WO2020037845A1 - Nanocristaux de sulfure de cobalt creux à base de graphène capables d'activer efficacement le persulfate et leur procédé de préparation - Google Patents

Nanocristaux de sulfure de cobalt creux à base de graphène capables d'activer efficacement le persulfate et leur procédé de préparation Download PDF

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WO2020037845A1
WO2020037845A1 PCT/CN2018/115125 CN2018115125W WO2020037845A1 WO 2020037845 A1 WO2020037845 A1 WO 2020037845A1 CN 2018115125 W CN2018115125 W CN 2018115125W WO 2020037845 A1 WO2020037845 A1 WO 2020037845A1
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graphene
graphene oxide
based hollow
preparation
cobalt sulfide
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PCT/CN2018/115125
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English (en)
Chinese (zh)
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刘福强
朱长青
凌晨
江昊
吴海德
李爱民
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南京大学
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Priority to JP2020545353A priority Critical patent/JP7011350B2/ja
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/184—Preparation
    • 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
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/04—Sulfides
    • B01J27/043—Sulfides with iron group metals or platinum group metals
    • B01J35/40—
    • B01J35/50—
    • 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
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/30—Sulfides
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds

Definitions

  • the invention belongs to the field of environmental catalyst synthesis, a graphene-based hollow cobalt sulfide nanocrystal capable of efficiently activating a persulfate salt, and a preparation method thereof.
  • Heterogeneous catalysis uses the surface active sites of solid catalysts. Point activation persulfate can effectively avoid the above problems.
  • researches on improving the efficiency of heterogeneous catalysis are mainly focused on two points, that is, enhancing the intrinsic catalytic activity by applying external energy to enhance or optimize the catalyst structure design.
  • the Chinese patent number is 201610174029.0, and the patent application document with an application publication date of March 24, 2016 discloses a method for electrochemically synergizing Ni-Fe-LDH / rGO catalyst to activate persulfate to treat organic wastewater;
  • Chinese patent number is 201510234345.8, the patent application file with an application publication date of May 11, 2015 discloses a construction and application method of a photo-assisted porous copper bismuthate-activated advanced oxidation technology for the treatment of persulfate brine.
  • External energy forms such as light to enhance the catalytic effect, but this type of method has high energy consumption and complex equipment, which is difficult to promote on a large scale.
  • cobalt has the best activation effect on persulfate.
  • Common cobalt-based catalysts are mostly cobalt or cobalt-containing oxides.
  • Chinese patent number 201510928060.4 and the application publication date of December 15, 2015 disclose a three-dimensional magnetic ordered mesoporous cobalt ferrite Method for treating dye wastewater by activating persulfate;
  • Chinese Patent No. 201510487197.0 and patent application filed on August 10, 2015 disclose a method for manganese-cobalt composite oxide to activate persulfate to degrade organic wastewater.
  • the resulting hollow Tricobalt tetrasulfide exhibits high electrocatalytic and photocatalytic hydrogen production efficiency (Huang et Cobalt-Based Bimetallic Sulfide Polyhedra for Efficient All-pH Value Electrochemical and Photocatalytic Hydrogen Evolution, J. Am. Chem. Soc. 2016, 138, 1359-1365).
  • the catalyst activity is still limited by the low conductivity of tricobalt tetrasulfide.
  • Kong et al. Used a solvothermal method to synthesize graphene-supported solid cobalt sulfide for lithium-ion batteries and photocatalysts (Kong et al.
  • the present invention solves the aforementioned technical problems in the prior art, and provides a graphene-based hollow cobalt sulfide nanocrystal capable of efficiently activating a persulfate salt and a preparation method thereof.
  • a method for preparing graphene-based hollow cobalt sulfide nanocrystals capable of efficiently activating persulfate salts includes the following steps:
  • step b Preparation of graphene-based hollow cobalt sulfide: The graphene-based hollow cobalt sulfide obtained in step b is placed in a tube furnace, and under the protection of an inert gas, the cobalt sulfide is desulfurized by high-temperature calcination. Graphene-based hollow cobalt sulfide nanocrystals.
