WO2022041852A1 - 一种在泡沫镍表面原位生长Ni-MOF薄膜光催化剂及其制备方法和应用 - Google Patents

一种在泡沫镍表面原位生长Ni-MOF薄膜光催化剂及其制备方法和应用 Download PDF

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WO2022041852A1
WO2022041852A1 PCT/CN2021/093779 CN2021093779W WO2022041852A1 WO 2022041852 A1 WO2022041852 A1 WO 2022041852A1 CN 2021093779 W CN2021093779 W CN 2021093779W WO 2022041852 A1 WO2022041852 A1 WO 2022041852A1
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mof
nickel
foamed nickel
nickel foam
photocatalyst
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安太成
丁心
刘宏利
李桂英
赵惠军
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Guangdong University of Technology
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    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/348—Electrochemical processes, e.g. electrochemical deposition or anodisation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/007—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by irradiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8678—Removing components of undefined structure
    • B01D53/8687—Organic components
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39—Photocatalytic properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B01D2257/708—Volatile organic compounds V.O.C.'s
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/80—Employing electric, magnetic, electromagnetic or wave energy, or particle radiation
    • B01D2259/802—Visible light
    • 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
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/847—Nickel

Definitions

  • the invention belongs to the technical field of photocatalytic materials, and more particularly relates to a Ni-MOF thin film photocatalyst grown on the surface of foamed nickel in situ and a preparation method and application thereof.
  • MOFs as a member of emerging porous materials, have been widely used in the fields of gas adsorption, separation, and drug release, and MOFs have a large number of metal active sites, structural diversity, controllable pore size, large The advantages of specific surface area and good stability make it also have great application potential in the field of catalysis.
  • the synthesis of MOFs generally requires higher temperature, certain pressure and longer reaction time.
  • the synthesis of MOFs films is mainly based on hydrothermal and solvothermal methods.
  • the hydrothermal method and solvothermal method have the problems of poor controllability, long cycle, and high energy consumption, which make the production of MOFs membranes still face the problems of low efficiency and difficult to achieve controllable preparation.
  • the purpose of the present invention is to overcome the defects of the prior art, and provide a preparation method for in-situ growth of Ni-MOF thin film photocatalyst on the surface of foamed nickel.
  • the method uses nickel foam as a nickel source, applies a certain oxidation voltage to the nickel foam to precipitate nickel ions, and then utilizes nickel ions and organic ligands to self-assemble on the surface of the nickel foam to grow MOFs films in situ.
  • Another object of the present invention is to provide a Ni-MOF thin film photocatalyst prepared by the above method for in-situ growth on the surface of nickel foam.
  • Another object of the present invention is to provide the application of in-situ growth of Ni-MOF thin film photocatalyst on the surface of foamed nickel.
  • a preparation method for in-situ growth of Ni-MOF thin film photocatalyst on the surface of foamed nickel comprising the following steps:
  • the surface-activated nickel foam is used as the working electrode, the Pt is used as the counter electrode, and the Ag/AgCl is used as the reference electrode, and the surface-activated nickel foam is immersed in the methanol solution of the electrolyte 2-methylimidazole;
  • step S3 React the mixing system of step S2 at 30-120°C, apply an oxidizing voltage to the nickel foam of the working electrode, and leave it to stand after each pressurization, so that the nickel ions precipitated by the nickel foam and the 2-formaldehyde in the surrounding electrolyte
  • the coordination of imidazole occurs, and the Ni-MOF film is grown in situ on the surface of the nickel foam.
  • the nickel foam is taken out and washed with alcohols and deionized water, and dried in vacuum, that is, in situ on the surface of the nickel foam. Growth of Ni-MOF thin film photocatalysts.
  • the ultrasonic time in step S1 is 5-60 min.
  • the inorganic acid in step S1 is hydrochloric acid, sulfuric acid or nitric acid, and the concentration of the inorganic acid is 0.5-5 mol/L.
  • the molar ratio of 2-methylimidazole to methanol in the methanol solution of 2-methylimidazole in step S2 is 1:(10-100).
