制备多孔CoO/CoP纳米管：将步骤1)制得的粉色粉末，在氧气气氛下，以0.5℃/min程序升温至300℃进行热处理，并在该温度下保持4h；2) Preparation of porous CoO/CoP nanotubes: heat the pink powder prepared in step 1) at a program temperature of 0.5°C/min to 300°C in an oxygen atmosphere, and keep it at this temperature for 4h;
3)步骤2)将得到的黑色粉末Co 3O 4与次亚磷酸钠(质量为Co 3O 4的20倍)置于瓷舟两端相隔5cm，在Ar/H 2气氛下，以5℃/min程序升温至350℃进行热处理，并在该温度下保持30min，然后冷却，即可得到最终产物。 3) Step 2) The obtained black powder and Co 3 O 4 hypophosphite (mass of Co 3 O 20 4 times) porcelain boat was placed at both ends spaced 5cm, under an atmosphere of Ar / H 2, at 5 ℃ /min program the temperature to 350°C for heat treatment, and keep it at this temperature for 30 minutes, and then cool down to obtain the final product.
实施例11Example 11
一种多孔CoO/CoP纳米管的制备方法，包括以下步骤:A method for preparing porous CoO/CoP nanotubes includes the following steps:
1)合成线状钴-天冬氨酸配合物：配制混合溶液(水：乙二醇体积比＝1:1)，3mmol天冬氨酸、3mmol Co(NO 3) 2和3mmolNaOH加入至溶于36mL混合溶液，搅拌至粉色，转移至反应釜，180℃反应5h。离心真空干燥得 到粉色粉末，即线状钴-天冬氨酸配合物； 1) Synthesis of linear cobalt-aspartic acid complex: prepare a mixed solution (water: ethylene glycol volume ratio = 1:1), 3mmol aspartic acid, 3mmol Co(NO 3 ) 2 and 3mmol NaOH are added to the solution 36mL of the mixed solution, stirred to pink, transferred to the reactor, and reacted at 180°C for 5h. Centrifugal vacuum drying to obtain pink powder, namely linear cobalt-aspartic acid complex;
2)制备多孔CoO/CoP纳米管：将步骤1)制得的粉色粉末，在氧气气氛下，以0.5℃/min程序升温至300℃进行热处理，并在该温度下保持4h；2) Preparation of porous CoO/CoP nanotubes: heat the pink powder prepared in step 1) at a program temperature of 0.5°C/min to 300°C in an oxygen atmosphere, and keep it at this temperature for 4h;
3)步骤2)将得到的黑色粉末Co 3O 4与次亚磷酸钠(质量为Co 3O 4的20倍)置于瓷舟两端相隔5cm，在Ar气氛下，以5℃/min程序升温至350℃进行热处理，并在该温度下保持120min，然后冷却，即可得到最终产物。 3) Step 2) Place the obtained black powder Co 3 O 4 and sodium hypophosphite ( 20 times the mass of Co 3 O 4 ) on the two ends of the porcelain boat at a distance of 5 cm. Heat up to 350°C for heat treatment, keep it at this temperature for 120 minutes, and then cool down to obtain the final product.
实施例12Example 12
一种多孔CoO/CoP纳米管的制备方法，包括以下步骤:A method for preparing porous CoO/CoP nanotubes includes the following steps:
1)合成线状钴-天冬氨酸配合物：配制混合溶液(水：乙二醇体积比＝1:1)，3mmol天冬氨酸、3mmol Co(NO 3) 2和3mmolNaOH加入至溶于36mL混合溶液，搅拌至粉色，转移至反应釜，180℃反应5h。离心真空干燥得到粉色粉末，即线状钴-天冬氨酸配合物； 1) Synthesis of linear cobalt-aspartic acid complex: prepare a mixed solution (water: ethylene glycol volume ratio = 1:1), 3mmol aspartic acid, 3mmol Co(NO 3 ) 2 and 3mmol NaOH are added to the solution 36mL of the mixed solution, stirred to pink, transferred to the reactor, and reacted at 180°C for 5h. Centrifugal vacuum drying to obtain pink powder, namely linear cobalt-aspartic acid complex;
2)制备多孔CoO/CoP纳米管：将步骤1)制得的粉色粉末，在氧气气氛下，以0.5℃/min程序升温至300℃进行热处理，并在该温度下保持4h；2) Preparation of porous CoO/CoP nanotubes: heat the pink powder prepared in step 1) at a program temperature of 0.5°C/min to 300°C in an oxygen atmosphere, and keep it at this temperature for 4h;
3)步骤2)将得到的黑色粉末Co 3O 4与次亚磷酸钠(质量为Co 3O 4的20倍)置于瓷舟两端相隔5cm，在Ar气氛下，以2℃/min程序升温至350℃进行热处理，并在该温度下保持30min，然后冷却，即可得到最终产物。 3) Step 2) Put the obtained black powder Co 3 O 4 and sodium hypophosphite ( 20 times the mass of Co 3 O 4 ) on the two ends of the porcelain boat at a distance of 5 cm, in an Ar atmosphere, with a program of 2°C/min Heat up to 350°C for heat treatment, keep it at this temperature for 30 minutes, and then cool down to obtain the final product.
采用TEM、SEM和XRD等途径对以上实施例制备的多孔CoO/CoP纳米管进行物理表征。从TEM、SEM图谱(图1和图2)，可以看出所制备前驱体的线状结构。图3是根据本发明方法制备的多孔Co 3O 4纳米管的TEM和SEM图谱，从图3可以看出Co 3O 4的空心管状结构。图4是根据本发明方法制备的多孔Co 3O 4纳米管的XRD图谱，由图4可以看出，催化剂的衍射峰可与Co 3O 4的标准卡片吻合。图5是根据本发明方法制备的多孔CoO/CoP纳米管的TEM图谱，从图5可以看出磷化后催化剂的空心管状结构，显示CoO和CoP分布均匀异质结构界面相互渗透。图6是根据本发明方法制备的多孔CoO/CoP纳米管的XRD图谱，由图6可以看出，催化剂的衍射峰可与CoO和CoP的标准卡片吻合。最后，以商业化20％Pt/C为参照催化剂，将所制备的多孔CoO/CoP纳米管应用在HER反应上，并与纯相CoP的HER性能进行对比。图7是根据本发明方法制备的多孔CoO/CoP纳米管与纯相CoP的HER的LSV图谱，由图7可知， 在10mA·cm -2处，多孔CoO/CoP纳米管过电势为65mV，优于纯相CoP的过电势92mV。图8是根据本发明方法制备的多孔CoO/CoP纳米管的循环1000圈前后的HER对比图谱，图8表明，经过1000圈的加速耐久力稳定性测试后过电位仅稍有改变。 The porous CoO/CoP nanotubes prepared in the above examples were physically characterized by TEM, SEM and XRD. From the TEM and SEM spectra (Figure 1 and Figure 2), the linear structure of the prepared precursor can be seen. Fig. 3 is the TEM and SEM spectra of the porous Co 3 O 4 nanotubes prepared according to the method of the present invention. From Fig. 3, the hollow tubular structure of Co 3 O 4 can be seen. Figure 4 is the XRD pattern of the porous Co 3 O 4 nanotubes prepared according to the method of the present invention. It can be seen from Figure 4 that the diffraction peak of the catalyst can be consistent with the standard card of Co 3 O 4. Fig. 5 is a TEM chart of the porous CoO/CoP nanotubes