WO2020037845A1 - Graphene-based hollow cobalt sulphide nanocrystals capable of efficiently activating persulphate, and preparation method therefor - Google Patents

Graphene-based hollow cobalt sulphide nanocrystals capable of efficiently activating persulphate, and preparation method therefor 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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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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    • 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

Graphene-based hollow cobalt sulphide nanocrystals capable of efficiently activating persulphate, and a preparation method therefor: first growing a zeolite-type imidazolate framework 67 on the surface of graphene oxide by means of a precipitation method; using the imidazolate framework 67 as a self-template and thioacetamide as a sulphur source, preparing a hollow structure tricobalt tetrasulphide by means of a solvothermal reaction; calcining in an inert atmosphere, converting the tricobalt tetrasulphide into hollow cobalt sulphide by means of a desulphurisation reaction, and simultaneously reducing graphene oxide to graphene, to thereby produce graphene-based hollow cobalt sulphide nanocrystals.

Description

一种可高效活化过硫酸盐的石墨烯基中空硫化钴纳米晶及其制备方法Graphene-based hollow cobalt sulfide nanocrystal capable of efficiently activating persulfate and preparation method thereof 技术领域Technical field
本发明属于环境催化剂合成领域，一种可高效活化过硫酸盐的石墨烯基中空硫化钴纳米晶及其制备方法。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.
背景技术Background technique
工业、生活和医药等有机废水的无节制排放引发了越发严重的水污染。对于高毒性和持久性有机物，传统吸附、膜处理等物化方法只可转移但难以削减其毒性，生化方法中微生物对高毒有机物耐受性不强，处理效果不佳。高级氧化技术可降解甚至矿化有机物，能显著降低其毒性并提升可生物降解性，可置于水处理工艺前端或末端实现对有机污染物的高效去除。The uncontrolled discharge of organic, industrial, domestic and pharmaceutical organic wastewater has caused more and more serious water pollution. For highly toxic and persistent organics, traditional physicochemical methods such as adsorption and membrane treatment can only be transferred but it is difficult to reduce their toxicity. In biochemical methods, microorganisms do not have high tolerance to highly toxic organics and their treatment effects are not good. Advanced oxidation technology can degrade and even mineralize organic matter, which can significantly reduce its toxicity and improve biodegradability. It can be placed at the front or end of the water treatment process to achieve efficient removal of organic pollutants.
基于羟基自由基和基于硫酸根自由基的氧化技术是两类重要的高级氧化技术。相对于羟基自由基，硫酸根自由基因具有氧化还原电位更高(2.5-3.1V vs 1.8-2.7V)、pH适用范围更广、半衰期更长(t 1/2＝30-40μs vs 10-3μs)等内在优势而成为研究热点。硫酸根自由基可由过硫酸盐通过均相或非均相催化产生，其中均相催化过程催化剂用量大，易造成二次污染且催化剂难以回用，而非均相催化利用固体催化剂的表面活性位点活化过硫酸盐，可有效规避以上难题。目前，提高非均相催化效率的研究主要集中在两点，即通过施加外部能量增强或优化催化剂结构设计提升其内在催化活性。如中国专利号为201610174029.0，申请公开日为2016年3月24日的专利申请文件公开了一种电化学协同Ni-Fe-LDH/rGO催化剂活化过硫酸盐 处理有机废水的方法；中国专利号为201510234345.8，申请公开日为2015年5月11日的专利申请文件公开了一种光助多孔铋酸铜活化过硫酸盐水处理高级氧化技术的构筑与应用方法，上述两份对比文件分别通过施加电、光等外部能量形式来增强催化效果，但该类方法能耗高，所需装置复杂，难以大规模推广。 Oxidation technologies based on hydroxyl radicals and sulfate radicals are two important types of advanced oxidation techniques. Relative to hydroxyl radicals, the sulfate free gene has a higher redox potential (2.5-3.1V vs 1.8-2.7V), a wider pH range, and a longer half-life (t 1/2 = 30-40 μs vs 10-3 μs ) And other inherent advantages have become research hotspots. Sulfate radicals can be generated by persulfate through homogeneous or heterogeneous catalysis, in which the amount of catalyst used in the homogeneous catalysis process is large, and it is easy to cause secondary pollution and the catalyst is difficult to reuse. Heterogeneous catalysis uses the surface active sites of solid catalysts. Point activation persulfate can effectively avoid the above problems. At present, 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. For example, 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.