  • step S3 the number of times of applying the oxidation voltage is 1-10 times, the application of the oxidation voltage is 1-10V/time, and the time of applying the oxidation voltage is 1-1800s/time.
  • the alcohol substance in step S3 is methanol or ethanol.
  • a photocatalyst for in-situ growth of Ni-MOF thin film on the surface of foamed nickel is prepared by the method.
  • Ni-MOF thin film photocatalyst on the surface of nickel foam to degrade volatile organic compounds in the atmosphere driven by sunlight.
  • the volatile organic compound is ethyl acetate.
  • the photocatalytic degradation rate of the Ni-MOF film to gas-phase ethyl acetate reaches more than 72%, and the mineralization rate of the complete decomposition of ethyl acetate into CO 2 and H 2 O reaches more than 54%.
  • the invention uses foamed nickel with good electrical and thermal conductivity as a base, and prepares the surface of the foamed nickel by an electrochemical deposition method to grow Ni-MOF thin film photocatalysts in situ.
  • This method can rapidly synthesize MOFs under mild conditions, which greatly saves the reaction time and energy consumption, and has the advantages of simple process, easy operation, safety and environmental protection, and convenient application.
  • the electrochemical deposition method Metal ions can be released through electrode oxidation, avoiding subsequent steps of removing ions such as NO 3 - or Cl - involved in traditional preparation methods using metal salts.
  • the material synthesis method obtained by this preparation method is universal, and defects, pore size and particle size can be controlled and optimized by electrolyte, potential and reaction temperature.
  • the prepared photocatalyst film can efficiently catalyze the degradation of low-concentration VOCs under the driving of sunlight, and has excellent stability. This is because the MOFs film is highly dispersed on the surface of the nickel foam with macropores, which not only enhances the absorption and utilization of light, but also improves the mass transfer of VOCs; and because the conductivity of the nickel foam is conducive to the transmission of photogenerated electrons, reducing the amount of electrons. - The bulk recombination of holes can effectively improve the separation efficiency of photogenerated carriers, thereby improving the photocatalytic activity and stability of composite photocatalysts, and at the same time solving the assembly and application problems of MOFs catalysts in atmospheric treatment.
  • the present invention has the following beneficial effects:
  • the present invention utilizes the characteristics of foamed nickel with good electrical and thermal conductivity, and uses electrochemical deposition to prepare a Ni-MOF thin film photocatalyst in situ growth on the surface of foamed nickel. Combined with the semiconductor characteristics of MOFs and the characteristics of MOFs with good adsorption capacity for VOCs, the precipitated nickel ions are self-assembled with 2-methylimidazole in the electrolyte, and Ni-MOF film materials can be obtained on the surface of nickel foam.
  • the method of the present invention can not only overcome the problems of excessively long synthesis time and high energy consumption in common solvothermal methods, but also realize the controllable preparation of MOFs materials on the surface of foamed nickel, and at the same time solve the assembly and application problems of MOFs catalysts in atmospheric treatment. .
  • Ni-MOF thin film photocatalyst on the surface of nickel foam prepared by electrodeposition method in the present invention exhibits good adsorption capacity and excellent catalytic activity for typical VOCs (ethyl acetate).
  • VOCs ethyl acetate
  • the results of dark adsorption experiments showed that the adsorption of ethyl acetate on Ni-MOF films synthesized by electrochemical deposition reached the equilibrium of adsorption and desorption within 60 min, and the maximum adsorption rate was 24.1% of the initial concentration of ethyl acetate.
  • the photocatalytic degradation rate of gas-phase ethyl acetate can reach 86.8%, and the mineralization rate of ethyl acetate being completely decomposed into CO 2 and H 2 O also reaches 64.5%. It can be seen that the composite catalyst can solve the assembly and application problems of MOFs catalysts in atmospheric treatment, has great potential for large-scale preparation of supported photocatalyst materials, and is more conducive to industrial applications.
  • Example 1 is a scanning electron microscope photograph of in-situ growth of Ni-MOF films on the surface of nickel foam prepared in Example 1.