prepared according to the method of the present invention. From Fig. 5, the hollow tubular structure of the catalyst after phosphating can be seen, showing that CoO and CoP are uniformly distributed and the heterostructure interface permeates each other. Figure 6 is the XRD pattern of the porous CoO/CoP nanotubes prepared according to the method of the present invention. It can be seen from Figure 6 that the diffraction peaks of the catalyst can be consistent with the standard cards of CoO and CoP. Finally, using the commercialized 20% Pt/C as a reference catalyst, the prepared porous CoO/CoP nanotubes were applied to the HER reaction, and the HER performance of pure-phase CoP was compared. Figure 7 is the LSV spectrum of the HER of the porous CoO/CoP nanotubes and pure CoP prepared according to the method of the present invention. It can be seen from Figure 7 that at 10mA·cm -2 , the overpotential of the porous CoO/CoP nanotubes is 65mV, which is excellent The overpotential of pure phase CoP is 92mV. Fig. 8 is a comparison chart of HER before and after 1000 cycles of the porous CoO/CoP nanotubes prepared according to the method of the present invention. Fig. 8 shows that the overpotential changes only slightly after the 1000 cycles of accelerated endurance stability test.
以上实施例的说明只是用于帮助理解本发明的方法及其核心思想。应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以对本发明进行若干改进和修饰，这些改进和修饰也落入本发明权利要求的保护范围内。对这些实施例的多种修改对本领域的专业技术人员来说是显而易见的，本文中所定义的一般原理可以在不脱离本发明的精神或范围的情况下在其它实施例中实现。因此，本发明将不会被限制于本文所示的这些实施例，而是要符合与本文所公开的原理和新颖特点相一致的最宽的范围。The description of the above embodiments is only used to help understand the method and the core idea of the present invention. It should be pointed out that for those of ordinary skill in the art, without departing from the principle of the present invention, several improvements and modifications can be made to the present invention, and these improvements and modifications also fall within the protection scope of the claims of the present invention. Various modifications to these embodiments are obvious to those skilled in the art, and the general principles defined herein can be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention will not be limited to the embodiments shown in this document, but should conform to the widest scope consistent with the principles and novel features disclosed in this document.