对于提升非均相催化剂的内在活性，可通过增加表面活性位点的密度、加快电子传输速率、增强对目标污染物的富集能力三方面来实现。根据已有报道，在金属催化剂中，钴对过硫酸盐的活化效果最佳。常见的钴系催化剂多为钴或含钴的氧化物，如中国专利号为201510928060.4，申请公开日为2015年12月15日的专利申请文件公开了一种基于三维磁性有序介孔铁酸钴活化过硫酸盐处理染料废水的方法；中国专利号为201510487197.0，申请公开日为2015年8月10日的专利申请文件公开了一种锰钴复合氧化物活化过硫酸盐降解有机废水的方法。然而，上述两份对比文件所述催化剂均难以同时满足以上三方面要求，因此催化效果不佳，催化活性有待进一步提升。近期，Huang等人以含钴的沸石型咪唑酯框架67为自模版，通过溶剂热硫化反应使沸石型咪唑酯框架67内部的钴离子向表面迁移从而形成高密度表面催化位点，所得的中空四硫化三钴表现出很高的电催化和光催化产氢效率(Huang et al.Hollow Cobalt-Based Bimetallic Sulfide Polyhedra for Efficient All-pH Value Electrochemical and Photocatalytic Hydrogen Evolution,J.Am.Chem.Soc.2016,138,1359-1365)。然而，该催化剂活性仍受制于 四硫化三钴的低导电能力。Kong等通过溶剂热法一步合成了石墨烯负载的实心硫化钴用作锂离子电池和光催化剂(Kong et al.Morphological Effect of Graphene Nanosheets on Ultrathin CoS Nanosheets and Their Applications for High-Performance Li-Ion Batteries and Photocatalysis,J.Phys.Chem.C 2014,118,25355-25364)，但实心硫化钴表面催化位点密度低，内部位点利用率不高。To improve the intrinsic activity of heterogeneous catalysts, it can be achieved by increasing the density of surface active sites, accelerating the electron transport rate, and enhancing the enrichment ability of target pollutants. According to reports, among metal catalysts, cobalt has the best activation effect on persulfate. Common cobalt-based catalysts are mostly cobalt or cobalt-containing oxides. For example, 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. However, the catalysts mentioned in the two comparative documents are difficult to meet the above three requirements at the same time, so the catalytic effect is not good, and the catalytic activity needs to be further improved. Recently, Huang et al. Used cobalt-containing zeolite-type imidazolate frame 67 as a self-template and used a solvothermal vulcanization reaction to move the cobalt ions inside the zeolite-type imidazolate frame 67 to the surface to form a high-density surface catalytic site. 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). However, 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. Morphological Effect of Graphene Nanosheets on Ultrathin CoS Nanosheets and Their Applications for High-Performance Li-Ion Batteries and And Photocatalysis , J. Phys. Chem. C 2014, 118, 25355-25364), but the density of catalytic sites on the surface of solid cobalt sulfide is low and the utilization rate of internal sites is not high.
发明内容Summary of the Invention
本发明解决现有技术中存在的上述技术问题，提供一种可高效活化过硫酸盐的石墨烯基中空硫化钴纳米晶及其制备方法。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.