  • the concentration of the graphene oxide dispersion in step a is 0.5 to 3 mg / mL, and the dosage of cobalt nitrate hexahydrate is 10 to 20 mg / mL.
  • the concentration of the 2-methylimidazole aqueous solution in step a is 45-115 mg / mL.
  • the concentration of the graphene oxide zeolite-type imidazole ester frame 67 ethanol dispersion is 1 to 3 mg / mL, and the dosage of thioacetamide is 1.5 to 4.5 mg / mL.
  • the solvothermal reaction temperature in the step b is 120-140 ° C, and the reaction time is 3-6 hours.
  • the inert gas in step c is one of high-purity nitrogen or argon.
  • the calcination temperature in the step c is 600-700 ° C
  • the calcination time is 2-6h
  • the heating rate is 1-10 ° C / min.
  • the graphene-based hollow cobalt sulfide nanocrystals can be used as a catalyst to activate persulfate and degrade organic matter.
  • Method 1 After the graphene-based hollow cobalt sulfide nanocrystals are thoroughly mixed with a solution containing an organic substance, persulfate is added.
  • the graphene-based hollow cobalt sulfide nanocrystals are trapped on a filter membrane, and are used to filter a mixed solution containing persulfate and organic matter.
  • the persulfate includes one or more of sodium persulfate, potassium persulfate, and potassium persulfate complex salts.
  • the present invention uses a simple organometallic frame self-stenciling method, combined with solvent thermal vulcanization and high temperature desulfurization reaction, to prepare a new type of graphene-supported cobalt sulfide nanocrystals with hollow structure; the composite material integrates graphene Enrichment of common organic pollutants, rapid transport of electrons, and the efficient activation of persulfate by cobalt sulfide can quickly degrade organic pollutants in water.
  • the graphene-based hollow cobalt sulfide nanocrystals prepared by the present invention can overcome the large amount of homogeneous catalytic agents and the difficulty of recovering the catalyst.
  • the common external energy combined with the heterogeneous heterogeneous catalysis has high energy consumption, complicated equipment, and ordinary heterogeneous.
  • the catalyst has the disadvantages of low activation efficiency of persulfate, etc. It is a new type of catalyst with high efficiency, low consumption, and multiple times of reuse. It can greatly save the amount of catalyst and oxidant while treating pollutants quickly, and has significant environmental and economic significance.
  • the present invention focuses on conventional cobalt-based heterogeneous catalysts that are mostly cobalt or cobalt-containing oxides.
  • cobalt sulfides have been used to activate persulfates, providing an advanced oxidation technology based on sulfate radicals. This kind of new-type high-efficiency catalyst has broad application prospects.
  • FIG. 1 is a (A) scanning and (B) transmission electron microscope image of a graphene-based hollow cobalt sulfide nanocrystal in the present invention
  • Example 2 is a graph showing the degradation effect of graphene-based hollow cobalt sulfide nanocrystals on bisphenol A in Example 1 of the present invention
  • FIG. 3 is a graphene-based hollow cobalt sulfide nanocrystal-based catalytic membrane structure (A) and its reuse performance (B) in Example 1 of the present invention.
  • step b Preparation of graphene-based hollow cobalt sulfide: The graphene-based hollow cobalt sulfide obtained in step b was placed in a tube furnace, and under a nitrogen atmosphere, the temperature was raised to 600 ° C and calcined at 5 ° C / min for 2h. A graphene-based hollow cobalt sulfide nanocrystal is obtained by inverse desulfurization reaction of tricobalt tetrasulfide.
  • FIG. 1 The scanning and transmission electron microscope images of the graphene-based hollow cobalt sulfide nanocrystals obtained in step c in this embodiment are shown in FIG. 1. It can be seen that hollow cobalt sulfide nanocrystals with a size of 10-40 nm are uniformly supported on the graphene nanosheets.
  • Bisphenol A is often used as an additive in plastics and resins. It is widely found in water as an endocrine disruptor.
  • the obtained graphene-based hollow cobalt sulfide nanocrystals were used to test the potassium bisulfate composite salt for degradation of bisphenol A.
  • the specific experimental conditions were: 2 mg of catalyst was placed in 20 mL of bisphenol A solution, and The concentration of phenol A was 20 mg / L, the initial pH was 6.65 and the pH was not adjusted during the experiment. The experimental temperature was 25 ° C. After the catalyst was dispersed ultrasonically, the adsorption-desorption equilibrium was reached for 30 minutes, and then 4 mg potassium persulfate was added. The composite salt initiates the reaction.