Claims (12)

  1. 一种多孔CoO/CoP纳米管的制备方法，其特征在于，包括：以钴盐为金属源，天冬氨酸为配位剂，通过溶剂热反应预先制备钴-天冬氨酸配合物，然后先将所述钴-天冬氨酸配合物煅烧氧化，再磷化处理，得到所述多孔CoO/CoP纳米管。A method for preparing porous CoO/CoP nanotubes, which is characterized in that it comprises: using cobalt salt as a metal source and aspartic acid as a complexing agent, pre-preparing a cobalt-aspartic acid complex through a solvothermal reaction, and then The cobalt-aspartic acid complex is first calcined and oxidized, and then phosphatized to obtain the porous CoO/CoP nanotubes.
  2. 根据权利要求1所述的多孔CoO/CoP纳米管的制备方法，其特征在于，所述钴盐选自Co(NO 3) 2和CoCl 2中的一种或两种。 The method for preparing porous CoO/CoP nanotubes according to claim 1, wherein the cobalt salt is selected from one or two of Co(NO 3 ) 2 and CoCl 2.
  3. 根据权利要求1所述的多孔CoO/CoP纳米管的制备方法，其特征在于，所述溶剂热反应，是将天冬氨酸、钴盐和氢氧化钠加入水和乙二醇的混合溶液中，混匀后，在140～200℃条件下进行溶剂热反应，反应时间4～10h。The method for preparing porous CoO/CoP nanotubes according to claim 1, wherein the solvothermal reaction involves adding aspartic acid, cobalt salt and sodium hydroxide into a mixed solution of water and ethylene glycol After mixing, solvothermal reaction is carried out at 140～200℃, and the reaction time is 4～10h.
  4. 根据权利要求3所述的多孔CoO/CoP纳米管的制备方法，其特征在于，所述水和乙二醇的混合溶液中，水和乙二醇的体积比为(0.1～99)：1；所述天冬氨酸、钴盐和氢氧化钠的摩尔比为(0.01～1)：(0.01～1)：(0.01～1)。The method for preparing porous CoO/CoP nanotubes according to claim 3, wherein in the mixed solution of water and ethylene glycol, the volume ratio of water to ethylene glycol is (0.1-99):1; The molar ratio of the aspartic acid, cobalt salt and sodium hydroxide is (0.01-1): (0.01-1): (0.01-1).
  5. 根据权利要求4所述的多孔CoO/CoP纳米管的制备方法，其特征在于，所述天冬氨酸与水和乙二醇的混合溶液的用量比为3mmol:36mL。The method for preparing porous CoO/CoP nanotubes according to claim 4, wherein the dosage ratio of the mixed solution of aspartic acid, water and ethylene glycol is 3mmol:36mL.
  6. 根据权利要求1所述的多孔CoO/CoP纳米管的制备方法，其特征在于，所述煅烧氧化，是将所述钴-天冬氨酸配合物在氧气气氛中，以程序升温的方式加热到300～400℃，保持3～8h，进行煅烧氧化。The method for preparing porous CoO/CoP nanotubes according to claim 1, wherein the calcining and oxidation is to heat the cobalt-aspartic acid complex in an oxygen atmosphere in a temperature-programmed manner. 300～400℃, keep for 3～8h for calcining and oxidation.
  7. 根据权利要求6所述的多孔CoO/CoP纳米管的制备方法，其特征在于，所述程序升温的速率为0.5～10℃/min。The method for preparing porous CoO/CoP nanotubes according to claim 6, wherein the rate of the temperature program is 0.5-10°C/min.
  8. 根据权利要求1所述的多孔CoO/CoP纳米管的制备方法，其特征在于，所述磷化处理，是将煅烧氧化后产品与次亚磷酸钠在惰性气氛中，以程序升温的方式加热至300～350℃，保持20～80min，进行磷化。The method for preparing porous CoO/CoP nanotubes according to claim 1, wherein the phosphating treatment is to heat the calcined and oxidized product with sodium hypophosphite in an inert atmosphere in a temperature-programmed manner. 300～350℃, keep for 20～80min, phosphating.
  9. 根据权利要求8所述的多孔CoO/CoP纳米管的制备方法，其特征在于，所述惰性气氛包括Ar、Ar/H 2和N 2中的至少一种；所述程序升温的速率为1～20℃/min。 The method for preparing porous CoO/CoP nanotubes according to claim 8, wherein the inert atmosphere includes at least one of Ar, Ar/H 2 and N 2 ; the rate of the programmed temperature rise is 1~ 20°C/min.
  10. 根据权利要求8所述的多孔CoO/CoP纳米管的制备方法，其特征在于，所述煅烧氧化后产品与次亚磷酸钠的质量比为1:20。The method for preparing porous CoO/CoP nanotubes according to claim 8, wherein the mass ratio of the calcined and oxidized product to sodium hypophosphite is 1:20.
  11. 一种由权利要求1～10任一项所述的制备方法制备的多孔CoO/CoP纳米管。A porous CoO/CoP nanotube prepared by the preparation method of any one of claims 1-10.
  12. 权利要求11所述的多孔CoO/CoP纳米管作为析氢反应催化剂的应用。The use of the porous CoO/CoP nanotubes of claim 11 as a catalyst for hydrogen evolution reaction.
PCT/CN2020/134252 2020-05-21 2020-12-07 Porous coo/cop nanotubes, preparation method therefor and use thereof WO2021232751A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202010434540.6A CN111437846B (en) 2020-05-21 2020-05-21 Porous CoO/CoP nanotube and preparation method and application thereof
CN202010434540.6 2020-05-21