为解决上述问题，本发明的技术方案如下：To solve the above problems, the technical solution of the present invention is as follows:
一种可高效活化过硫酸盐的石墨烯基中空硫化钴纳米晶的制备方法，包括以下步骤：A method for preparing graphene-based hollow cobalt sulfide nanocrystals capable of efficiently activating persulfate salts includes the following steps:
a.氧化石墨烯基沸石型咪唑酯框架67制备：将氧化石墨烯通过超声均匀分散在水中得氧化石墨烯分散液，然后向其中加入六水合硝酸钴，常温下搅拌0.5～2h使钴离子吸附到氧化石墨烯表面，然后加入2-甲基咪唑水溶液，常温下搅拌5～30min后，再离心、水洗、烘干即得氧化石墨烯基沸石型咪唑酯框架67；a. Preparation of graphene oxide zeolite-type imidazole ester frame 67: Graphene oxide is dispersed uniformly in water by ultrasound to obtain a graphene oxide dispersion, and then cobalt nitrate hexahydrate is added thereto, and stirred for 0.5 to 2 hours at room temperature to adsorb cobalt ions. Onto the surface of graphene oxide, then add an aqueous solution of 2-methylimidazole, stir at room temperature for 5-30 minutes, and then centrifuge, wash and dry to obtain a graphene oxide zeolite-type imidazole ester frame 67;
b.氧化石墨烯基中空四硫化三钴制备：将步骤a中所得的氧化石墨烯基沸石型咪唑酯框架67通过超声均匀分散在乙醇中得氧化石墨烯基沸石型咪唑酯框架67乙醇分散液，然后向其中加入硫代乙酰胺，搅拌使其溶解后，将混合液转入水热反应釜中，加热反应后将产 物经离心、水洗、烘干后即得氧化石墨烯基中空四硫化三钴；b. Preparation of graphene oxide hollow tricobalt tetrasulfide: The graphene oxide zeolite-type imidazole ester frame 67 obtained in step a was uniformly dispersed in ethanol to obtain a graphene oxide zeolite-type imidazole ester frame 67 ethanol dispersion. Then, add thioacetamide to it, stir to dissolve it, transfer the mixed solution to a hydrothermal reactor, heat the reaction, centrifuge the product, wash with water, and dry to obtain graphene oxide hollow tetrasulfide. cobalt;
c.石墨烯基中空硫化钴制备：将步骤b中所得氧化石墨烯基中空四硫化三钴置入管式炉中，在惰性气体保护下，高温煅烧使四硫化三钴反生脱硫反应即得石墨烯基中空硫化钴纳米晶。c. 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.
优选地，所述的步骤a中的氧化石墨烯分散液的浓度为0.5～3mg/mL，六水合硝酸钴的投加量为10～20mg/mL。Preferably, 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.
优选地，所述的步骤a中的2-甲基咪唑水溶液浓度为45～115mg/mL。Preferably, the concentration of the 2-methylimidazole aqueous solution in step a is 45-115 mg / mL.
优选地，所述的步骤b中氧化石墨烯基沸石型咪唑酯框架67乙醇分散液的浓度为1～3mg/mL，硫代乙酰胺的投加量为1.5～4.5mg/mL。Preferably, in the step b, 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.
优选地，所述的步骤b中的溶剂热反应温度为120～140℃，反应时间为3～6h。Preferably, the solvothermal reaction temperature in the step b is 120-140 ° C, and the reaction time is 3-6 hours.
优选地，所述的步骤c中的惰性气体为高纯氮气或氩气中的一种。Preferably, the inert gas in step c is one of high-purity nitrogen or argon.
优选地，所述的步骤c中的煅烧温度为600～700℃，煅烧时间为2～6h，升温速率为1～10℃/min。Preferably, the calcination temperature in the step c is 600-700 ° C, the calcination time is 2-6h, and the heating rate is 1-10 ° C / min.
石墨烯基中空硫化钴纳米晶在有机物降解中的应用。Application of Graphene-based Hollow Cobalt Sulfide Nanocrystals in Organic Degradation.
所述石墨烯基中空硫化钴纳米晶可作为催化剂活化过硫酸盐，降解有机物。The graphene-based hollow cobalt sulfide nanocrystals can be used as a catalyst to activate persulfate and degrade organic matter.
具体方法为：The specific method is:
方法一，将所述石墨烯基中空硫化钴纳米晶与包含有机物的溶液充分混合后，加入过硫酸盐。Method 1: After the graphene-based hollow cobalt sulfide nanocrystals are thoroughly mixed with a solution containing an organic substance, persulfate is added.