  • Example 2 is the kinetic curve of adsorption and photocatalytic degradation of gas-phase ethyl acetate by in-situ growth of Ni-MOF film on the surface of nickel foam obtained in Example 1.
  • step S2 The mixing system of step S2 is reacted at 50°C, and an oxidation voltage of 2V is applied to the nickel foam of the working electrode for 1 s, and the pressure is 10 times. , coordinated with 2-methylimidazole in the electrolyte to synthesize Ni-MOF film on the surface of nickel foam;
  • step S4 Take out the synthetic nickel foam obtained in step S3 and grow the Ni-MOF film in situ on the surface. After cross-washing with alcohols and deionized water, put it into a vacuum drying oven for drying to obtain the in-situ growth of Ni-MOF on the nickel foam. MOF photocatalyst thin film.
  • FIG. 1 is a scanning electron microscope photograph of the Ni-MOF film grown in situ on the surface of the nickel foam obtained in Example 1. It can be seen from Figure 1 that Ni-MOF grows on the surface of nickel foam in the form of a dense film.
  • 2 is the adsorption kinetic curve and photocatalytic degradation kinetic curve of the Ni-MOF film material obtained in Example 1 to gas-phase ethyl acetate. It can be seen from Figure 2 that within 60 min, the adsorption of ethyl acetate by the Ni-MOF film synthesized by electrodeposition method reached the equilibrium of adsorption and desorption, and the maximum adsorption rate was 24.1% of the initial concentration of ethyl acetate.
  • the photocatalytic degradation rate of ethyl acetate in gas phase by Ni-MOF film can reach 86.8%, and the mineralization rate at this time is 64.5%.
  • the results show that the photocatalyst has certain adsorption performance and high visible light catalytic activity.
  • the Ni-MOF thin film photocatalyst is a new material with certain adsorption capacity for VOCs and high photocatalytic activity.
  • step S2 The mixing system of step S2 is reacted at 120°C, and an oxidation voltage of 10V is applied to the nickel foam of the working electrode, the time is 1s, and the pressure is 1 time. , coordinated with 2-methylimidazole in the electrolyte to synthesize Ni-MOF film on the surface of nickel foam;
  • step S4 After the in-situ growth of the Ni-MOF film on the surface of the synthesized nickel foam obtained in step S3 is cross-washed with alcohols and deionized water, put it into a vacuum drying oven to dry, and obtain an in-situ on the surface of the nickel foam using an electrodeposition method. Growth of Ni-MOF thin film photocatalysts.
  • the adsorption of ethyl acetate on Ni-MOF films synthesized by electrodeposition reached the equilibrium of adsorption and desorption, and the maximum adsorption rate was 22.8% of the initial concentration of ethyl acetate.
  • the photocatalytic degradation rate of ethyl acetate in gas phase by Ni-MOF film can reach 78.2%, and the mineralization rate at this time is 59.5%.
  • step S2 The mixing system of step S2 is reacted at 70°C, and the oxidation voltage of 3V is applied to the nickel foam of the working electrode for 600s, and the pressure is 5 times. , coordinated with 2-methylimidazole in the electrolyte to synthesize Ni-MOF film on the surface of nickel foam;
  • step S4 in-situ growth of the Ni-MOF film on the surface of the synthesized nickel foam obtained in step S3, cross-washing with alcohols and deionized water, and drying in a vacuum drying oven to obtain the original raw material on the surface of the nickel foam using an electrodeposition method.
  • step S4 in-situ growth of the Ni-MOF film on the surface of the synthesized nickel foam obtained in step S3, cross-washing with alcohols and deionized water, and drying in a vacuum drying oven to obtain the original raw material on the surface of the nickel foam using an electrodeposition method.
  • the adsorption of ethyl acetate on Ni-MOF films synthesized by electrodeposition reached the equilibrium of adsorption and desorption, and the maximum adsorption rate was 27.3% of the initial concentration of ethyl acetate.