Publications (1)

Publication Number Publication Date
WO2021232751A1 true WO2021232751A1 (en) 2021-11-25

Family

ID=71657119

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2020/134252 WO2021232751A1 (en) 2020-05-21 2020-12-07 Porous coo/cop nanotubes, preparation method therefor and use thereof

Country Status (2)

Country Link
CN (1) CN111437846B (en)
WO (1) WO2021232751A1 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114558597A (en) * 2022-04-02 2022-05-31 合肥工业大学 Preparation method and application of P-Co/CoO heterojunction nano material
CN114870874A (en) * 2022-05-10 2022-08-09 桂林电子科技大学 Nitrogen-doped porous carbon-coated ruthenium-embedded cobalt phosphide composite material based on graphene oxide
CN115364879A (en) * 2022-09-14 2022-11-22 南京理工大学 Preparation method and application of cobalt phosphide nanosheet array three-function catalyst

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111437846B (en) * 2020-05-21 2021-09-07 南京师范大学 Porous CoO/CoP nanotube and preparation method and application thereof
CN113060770B (en) * 2021-02-25 2023-01-31 南京师范大学 Preparation method of heterojunction CoO/CoS porous nanorod, obtained material and application
CN114590844A (en) * 2022-05-04 2022-06-07 台州学院 Mesoporous Co3O4CoO/CoP and preparation method thereof

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150259810A1 (en) * 2014-03-17 2015-09-17 California Institute Of Technology Hydrogen evolution reaction catalysis
CN105803580A (en) * 2016-04-15 2016-07-27 东华大学 Preparation method of cobalt phosphide hollow nano-fiber material
CN105977467A (en) * 2016-07-01 2016-09-28 北京工业大学 Preparation method for preparing Co3O4@CoP composite electrode based on MOF template
CN107245727A (en) * 2017-05-09 2017-10-13 南昌航空大学 A kind of preparation method of porous phosphatization cobalt nanowire catalyst
CN109841422A (en) * 2019-03-20 2019-06-04 武汉理工大学 Co3O4/Co2P coaxial heterogeneous structure material and its preparation method and application
CN110871074A (en) * 2018-08-29 2020-03-10 天津大学 Porous nanosheet-based NiCo2O4Nanotube for high efficiency catalytic elimination of soot
CN111437846A (en) * 2020-05-21 2020-07-24 南京师范大学 Porous CoO/CoP nanotube and preparation method and application thereof

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150259810A1 (en) * 2014-03-17 2015-09-17 California Institute Of Technology Hydrogen evolution reaction catalysis
CN105803580A (en) * 2016-04-15 2016-07-27 东华大学 Preparation method of cobalt phosphide hollow nano-fiber material
CN105977467A (en) * 2016-07-01 2016-09-28 北京工业大学 Preparation method for preparing Co3O4@CoP composite electrode based on MOF template
CN107245727A (en) * 2017-05-09 2017-10-13 南昌航空大学 A kind of preparation method of porous phosphatization cobalt nanowire catalyst
CN110871074A (en) * 2018-08-29 2020-03-10 天津大学 Porous nanosheet-based NiCo2O4Nanotube for high efficiency catalytic elimination of soot
CN109841422A (en) * 2019-03-20 2019-06-04 武汉理工大学 Co3O4/Co2P coaxial heterogeneous structure material and its preparation method and application
CN111437846A (en) * 2020-05-21 2020-07-24 南京师范大学 Porous CoO/CoP nanotube and preparation method and application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PENG SHAOQIN; CAO YANG; ZHOU FENGXIAN; XU ZHAODI; LI YUEXIANG: "CoP decorated with Co3O4as a cocatalyst for enhanced photocatalytic hydrogen evolution via dye sensitization", APPLIED SURFACE SCIENCE, ELSEVIER, AMSTERDAM, NL, vol. 487, 1 January 1900 (1900-01-01), AMSTERDAM, NL , pages 315 - 321, XP085720913, ISSN: 0169-4332, DOI: 10.1016/j.apsusc.2019.05.113 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114558597A (en) * 2022-04-02 2022-05-31 合肥工业大学 Preparation method and application of P-Co/CoO heterojunction nano material
CN114558597B (en) * 2022-04-02 2023-11-21 合肥工业大学 Preparation method and application of P-Co/CoO heterojunction nano material
CN114870874A (en) * 2022-05-10 2022-08-09 桂林电子科技大学 Nitrogen-doped porous carbon-coated ruthenium-embedded cobalt phosphide composite material based on graphene oxide
CN115364879A (en) * 2022-09-14 2022-11-22 南京理工大学 Preparation method and application of cobalt phosphide nanosheet array three-function catalyst
CN115364879B (en) * 2022-09-14 2023-11-17 南京理工大学 Preparation method and application of cobalt phosphide nano-sheet array three-function catalyst