方法二，将所述石墨烯基中空硫化钴纳米晶过滤截留在滤膜上，用于过滤包含过硫酸盐和有机物的混合溶液。In a second method, 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.
优选地，所述过硫酸盐包括过硫酸钠、过硫酸钾、过硫酸氢钾复合盐中的一种或几种。Preferably, the persulfate includes one or more of sodium persulfate, potassium persulfate, and potassium persulfate complex salts.
相对于现有技术，本发明的优点如下，Compared with the prior art, the advantages of the present invention are as follows,
(1)本发明利用一种简单的有机金属框架自模版法，结合溶剂热硫化和高温脱硫反应制备了一种新型石墨烯负载的具有中空结构的硫化钴纳米晶；该复合材料整合了石墨烯对常见有机污染物的富集、对电子的快速传输以及硫化钴对过硫酸盐的高效活化能力，因此可快速降解水中有机污染物。(1) 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.
(2)本发明所制备的石墨烯基中空硫化钴纳米晶可克服均相催化药剂投加量大、催化剂难以回收，常见外加能量协同非均相催化能耗高、装置复杂，普通非均相催化剂对过硫酸盐活化效率不高等缺点，是一种高效低耗、可多次回用的新型催化剂，在快速处理污染物的同时可大大节约催化剂、氧化剂用量，环境和经济意义显著。(2) 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.
(3)本发明针对常规钴系非均相催化剂多集中为钴或含钴的氧化物，首次将钴的硫化物应用于活化过硫酸盐，为基于硫酸根自由基的高级氧化技术提供了一类新型高效催化剂，应用前景广阔。(3) The present invention focuses on conventional cobalt-based heterogeneous catalysts that are mostly cobalt or cobalt-containing oxides. For the first time, 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.
附图说明BRIEF DESCRIPTION OF THE DRAWINGS
图1为本发明中的石墨烯基中空硫化钴纳米晶的(A)扫描和(B)透射电镜图；1 is a (A) scanning and (B) transmission electron microscope image of a graphene-based hollow cobalt sulfide nanocrystal in the present invention;
图2为本发明中实施例1中的石墨烯基中空硫化钴纳米晶对双酚A的降解效果图；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;
图3为本发明实施例1中的基于石墨烯基中空硫化钴纳米晶的催化膜构筑(A)及其重复利用性能(B)。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.
具体实施方式detailed description
实施例1Example 1
一种可高效活化过硫酸盐的石墨烯基中空硫化钴纳米晶及其制备方法，其步骤为：A graphene-based hollow cobalt sulfide nanocrystal capable of efficiently activating persulfate and a preparation method thereof, the steps are as follows:
a.氧化石墨烯基沸石型咪唑酯框架67制备：将氧化石墨烯通过超声均匀分散在水中得浓度为3mg/mL的氧化石墨烯分散液，然后向其中加入六水合硝酸钴，浓度为12mg/mL，常温下搅拌0.5～2h使钴离子吸附到氧化石墨烯表面，然后加入浓度为54mg/mL的2-甲基咪唑水溶液，常温下搅拌5～30min后，再离心、水洗、烘干即得氧化石墨烯基沸石型咪唑酯框架67。a. Preparation of graphene oxide zeolite-type imidazole ester frame 67: Graphene oxide was uniformly dispersed in water by ultrasound to obtain a graphene oxide dispersion having a concentration of 3 mg / mL, and then cobalt nitrate hexahydrate was added thereto at a concentration of 12 mg / mL, stirring at room temperature for 0.5 ～ 2h to adsorb cobalt ions on the surface of graphene oxide, and then adding a 2-methylimidazole aqueous solution with a concentration of 54mg / mL, stirring at room temperature for 5 ～ 30min, then centrifuging, washing and drying to obtain Graphene oxide zeolite-type imidazole ester frame 67.