  • the photocatalytic degradation rate of ethyl acetate in gas phase by Ni-MOF film can reach 80.5%, and the mineralization rate at this time is 62.1%.
  • step S2 The mixing system of step S2 is reacted at 70°C, and an oxidation voltage of 1V is applied to the nickel foam of the working electrode, the time is 1800s, and the pressure is applied once. , coordinated with 2-methylimidazole in the electrolyte to synthesize Ni-MOF film on the surface of nickel foam;
  • step S4 in-situ growth of the Ni-MOF film on the surface of the synthesized nickel foam obtained in step S3, cross-washing with alcohols and deionized water, and drying in a vacuum drying oven to obtain the raw material on the surface of the nickel foam using an electrodeposition method.
  • step S4 in-situ growth of the Ni-MOF film on the surface of the synthesized nickel foam obtained in step S3, cross-washing with alcohols and deionized water, and drying in a vacuum drying oven to obtain the raw material on the surface of the nickel foam using an electrodeposition method.
  • the adsorption of ethyl acetate on Ni-MOF films synthesized by electrodeposition reached the equilibrium of adsorption and desorption, and the maximum adsorption rate was 20.7% of the initial concentration of ethyl acetate.
  • the photocatalytic degradation rate of ethyl acetate in gas phase by Ni-MOF film can reach 72%, and the mineralization rate at this time is 54%.
  • the adsorption of ethyl acetate by the Ni-MOF film synthesized by the electrodeposition method of the invention reaches the equilibrium of adsorption and desorption, and within 60 minutes, the maximum adsorption rate is more than 20.7% of the initial concentration of ethyl acetate.