Also Published As

Publication number Publication date
CN111437846B (en) 2021-09-07
CN111437846A (en) 2020-07-24

Similar Documents

Publication Publication Date Title
WO2021232751A1 (en) Porous coo/cop nanotubes, preparation method therefor and use thereof
CN108671948B (en) Preparation method of self-assembled ultrathin flower-shaped nickel-cobalt phosphide electro-catalytic material
CN107349937B (en) Preparation method of graphene-based bimetallic sulfide nano composite photocatalyst
CN109746011B (en) MOF-based derived composite photocatalyst and preparation method thereof
CN104941674A (en) Catalyst for loading cobalt phosphide on activated carbon as well as preparation and application of catalyst
CN112481653B (en) Defect-rich molybdenum-doped cobalt selenide/nano carbon electrocatalyst and preparation method and application thereof
CN109876843B (en) Copper alloy modified titanium dioxide/carbon nitride heterojunction photocatalyst and preparation method thereof
CN111659439B (en) Nitrogen-doped carbon nano composite material loaded with NiS/NiO heterojunction and preparation method and application thereof
CN111659427B (en) High-efficiency electrolytic water hydrogen evolution catalyst MoO2-CeF3/NF and preparation method thereof
CN113529107B (en) Silver nanowire and cobalt-nickel alloy composite oxygen evolution catalytic material and preparation method thereof
CN113512738B (en) Ternary iron-nickel-molybdenum-based composite material water electrolysis catalyst, and preparation method and application thereof
CN110854396A (en) PtAg nanocrystalline with porous double-hollow-sphere structure and preparation method and application thereof
Han et al. Design yolk-shelled FeCo layered double hydroxide via a “one-stone-two-birds” strategy for oxygen evolution reaction
CN111151281B (en) C 3 N 4 Modified Co 3 O 4 Self-supported ultrathin porous nanosheet and preparation method and application thereof
CN109097788B (en) Double-carbon coupling transition metal nickel-based quantum dot electrocatalyst and preparation method thereof
CN108306023B (en) BN/CuAg/CNT composite material and preparation method and application thereof
CN106745525B (en) Metal composite material, preparation method and application thereof
CN112779550B (en) Three-dimensional micron tubular hydrogen evolution reaction electrocatalyst and preparation method thereof
CN115305480A (en) Alloy nano material catalyst and preparation method and application thereof
CN115305496A (en) Preparation method and application of rare earth cerium-doped cobalt phosphide/iron phosphide heterogeneous material
CN109852993B (en) Iron alkoxide oxygen evolution catalyst based on eutectic solvent, preparation method and electrocatalytic oxygen evolution application thereof
CN109569659B (en) Photocatalytic auxiliary agent for reducing carbon dioxide and preparation method thereof
CN112657516A (en) Direct Z-type photocatalyst and preparation method and application thereof
CN115125578B (en) Preparation method of B-S co-doped nickel-cobalt-based electrolytic water oxygen evolution catalyst
CN115532298B (en) Preparation method of diatomic cluster photocatalyst

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 20936968

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 20936968

Country of ref document: EP

Kind code of ref document: A1