b.氧化石墨烯基中空四硫化三钴制备：将步骤a中所得的氧化石墨烯基沸石型咪唑酯框架67通过超声均匀分散在乙醇中得浓度为1.5mg/mL的氧化石墨烯基沸石型咪唑酯框架67乙醇分散液，然后向其中加入硫代乙酰胺，浓度为2.25mg/mL，搅拌使其溶解后，将混合液转入水热反应釜中，于120℃加热反应4h后将产物经离心、水洗、烘干后即得氧化石墨烯基中空四硫化三钴；b. Preparation of graphene oxide hollow tricobalt tetrasulfide: The graphene oxide zeolite-type imidazole ester frame 67 obtained in step a was uniformly dispersed in ethanol by ultrasound to obtain a graphene oxide zeolite type having a concentration of 1.5 mg / mL. The imidazolate frame 67 ethanol dispersion was added with thioacetamide at a concentration of 2.25 mg / mL. After stirring to dissolve it, the mixture was transferred to a hydrothermal reactor, and the product was heated at 120 ° C for 4 hours to react the product. After centrifugation, washing and drying, graphene oxide hollow tricobalt tetrasulfide is obtained;
c.石墨烯基中空硫化钴制备：将步骤b中所得氧化石墨烯基中空四硫化三钴置入管式炉中，在氮气保护下，以5℃/min的升温速率升至600℃煅烧2h使四硫化三钴反生脱硫反应即得石墨烯基中空硫化钴纳米晶。c. 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.
本实施例中步骤c中所得石墨烯基中空硫化钴纳米晶的扫描和透射电镜图见附图1。可以看出，尺寸在10～40nm的中空硫化钴纳米晶均匀负载在石墨烯纳米片上。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.
双酚A常被用于塑料和树脂的添加剂，其作为一种内分泌干扰物广泛存在于水体中。该实施例将所得石墨烯基中空硫化钴纳米晶活化过硫酸氢钾复合盐来测试其对双酚A的降解性能，具体实验条件为：将2mg催化剂置于20mL双酚A溶液中，其中双酚A的浓度为20mg/L，初始pH为6.65并且在实验过程中不调节pH，实验温度为25℃，将催化剂超声分散后，吸附30min达到吸附-脱附平衡，然后加入4mg过硫酸氢钾复合盐引发反应，双酚A的降解结果如图2所示，由结果可知双酚A在8min的降解率可达97％，验证了该催化剂的高效性。Bisphenol A is often used as an additive in plastics and resins. It is widely found in water as an endocrine disruptor. In this example, 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.
具有优良重复利用性能的催化剂可有效降低废水处理成本。本实施例首先将0.5mg石墨烯基中空硫化钴纳米晶超声均匀分散在5mL水中，然后过滤截留在惰性的圆形聚四氟乙烯滤膜(孔径：0.22μm，直径：1.5cm)上。将2mL含有浓度为10mg/mL的双酚A和浓度为0.2mg/mL的过硫酸氢钾复合盐的混合液通过注射器挤压透过第一个滤膜(M1)，过滤速度为1mL/min，完成第一次降解，如图3A。然后立即将滤出液重新按照以上速率再次滤过第二个过滤膜(M2)完成第二次降解。待两次降解完成，用超纯水简单冲洗两个滤头，然后取另一份同样的反应液，重复以上操作来考察材料的稳定性。图3B给出了吸附剂在3个循环中的催化效率变化图，可以发现3个循环中催化 剂的催化效率没有明显下降。A catalyst with excellent reuse performance can effectively reduce wastewater treatment costs. In this embodiment, 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 μm, 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. Then immediately filter the filtrate again through the second filter membrane (M2) at the above rate to complete the second degradation. After the two degradations are completed, simply rinse the two filter heads with ultrapure water, then take another part of the same reaction solution, and repeat the above operation to check the stability of the material. 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.
实施例2Example 2
同实施例1，所不同的是：Same as in Example 1, except that:
步骤a中氧化石墨烯分散液的浓度为0.5mg/mL；The concentration of the graphene oxide dispersion in step a is 0.5 mg / mL;
步骤b中氧化石墨烯基沸石型咪唑酯框架67乙醇分散液的浓度为3mg/mL，硫代乙酰胺的浓度为4.5mg/mL，溶剂热反应温度为140℃，反应时间为6h；In 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;
步骤c中惰性保护气为氩气，升温速率为10℃/min。In step c, the inert protective gas is argon, and the heating rate is 10 ° C / min.