  • the catalytic degradation rate can reach over 72%, and the corresponding mineralization rate is over 54%.
  • the results show that the Ni-MOF thin film photocatalyst has a certain adsorption capacity for VOCs, good photocatalytic activity and stability, which can not only overcome the problems of long synthesis time and high energy consumption by common solvothermal methods, but also facilitate the regulation of MOFs on the surface of nickel foam. film thickness. Driven by sunlight, the photocatalyst material can effectively degrade VOCs in the atmosphere, and at the same time, it can solve the assembly and application problems of MOFs catalysts in atmospheric treatment.

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Abstract

本发明属于光催化材料技术领域，公开了一种在泡沫镍表面原位生长Ni-MOF薄膜光催化剂及其制备方法和应用。该方法是将泡沫镍置于无机酸中浸泡超声，清洗和干燥后，制得表面活化的泡沫镍；然后采用三电极体系，将表面活化的泡沫镍作为工作电极，Pt作为对电极，Ag/AgCl作为参比电极，将该泡沫镍浸入电解液2-甲基咪唑的甲醇溶液中，在30～120℃下施加氧化电压，使泡沫镍表面释放出的镍离子与其周围电解液中的2-甲基咪唑进行自组装，冷却后取出泡沫镍并洗涤，干燥制得薄膜光催化剂。本发明光催化剂具有良好的光催化活性和稳定性，在太阳光的驱动下有效降解大气中的VOCs，同时解决MOFs催化剂在大气处理中的组装难题。

Description

一种在泡沫镍表面原位生长Ni-MOF薄膜光催化剂及其制备方法和应用 技术领域
本发明属于光催化材料技术领域，更具体地，涉及一种在泡沫镍表面原位生长Ni-MOF薄膜光催化剂及其制备方法和应用。
背景技术
近年来，MOFs材料作为新兴多孔材料的一员，已被广泛用于气体吸附、分离和药物释放等领域，而且MOFs材料具有大量的金属活性位点、结构多样性、可控的孔径、较大比表面积和良好的稳定性等优点，使其在催化领域也有着巨大的应用潜力。MOFs材料的合成一般需要较高的温度、一定的压力和较长的反应时间。而且大多数研究中，MOFs薄膜的合成主要以水热法和溶剂热法为主。但是水热法和溶剂热法具有可控性差、周期长、能量消耗大等问题，这使得MOFs膜的生产仍面临效率低且难以实现可控制备的问题。
发明内容
本发明的目的是为了克服现有技术的缺陷，提供了一种在泡沫镍表面原位生长Ni-MOF薄膜光催化剂的制备方法。该方法以泡沫镍为镍源，对泡沫镍加一定的氧化电压，使其析出镍离子，随后利用镍离子与有机配体在泡沫镍表面进行自组装，原位生长MOFs薄膜。
本发明的另一目的在于提供上述方法这制备的在泡沫镍表面原位生长Ni-MOF薄膜光催化剂。
本发明的再一目的在于提供在泡沫镍表面原位生长Ni-MOF薄膜光催化剂的应用。
本发明上述目的通过以下技术方案予以实现：
一种在泡沫镍表面原位生长Ni-MOF薄膜光催化剂的制备方法，包括如下步骤：
S1.将泡沫镍置于无机酸中浸泡超声，然后用去离子水清洗干净，经干燥，制得表面活化处理的泡沫镍；
S2.采用三电极体系，将表面活化的泡沫镍作为工作电极，Pt作为对电极，Ag/AgCl作为参比电极，将表面活化的泡沫镍浸入电解液2-甲基咪唑的甲醇溶液中；