  • the degradation results of bisphenol A are shown in Figure 2. From the results, it can be seen that the degradation rate of bisphenol A can reach 97% in 8 minutes, which verifies the efficiency of the catalyst.
  • a catalyst with excellent reuse performance can effectively reduce wastewater treatment costs.
  • 0.5 mg of graphene-based hollow cobalt sulfide nanocrystals are first uniformly dispersed in 5 mL of water, and then filtered and trapped on an inert circular polytetrafluoroethylene filter membrane (pore diameter: 0.22 ⁇ m, diameter: 1.5 cm).
  • 2 mL of a mixed solution containing bisphenol A at a concentration of 10 mg / mL and a potassium persulfate complex salt at a concentration of 0.2 mg / mL was squeezed through a first filter membrane (M1) through a syringe, and the filtration speed was 1 mL / min To complete the first degradation, as shown in Figure 3A.
  • Fig. 3B shows the change of the catalytic efficiency of the adsorbent in the three cycles. It can be found that the catalytic efficiency of the catalyst does not decrease significantly in the three cycles.
  • the concentration of the graphene oxide dispersion in step a is 0.5 mg / mL;
  • step b the concentration of the graphene oxide zeolite-type imidazole ester frame 67 ethanol dispersion is 3 mg / mL, the concentration of thioacetamide is 4.5 mg / mL, the solvothermal reaction temperature is 140 ° C., and the reaction time is 6 h;
  • step c the inert protective gas is argon, and the heating rate is 10 ° C / min.
  • the obtained catalyst had a degradation rate of bisphenol A of 88% within 8 minutes.
  • the concentration of cobalt nitrate hexahydrate in step a is 20 mg / mL, and the concentration of 2-methylimidazole is 90 mg / mL;
  • step b the concentration of the graphene oxide zeolite-type imidazole ester frame 67 ethanol dispersion is 1 mg / mL, the concentration of thioacetamide is 1.5 mg / mL, the solvothermal reaction temperature is 120 ° C., and the reaction time is 3 h;
  • the obtained catalyst had a degradation rate of bisphenol A of 99% within 8 minutes.
  • the concentration of cobalt nitrate hexahydrate in step a is 10 mg / mL, and the concentration of 2-methylimidazole is 45 mg / mL;
  • step b the concentration of the graphene oxide zeolite-type imidazole ester frame 67 ethanol dispersion is 2 mg / mL, the concentration of thioacetamide is 3 mg / mL, the solvothermal reaction temperature is 130 ° C., and the reaction time is 5 h;
  • the obtained catalyst had a degradation rate of bisphenol A of 89% within 8 minutes.
  • Example 1 Same as in Example 1, except that the calcination temperature in step c is 650 ° C, the heating time is 4h, and the heating rate is 2 ° C / min. Under the same experimental conditions as in Example 1, the obtained catalyst had a degradation rate of 98% of bisphenol A within 8 minutes.
  • Example 2 Same as in Example 1, except that the calcination temperature in step c was 700 ° C, the heating time was 6 hours, and the heating rate was 1 ° C / min.
  • the obtained catalyst was treated with bisphenol A in 8 minutes under the same experimental conditions as in Example 1. The degradation rate is 99%.
  • Example 2 Same as in Example 1, except that the concentration of the graphene oxide dispersion was 2 mg / mL, and the degradation rate of bisphenol A by the catalyst was 95% under the same experimental conditions as in Example 1 within 8 minutes.
  • Example 2 Same as in Example 1, except that the persulfate used is one or a mixture of sodium persulfate or potassium persulfate, and the catalyst degrades bisphenol A within 8 minutes under the same experimental conditions as in Example 1. The rate is 86%.
  • step c Same as in Example 1, except that the calcination temperature in step c is 500 ° C. Because this temperature cannot trigger desulfurization reaction of tricobalt tetrasulfide to generate cobalt sulfide, the final material obtained is graphene-based hollow tricobalt tetrasulfide nanocrystals. Under the same experimental conditions as in Example 1, the degradation rate of bisphenol A within 75 minutes was 75%.
  • step c Same as in Example 1, except that the calcination temperature in step c is 800 ° C. At this temperature, tricobalt tetrasulfide undergoes two desulfurization reactions to produce non-cobalt octasulfide, so the final material obtained is graphene-based hollow non-cobalt octasulfide. Nanocrystals, when stored or placed in water, will react with oxygen in the air or water in an unstable manner and easily cause the loss of cobalt, which is not suitable as a catalyst for the degradation of pollutants in water.