所得催化剂在与实施例1相同的实验条件下在8min内对双酚A的降解率为88％。Under the same experimental conditions as in Example 1, the obtained catalyst had a degradation rate of bisphenol A of 88% within 8 minutes.
实施例3Example 3
同实施例1，所不同的是：Same as in Example 1, except that:
步骤a中六水合硝酸钴的浓度为20mg/mL，2-甲基咪唑的浓度为90mg/mL；The concentration of cobalt nitrate hexahydrate in step a is 20 mg / mL, and the concentration of 2-methylimidazole is 90 mg / mL;
步骤b中氧化石墨烯基沸石型咪唑酯框架67乙醇分散液的浓度为1mg/mL，硫代乙酰胺的浓度为1.5mg/mL，溶剂热反应温度为120℃，反应时间为3h；In 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;
所得催化剂在与实施例1相同的实验条件下在8min内对双酚A的降解率为99％。Under the same experimental conditions as in Example 1, the obtained catalyst had a degradation rate of bisphenol A of 99% within 8 minutes.
实施例4Example 4
同实施例1，所不同的是：Same as in Example 1, except that:
步骤a中六水合硝酸钴的浓度为10mg/mL，2-甲基咪唑的浓度为45mg/mL；The concentration of cobalt nitrate hexahydrate in step a is 10 mg / mL, and the concentration of 2-methylimidazole is 45 mg / mL;
步骤b中氧化石墨烯基沸石型咪唑酯框架67乙醇分散液的浓度为2mg/mL，硫代乙酰胺的浓度为3mg/mL，溶剂热反应温度为130℃，反应时间为5h；In 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;
所得催化剂在与实施例1相同的实验条件下在8min内对双酚A的降解率为89％。Under the same experimental conditions as in Example 1, the obtained catalyst had a degradation rate of bisphenol A of 89% within 8 minutes.
实施例5Example 5
同实施例1，所不同的是步骤c中煅烧温度为650℃，加热时间为4h，升温速率为2℃/min。所得催化剂在与实施例1相同的实验条件下在8min内对双酚A的降解率为98％。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.
实施例6Example 6
同实施例1，所不同的是步骤c中煅烧温度为700℃，加热时间为6h，升温速率为1℃/min，所得催化剂在与实施例1相同的实验条件下在8min内对双酚A的降解率为99％。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%.
实施例7Example 7
同实施例1，所不同的是氧化石墨烯分散液的浓度为2mg/mL，催化剂在与实施例1相同的实验条件下在8min内对双酚A的降解率为95％。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.
实施例8Example 8
同实施例1，所不同的是使用的过硫酸盐为过硫酸钠或过硫酸钾中的一种或其混合物，催化剂在与实施例1相同的实验条件下在8min内对双酚A的降解率为86％。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%.
实施例9Example 9
为验证该催化剂对不同典型有机污染物的降解效果的广谱性，同实施例1，所不同的催化实验所用污染物改为甲基橙、苯酚、磺胺甲恶唑中的一种，在与实施例1相同的实验条件下8min内对这些污染物的降解率分别为99％、96％和98％，说明该催化剂对水中常见有机污染物均有优异去除效果。In order to verify the broad spectrum of the degradation effect of the catalyst on different typical organic pollutants, the same pollutants used in the different catalytic experiments were changed to one of methyl orange, phenol, and sulfamethoxazole. Under the same experimental conditions in Example 1, the degradation rates of these pollutants within 8 minutes were 99%, 96%, and 98%, respectively, indicating that the catalyst has excellent removal effect on common organic pollutants in water.
对比例1Comparative Example 1
同实施例1，所不同的是步骤c中煅烧温度为500℃，因该温度无法引发四硫化三钴发生脱硫反应生成硫化钴，因此所得最终材料为石墨烯基中空四硫化三钴纳米晶，其在与实施例1相同的实验条件下在8min内对双酚A的降解率为75％。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%.