S3.将步骤S2的混合系统在30～120℃下反应，在工作电极泡沫镍上施加氧化电压，每次加压后静置，使泡沫镍析出的镍离子与周围电解液中的2-甲基咪唑发生配位作用，在泡沫镍表面原位生长Ni-MOF薄膜，冷却至室温后，取出泡沫镍并将其用醇类物质和去离子水洗涤，真空干燥，即在泡沫镍表面原位生长Ni-MOF薄膜光催化剂。
优选地，步骤S1中所述超声的时间为5～60min。
优选地，步骤S1中所述无机酸为盐酸、硫酸或硝酸，所述无机酸的浓度为0.5～5mol/L。
优选地，步骤S2中所述2-甲基咪唑的甲醇溶液中2-甲基咪唑和甲醇的摩尔比为1：(10～100)。
优选地，步骤S3中所述施加氧化电压的次数为1～10次，所述施加氧化电压为1～10V/次，所述施加氧化电压的时间为1～1800s/次。
优选地，步骤S3中所述醇类物质为甲醇或乙醇。
一种在泡沫镍表面原位生长Ni-MOF薄膜光催化剂是由所述方法制备得到。
所述的在泡沫镍表面原位生长Ni-MOF薄膜光催化剂在太阳光驱动下降解大气中挥发性有机物中的应用。
优选地，所述挥发性有机物为乙酸乙酯。
优选地，所述Ni-MOF薄膜对气相乙酸乙酯的光催化降解率达到72％以上，同时乙酸乙酯完全分解成CO 2和H 2O的矿化率达到54％以上。。
本发明以具有良好导电/导热的泡沫镍为基底，通过电化学沉积法，制备出的泡沫镍表面原位生长Ni-MOF薄膜光催化剂。该方法可在温和的条件下快速合成MOFs材料，极大节约了反应时间和反应能耗，并且具有工艺简单、易操作、安全环保以及应用方便等优势，更为关键的是，电化学沉积法可通过电极氧化释放出金属离子，避免了传统制备方法使用金属盐涉及的NO 3 -或Cl -等后续对离子的去除步骤。这种制备方法得到的材料合成方法具有普适性，缺陷、孔径和粒径尺寸等都可以通过电解质、电位以及反应温度来进行调控和优化。制备所得的光催化剂薄膜在太阳光驱动下可高效催化降解低浓度VOCs，并具有优异的稳定性。这是由于MOFs薄膜高度分散在具有大孔的泡沫镍表面，既增强了对光的吸收和利用，又提高了VOC的传质；而且由于泡沫镍的导电性有利于光生电子的传输， 减少电子-空穴的体相复合，可有效提高光生载流子的分离效率，进而提高复合光催化剂的光催化活性和稳定性，同时解决了MOFs催化剂在大气处理中的组装和应用难题。
与现有技术相比，本发明具有以下有益效果：
1.本发明利用良好导电/导热性能的泡沫镍特性，使用电化学沉积制备出在泡沫镍表面原位生长Ni-MOF薄膜光催化剂。结合MOFs半导体特性和对VOCs具有良好吸附能力的MOFs的特性，使析出的镍离子与电解液中的2-甲基咪唑自组装，在泡沫镍表面可得到Ni-MOF膜材料。
2.本发明方法不仅能克服常用溶剂热法合成时间过长和能耗高等问题，而且还可实现泡沫镍表面MOFs材料的可控制备，同时解决了MOFs催化剂在大气处理中的组装和应用难题。
3.本发明使用电沉积法制备出的泡沫镍表面原位生长Ni-MOF薄膜光催化剂对典型VOCs(乙酸乙酯)展现出很好的吸附能力和优异的催化活性。暗吸附实验结果表明，在60min内，电化学沉积法合成的Ni-MOF薄膜对乙酸乙酯的吸附达到吸脱附平衡，最大吸附率为乙酸乙酯初始浓度的24.1％。同时对气相乙酸乙酯的光催化降解率可达到86.8％，此时乙酸乙酯完全分解成CO 2和H 2O的矿化率也达到64.5％。由此可见，该复合催化剂可解决MOFs催化剂在大气处理中的组装和应用难题，对于大规模制备负载型光催化剂材料具有非常大的潜力，更有利于工业应用。
附图说明
图1为实施例1制备出的泡沫镍表面原位生长Ni-MOF薄膜的扫描电镜照片。
图2为实施例1所得泡沫镍表面原位生长Ni-MOF薄膜对气相乙酸乙酯的吸附和光催化降解动力学曲线。
具体实施方式
下面结合说明书附图和具体实施例进一步说明本发明的内容，但不应理解为对本发明的限制。若未特别指明，实施例中所用的技术手段为本领域技术人员所熟知的常规手段。除非特别说明，本发明采用的试剂、方法和设备为本技术领域常规试剂、方法和设备。
实施例1
1.泡沫镍表面原位生长Ni-MOF薄膜的制备
S1.将泡沫镍置于1mol/L稀盐酸中浸泡超声10min，然后用去离子水清洗干净，经干燥制得表面活化处理的泡沫镍；