Abstract

L'invention concerne des nanocristaux de sulfure de cobalt creux à base de graphène capables d'activer efficacement le persulfate et un procédé de préparation associé : tout d'abord la croissance d'une structure d'imidazolate zéolitique 67 sur la surface d'oxyde de graphène au moyen d'un procédé de précipitation ; l'utilisation de la structure d'imidazolate 67 en tant qu'automatrice et de thioacétamide en tant que source de soufre, la préparation d'un tétrasulfure de tricobalt à structure creuse au moyen d'une réaction solvothermale ; la calcination dans une atmosphère inerte, la conversion du tétrasulfure de tricobalt en sulfure de cobalt creux au moyen d'une réaction de désulfuration, et la réduction simultanée de l'oxyde de graphène en graphène, pour ainsi produire des nanocristaux de sulfure de cobalt creux à base de graphène.
PCT/CN2018/115125 2018-08-20 2018-11-13 Nanocristaux de sulfure de cobalt creux à base de graphène capables d'activer efficacement le persulfate et leur procédé de préparation WO2020037845A1 (fr)

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CN111545211A (zh) * 2020-04-26 2020-08-18 闽南师范大学 一种氧化石墨烯-氧化镧-氢氧化钴复合材料、合成方法及其应用
CN111545211B (zh) * 2020-04-26 2023-01-10 闽南师范大学 一种氧化石墨烯-氧化镧-氢氧化钴复合材料、合成方法及其应用
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CN113751074B (zh) * 2021-09-02 2023-04-25 北京建筑大学 固载型催化剂及其制备方法和应用
CN114011411A (zh) * 2021-11-08 2022-02-08 安徽科技学院 一种CoO-Co3O4碳复合物的制备方法及其应用
CN114011411B (zh) * 2021-11-08 2023-05-26 安徽科技学院 一种CoO-Co3O4碳复合物的制备方法及其应用
CN114160162A (zh) * 2021-12-29 2022-03-11 天津工业大学 一种Au/Co（OH）2层状金属氢氧化物空心结构光催化剂及其制备方法
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CN114566627A (zh) * 2022-03-03 2022-05-31 北京理工大学 一种Co3S4-CoN@NC钠离子电极材料的制备方法
CN114566627B (zh) * 2022-03-03 2023-11-28 北京理工大学 一种Co3S4-CoN@NC钠离子电极材料的制备方法
CN114604903A (zh) * 2022-04-07 2022-06-10 苏州大学 一种硫化钴/还原氧化石墨烯复合物及在气体传感器中的应用
CN114917926A (zh) * 2022-04-24 2022-08-19 湖南大学 负载单原子钌的ldh催化剂及其制备方法和在病原菌消杀中的应用
CN114917926B (zh) * 2022-04-24 2023-10-20 湖南大学 负载单原子钌的ldh催化剂及其制备方法和在病原菌消杀中的应用
CN114804220B (zh) * 2022-04-25 2023-07-07 广东邦普循环科技有限公司 一种多孔隙球形钴氧化物颗粒及其制备方法
CN114804220A (zh) * 2022-04-25 2022-07-29 广东邦普循环科技有限公司 一种多孔隙球形钴氧化物颗粒及其制备方法
CN114849748B (zh) * 2022-05-13 2023-09-08 华东理工大学 一种CoS/Ti3C2MXene复合材料的制备及其应用
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CN114976069B (zh) * 2022-06-23 2023-11-17 香港科技大学深圳研究院 一种类沸石咪唑酯骨架/石墨烯催化剂的制备方法及其应用
CN114976069A (zh) * 2022-06-23 2022-08-30 香港科技大学深圳研究院 一种类沸石咪唑酯骨架/石墨烯催化剂的制备方法及其应用
CN115672354A (zh) * 2022-10-17 2023-02-03 常州大学 一种zif-67衍生的空心硫化钴/硫化锰镉复合光催化剂的制备方法及其应用
CN115672374A (zh) * 2022-10-31 2023-02-03 中国科学技术大学 具有级联催化活性的金属单原子/金属纳米颗粒的纳米复合物及其制备与应用
CN115672374B (zh) * 2022-10-31 2024-02-23 中国科学技术大学 具有级联催化活性的金属单原子/金属纳米颗粒的纳米复合物及其制备与应用
CN116589970A (zh) * 2023-05-16 2023-08-15 广东昱昇新材料科技有限公司 一种耐老化密封胶及其制备方法

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