对比例2Comparative Example 2
同实施例1，所不同的是步骤c中煅烧温度为800℃，因该温度下四硫化三钴发生两次脱硫反应生成八硫化九钴，因此所得最终材料为石墨烯基中空八硫化九钴纳米晶，其在存放或置于水中时会与空气中或水中氧气反应而不稳定并易造成钴的流失，不宜用作降解水中污染物的催化剂。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.
对比例3Comparative Example 3
为更好突出本材料制备方法及其催化性能优势，按照背景技术中参考文献(Huang et al.Hollow Cobalt-Based Bimetallic Sulfide Polyhedra for Efficient All-pH Value Electrochemical and Photocatalytic Hydrogen Evolution,J.Am.Chem.Soc.2016,138,1359-1365)制得中空四硫化三钴，因该材料导电性不佳，且钴非全 部以正二价存在，其在与实施例1相同的实验条件下在8min内对双酚A的降解率为63％。In order to better highlight the material preparation method and its catalytic performance advantages, according to references in the background technology (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). Hollow tricobalt tetrasulfide was prepared. Due to the poor conductivity of the material, and not all of the cobalt exists in a positive divalent state, it was tested within 8 minutes under the same experimental conditions as in Example 1. The degradation rate of bisphenol A was 63%.
对比例4Comparative Example 4
为更好突出本材料制备方法及其催化性能优势，按照背景技术中参考文献(Kong et al.Morphological Effect of Graphene Nanosheets on Ultrathin CoS Nanosheets and Their Applications for High-Performance Li-Ion Batteries and Photocatalysis,J.Phys.Chem.C 2014,118,25355-25364)制得石墨烯负载的实心硫化钴，因实心结构导致活性位点密度低，其在与实施例1相同的实验条件下在8min内对双酚A的降解率为82％。In order to better highlight the material preparation method and its catalytic performance advantages, according to the references in the background technology (Kong et al. Morphological Effects of Graphene Nanosheets on Ultrathin CoS Nanosheets and Their Applications for High-Performance Li-Ion Batteries, and Photocatalysis, J. Phys. Chem. C 2014, 118, 25355-25364) to obtain graphene-supported solid cobalt sulfide, which has a low density of active sites due to the solid structure. It has the same experimental conditions as Example 1 for bisphenol in 8 min. The degradation rate of A was 82%.
需要说明的是上述实施例仅仅是本发明的较佳实施例，并没有用来限定本发明的保护范围，在上述基础上做出的等同替换或者替代均属于本发明的保护范围。It should be noted that the above-mentioned embodiments are merely preferred embodiments of the present invention, and are not used to limit the protection scope of the present invention. Equivalent substitutions or substitutions made on the basis of the above all belong to the protection scope of the present invention.

Claims (10)

  1. 一种可高效活化过硫酸盐的石墨烯基中空硫化钴纳米晶的制备方法，其特征在于，包括以下步骤：A method for preparing graphene-based hollow cobalt sulfide nanocrystals capable of efficiently activating persulfate salts, comprising the following steps:
    a.氧化石墨烯基沸石型咪唑酯框架67制备：将氧化石墨烯通过超声均匀分散在水中得氧化石墨烯分散液，然后向其中加入六水合硝酸钴，常温下搅拌0.5～2h，然后加入2-甲基咪唑水溶液，常温下搅拌5～30min后，再离心、水洗、烘干即得氧化石墨烯基沸石型咪唑酯框架67；a. Preparation of graphene oxide zeolite-type imidazolate frame 67: Graphene oxide is uniformly dispersed in water by ultrasound to obtain a graphene oxide dispersion, and then cobalt nitrate hexahydrate is added thereto, stirred at room temperature for 0.5 to 2 hours, and then added to 2 -Methyl imidazole aqueous solution, after stirring at normal temperature for 5-30 minutes, then centrifuging, washing and drying to obtain a graphene oxide zeolite-type imidazole ester frame 67;
    b.氧化石墨烯基中空四硫化三钴制备：将步骤a中所得的氧化石墨烯基沸石型咪唑酯框架67通过超声均匀分散在乙醇中得氧化石墨烯基沸石型咪唑酯框架67乙醇分散液，然后向其中加入硫代乙酰胺，搅拌使其溶解后，将混合液转入水热反应釜中，加热反应后将产物经离心、水洗、烘干后即得氧化石墨烯基中空四硫化三钴；b. Preparation of graphene oxide hollow tricobalt tetrasulfide: The graphene oxide zeolite-type imidazole ester frame 67 obtained in step a was uniformly dispersed in ethanol to obtain a graphene oxide zeolite-type imidazole ester frame 67 ethanol dispersion. Then, add thioacetamide to it, stir to dissolve it, transfer the mixed solution to a hydrothermal reactor, heat the reaction, centrifuge the product, wash with water, and dry to obtain graphene oxide hollow tetrasulfide. cobalt;
    c.石墨烯基中空硫化钴制备：将步骤b中所得氧化石墨烯基中空四硫化三钴置入管式炉中，在惰性气体保护下，高温煅烧，即得石墨烯基中空硫化钴纳米晶。c. Preparation of graphene-based hollow cobalt sulfide: The graphene-based hollow cobalt sulfide obtained in step b was placed in a tube furnace and calcined at high temperature under the protection of an inert gas to obtain graphene-based hollow cobalt sulfide nanocrystals. .