S2.将1：10的摩尔比的2-甲基咪唑与甲醇配成电解液；随后使用三电极体系进行实验，将表面活化的泡沫镍作为工作电极，Pt作为对电极，Ag/AgCl作为参比电极浸入电解液中；
S3.将步骤S2的混合系统在50℃下反应，在工作电极泡沫镍上加2V的氧化电压，时间为1s，加压10次，每次加压后静置30min，使泡沫镍析出镍离子，与电解液中的2-甲基咪唑发生配位作用，在泡沫镍表面合成Ni-MOF薄膜；
S4.取出步骤S3得到的合成的泡沫镍表面原位生长Ni-MOF薄膜，用醇类物质和去离子水交叉洗涤后，放入真空干燥箱中干燥，得到在泡沫镍上原位生长Ni-MOF光催化剂薄膜。
2.泡沫镍表面原位生长Ni-MOF薄膜的性能测试
图1为实施例1所得的在泡沫镍表面原位生长的Ni-MOF薄膜的扫描电镜照片。从图1中可知，Ni-MOF以致密的膜形式生长在泡沫镍表面。图2为实施例1所得的Ni-MOF薄膜材料对气相乙酸乙酯的吸附动力学曲线和光催化降解动力学曲线。由图2可看出，在60min内，电沉积法合成的Ni-MOF薄膜对乙酸乙酯的吸附达到吸脱附平衡，最大吸附率为乙酸乙酯初始浓度24.1％。并且在60min内，Ni-MOF膜对气相中乙酸乙酯的光催化降解率能达到86.8％，此时的矿化率为64.5％。结果表明，该光催化剂有一定的吸附性能，并且具有很高的可见光催化活性。该Ni-MOF薄膜光催化剂是对VOCs具有一定吸附能力和高光催化活性的新型材料。
实施例2
S1.将泡沫镍置于2mol/L稀盐酸中浸泡超声10min，然后用去离子水清洗干净，经干燥制得表面活化处理的泡沫镍；
S2.将1:100的摩尔比的2-甲基咪唑与甲醇配成电解液；随后使用三电极结构进行实验，将表面活化的泡沫镍作为工作电极，Pt作为对电极，Ag/AgCl作为参比电极浸入电解液中；
S3.将步骤S2的混合系统在120℃下反应，在工作电极泡沫镍上加10V的氧化电压，时间为1s，加压1次，每次加压后静置30min，使泡沫镍析出镍离子，与电解液中的2-甲基咪唑发生配位作用，在泡沫镍表面合成Ni-MOF薄膜；
S4.将步骤S3得到的合成的泡沫镍表面原位生长Ni-MOF膜用醇类物质和去离子水交叉洗涤后，放入真空干燥箱中干燥，得到使用电沉积法在泡沫镍表面原位生长Ni-MOF薄膜光催化剂。
在60min内，电沉积法合成的Ni-MOF薄膜对乙酸乙酯的吸附达到吸脱附平衡，最大吸附率为乙酸乙酯初始浓度22.8％。并且在60min内，Ni-MOF膜对气相中乙酸乙酯的光催化降解率能达到78.2％，此时的矿化率为59.5％。
实施例3
S1.将泡沫镍置于3mol/L稀盐酸中浸泡超声10min，然后用去离子水清洗干净，经干燥制得表面活化处理的泡沫镍；
S2.将1:50的摩尔比的2-甲基咪唑与甲醇配成电解液；随后使用三电极结构进行实验，将表面活化的泡沫镍作为工作电极，Pt作为对电极，Ag/AgCl作为参比电极浸入电解液中；
S3.将步骤S2的混合系统在70℃下反应，在工作电极泡沫镍上加3V的氧化电压，时间为600s，加压5次，每次加压后静置30min，使泡沫镍析出镍离子，与电解液中的2-甲基咪唑发生配位作用，在泡沫镍表面合成Ni-MOF薄膜；
S4.将步骤S3得到的合成的泡沫镍表面原位生长Ni-MOF膜,用醇类物质和去离子水交叉洗涤后，放入真空干燥箱中干燥，得到使用电沉积法在泡沫镍表面原位生长Ni-MOF薄膜光催化剂。
在60min内，电沉积法合成的Ni-MOF薄膜对乙酸乙酯的吸附达到吸脱附平衡，最大吸附率为乙酸乙酯初始浓度27.3％。并且在60min内，Ni-MOF膜对气相中乙酸乙酯的光催化降解率能达到80.5％，此时的矿化率为62.1％。
实施例4
S1.将泡沫镍置于4mol/L稀盐酸中浸泡超声10min，然后用去离子水清洗干净，经干燥制得表面活化处理的泡沫镍；
S2.将1:50的摩尔比的2-甲基咪唑与甲醇配成电解液；随后使用三电极结构进行实验，其中步骤S1中表面活化的泡沫镍作为工作电极，Pt作为对电极， Ag/AgCl作为参比电极浸入电解液中；
S3.将步骤S2的混合系统在70℃下反应，在工作电极泡沫镍上加1V的氧化电压，时间为1800s，加压1次，每次加压后静置30min，使泡沫镍析出镍离子，与电解液中的2-甲基咪唑发生配位作用，在泡沫镍表面合成Ni-MOF薄膜；