  2. 如权利要求1所述的制备方法，其特征在于，所述的步骤a中的氧化石墨烯分散液的浓度为0.5～3mg/mL，六水合硝酸钴的投加量为10～20mg/mL。The method according to claim 1, wherein 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.
  3. 如权利要求1所述的制备方法，其特征在于，所述的步骤a中的2-甲基咪唑水溶液浓度为45～115mg/mL。The method according to claim 1, wherein the concentration of the 2-methylimidazole aqueous solution in step a is 45-115 mg / mL.
  4. 如权利要求1所述的制备方法，其特征在于，所述的步骤b中氧 化石墨烯基沸石型咪唑酯框架67乙醇分散液的浓度为1～3mg/mL，硫代乙酰胺的投加量为1.5～4.5mg/mL。The method according to claim 1, wherein the concentration of the graphene oxide zeolite-type imidazole ester frame 67 ethanol dispersion in step b is 1 to 3 mg / mL, and the amount of thioacetamide is added. It is 1.5 to 4.5 mg / mL.
  5. 如权利要求1所述的制备方法，其特征在于，所述的步骤b中的溶剂热反应温度为120～140℃，反应时间为3～6h。The preparation method according to claim 1, wherein the solvothermal reaction temperature in step b is 120-140 ° C, and the reaction time is 3-6 hours.
  6. 如权利要求1所述的制备方法，其特征在于，所述的步骤c中的煅烧温度为600～700℃，煅烧时间为2～6h，升温速率为1～10℃/min。The preparation method according to claim 1, wherein the calcination temperature in step c is 600 to 700 ° C, the calcination time is 2 to 6h, and the heating rate is 1 to 10 ° C / min.
  7. 如权利要求1-6任一项所述的石墨烯基中空硫化钴纳米晶。The graphene-based hollow cobalt sulfide nanocrystals according to any one of claims 1-6.
  8. 如权利要求1-6任一项所述的石墨烯基中空硫化钴纳米晶在有机物降解中的应用。The use of the graphene-based hollow cobalt sulfide nanocrystals according to any one of claims 1 to 6 in the degradation of organic matter.
  9. 如权利要求8所述的应用，其特征在于，具体方法为：将所述石墨烯基中空硫化钴纳米晶与包含有机物的溶液充分混合后，加入过硫酸盐。The application according to claim 8, characterized in that the specific method is: after the graphene-based hollow cobalt sulfide nanocrystals are sufficiently mixed with a solution containing an organic substance, persulfate is added.
  10. 如权利要求8所述的应用，其特征在于，具体方法为：将所述石墨烯基中空硫化钴纳米晶过滤截留在滤膜上，用于过滤包含过硫酸盐和有机物的混合溶液。The application according to claim 8, characterized in that the specific method is: filtering the graphene-based hollow cobalt sulfide nanocrystals on a filter membrane for filtering a mixed solution containing persulfate and organic matter.
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