S4.将步骤S3得到的合成的泡沫镍表面原位生长Ni-MOF薄膜，用醇类物质和去离子水交叉洗涤后，放入真空干燥箱中干燥，得到使用电沉积法在泡沫镍表面原位生长Ni-MOF薄膜光催化剂。
在60min内，电沉积法合成的Ni-MOF薄膜对乙酸乙酯的吸附达到吸脱附平衡，最大吸附率为乙酸乙酯初始浓度20.7％。并且在60min内，Ni-MOF膜对气相中乙酸乙酯的光催化降解率能达到72％，此时的矿化率为54％。
本发明电沉积法合成的Ni-MOF薄膜对乙酸乙酯的吸附达到吸脱附平衡，在60min内，最大吸附率为乙酸乙酯初始浓度的20.7％以上，同时对气相中乙酸乙酯的光催化降解率能达到72％以上，相应的矿化率为54％以上。结果表明，该Ni-MOF薄膜光催化剂对VOCs具有一定吸附能力、良好的光催化活性和稳定性，不仅能克服常用溶剂热法合成时间过长和能耗高等问题，而且便于调控泡沫镍表面MOFs膜的厚度。该光催化剂材料在太阳光的驱动下，可以有效地降解大气中的VOCs，同时可以解决MOFs催化剂在大气处理中的组装和应用难题。
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合和简化，均应为等效的置换方式，都包含在本发明的保护范围之内。

Claims (10)

  1. 一种在泡沫镍表面原位生长Ni-MOF薄膜光催化剂的制备方法，其特征在于，包括如下步骤：
    S1.将泡沫镍置于无机酸中浸泡超声，然后用去离子水清洗干净，经干燥，制得表面活化处理的泡沫镍；
    S2.采用三电极体系，将表面活化的泡沫镍作为工作电极，Pt作为对电极，Ag/AgCl作为参比电极，将表面活化的泡沫镍浸入电解液2-甲基咪唑的甲醇溶液中；
    S3.将步骤S2的混合系统在30～120℃下反应，在工作电极泡沫镍上施加氧化电压，每次加压后静置，使泡沫镍析出的镍离子与周围电解液中的2-甲基咪唑发生配位作用，在泡沫镍表面原位生长Ni-MOF薄膜，冷却至室温后，取出泡沫镍并将其用醇类物质和去离子水洗涤，真空干燥，即在泡沫镍表面原位生长Ni-MOF薄膜光催化剂。
  2. 根据权利要求1所述的在泡沫镍表面原位生长Ni-MOF薄膜光催化剂的制备方法，其特征在于，步骤S1中所述超声的时间为5～60min。
  3. 根据权利要求1所述的在泡沫镍表面原位生长Ni-MOF薄膜光催化剂的制备方法，其特征在于，步骤S1中所述无机酸为盐酸、硫酸或硝酸，所述无机酸的浓度为0.5～5mol/L。
  4. 根据权利要求1所述的在泡沫镍表面原位生长Ni-MOF薄膜光催化剂的制备方法，其特征在于，步骤S2中所述2-甲基咪唑的甲醇溶液中2-甲基咪唑和甲醇的摩尔比为1：(10～100)。
  5. 根据权利要求1所述的在泡沫镍表面原位生长Ni-MOF薄膜光催化剂的制备方法，其特征在于，步骤S3中所述施加氧化电压的次数为1～10次，所述施加氧化电压为1～10V/次，所述施加氧化电压的时间为1～1800s/次。
  6. 根据权利要求1所述的在泡沫镍表面原位生长Ni-MOF薄膜光催化剂的制备方法，其特征在于，步骤S3中所述醇类物质为甲醇或乙醇。
  7. 一种在泡沫镍表面原位生长Ni-MOF薄膜光催化剂，其特征在于，所述光催化剂薄膜是由权利要求1-6任一项所述的方法制备得到。
  8. 权利要求7所述的在泡沫镍表面原位生长Ni-MOF薄膜光催化剂在太阳光驱动下降解大气中挥发性有机物中的应用。
  9. 根据权利要求8所述的在泡沫镍表面原位生长Ni-MOF薄膜光催化剂在太阳光驱动下降解大气中挥发性有机物中的应用，其特征在于，所述挥发性有机物为乙酸乙酯。
  10. 根据权利要求9所述的在泡沫镍表面原位生长Ni-MOF薄膜光催化剂在太阳光驱动下降解大气中挥发性有机物中的应用，其特征在于，所述Ni-MOF薄膜对气相乙酸乙酯的光催化降解率达到72％以上，同时乙酸乙酯完全分解成CO 2和H 2O的矿化率达到54％以上。
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