WO2016184322A1 - Nanometer composite photocatalytic material and preparation method thereof - Google Patents

Nanometer composite photocatalytic material and preparation method thereof Download PDF

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Publication number
WO2016184322A1
WO2016184322A1 PCT/CN2016/081387 CN2016081387W WO2016184322A1 WO 2016184322 A1 WO2016184322 A1 WO 2016184322A1 CN 2016081387 W CN2016081387 W CN 2016081387W WO 2016184322 A1 WO2016184322 A1 WO 2016184322A1
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graphene
sccm
metal
photocatalytic material
foam
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PCT/CN2016/081387
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French (fr)
Chinese (zh)
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杨与畅
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宝峰时尚国际控股有限公司
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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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/30—Tungsten
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/72—Copper
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • 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
    • B01J27/20—Carbon compounds
    • 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

Definitions

  • the invention belongs to the field of nano composite materials and photocatalysis technology, and particularly relates to a nano composite photocatalytic material and a preparation method thereof.
  • Metal oxides such as TiO 2 and WO 3 have become the most promising green environmentally friendly catalysts due to their stable chemical properties, strong resistance to photo-corrosion, poor solubility, non-toxicity, low cost and environmental friendliness.
  • the photocatalytic efficiency of pure TiO 2 and WO 3 is very low, and the absorption of sunlight is limited to the ultraviolet band, which greatly affects the utilization of solar energy and reduces the practical application value by composite doping of TiO 2 or WO 3 .
  • the formation of a composite material can effectively improve the photocatalytic activity of the photocatalytic metal oxide.
  • the technical problem to be solved by the present invention is to provide a nanocomposite photocatalytic material and a preparation method thereof, aiming at improving the photocatalytic activity of the photocatalytic material, increasing the utilization rate of the solar energy, and improving the practical value of the photocatalytic material.
  • the present invention is achieved by the method for preparing a nanocomposite photocatalytic material, comprising:
  • the metal foam is a porous structure, and the graphene is grown on a surface of the metal foam wall to form a three-dimensional structure;
  • a nano metal oxide catalytic material is grown on the graphene.
  • the present invention also provides a nanocomposite photocatalytic material comprising a porous metal foam, a plurality of graphenes grown on the metal foam, and a metal oxide catalyzed on the graphene.
  • the material, the plurality of graphenes are grown on the surface of the porous metal foam wall to form a three-dimensional structure.
  • the preparation method of the nano composite photocatalytic material has the following characteristics: (1) preparing a graphene to form a three-dimensional structure-supported composite material on a metal foam. (2) Make full use of foam metal-loaded graphene to form a three-dimensional structure to increase its specific surface area and the extremely high electron conductivity of graphene to improve the photocatalytic performance of the composite. (3)
  • the composite prepared by the invention combines the properties of graphene and metal oxide catalytic materials, and has good application prospects and economic benefits in the fields of environment, catalysis and the like.
  • FIG. 1 is a flow chart of a method for preparing a nanocomposite photocatalytic material provided by the present invention
  • FIG. 2 is a flow chart of a method for preparing a nanocomposite photocatalytic material provided by one embodiment of the present invention
  • Figure 3 is a scanning electron micrograph of foamed nickel-loaded graphene prepared by the preparation method provided in Figure 2;
  • FIG. 4 is a schematic perspective view of a three-dimensional structure formed by foam metal-loaded graphene
  • FIG. 5 is a schematic perspective view of a nanocomposite photocatalytic material formed
  • Figure 6 is a Raman spectrum of a nickel-supported single-layer graphene
  • Figure 7 is a Raman spectrum of foamed nickel-loaded double-layer graphene
  • Figure 8 is a scanning electron micrograph of a nickel-supported graphene-TiO 2 foam.
  • an embodiment of the present technical solution provides a method for preparing a nano composite photocatalytic material, and the method for preparing the nano composite photocatalytic material includes the steps of:
  • the metal foam may be nickel foam or copper foam or the like.
  • the surface of the metal foam can be polished by electrolysis, and the treatment process includes ionization reaction of the metal foam and high temperature treatment of impurities.
  • the ionization reaction process is: ionization reaction of the metal foam.
  • the nickel (or copper) foam is used as the anode, and the copper foil of the same size is used as the cathode.
  • the two poles are simultaneously immersed in the electrolytic cell, and the ionization reaction is performed for 5-8 minutes with a direct current voltage of 5-10 V, thereby removing the surface of the foam metal. Fine burrs and increased brightness.
  • the metal foam after the ionization reaction is washed and dried. Specifically, remove the foam metal and wash it with deionized water 30- After 60s, it was washed with anhydrous ethanol for 60-120s, and finally purged with high-purity nitrogen.
  • the high temperature processing of impurities is as follows: the surface treated foam metal is evacuated into the vacuum chamber (about 5-10 min). Then, the sample slowly enters the preheating chamber for heat treatment for 10-15 minutes, the temperature of the preheating chamber is 400-600 ° C, and the argon-oxygen mixed gas (70-90% argon gas 10-30%) is passed through the preheating chamber through 1000-2000 sccm. Oxygen), pressure 60-90Pa. Next, the sample enters the high temperature processing chamber for heat treatment at 800-950 ° C for 10-20 min, and the high temperature processing chamber is passed through 1000-3000 sccm of hydrogen and 300-700 sccm of argon gas at a pressure of 90-140 Pa.
  • the growth process is as follows:
  • the sample enters the growth chamber and is grown in four steps in the growth chamber.
  • the order is as follows: first, heating to 1000-1100 ° C and introducing 2000-3000 sccm of hydrogen and 1000-2000 sccm of methane / ethylene / acetylene for 15-20 min; secondly, introducing 1000-2000 sccm of hydrogen and 1300-1800 sccm of methane / ethylene / acetylene, time 10-20min; then, pass 1200-2200sccm of hydrogen and 500-1200sccm methane / ethylene / acetylene for 15-20min; reheat to 1000-1050 ° C and pass 500-1000sccm Hydrogen and 300-700 sccm methane/ethylene/acetylene for 5-10 min.
  • the sample enters the cooling chamber for rapid cooling for about 10-20 min and the chamber is passed through 2000-4000 sccm of hydrogen and 500-1000 sccm of methane/ethylene/acetylene. That is, a plurality of graphenes are grown on the pore walls of the metal foam to obtain a three-dimensional structure.
  • the three-dimensional structure formed by the growth of graphene on the porous metal foam wall has a high specific surface area and excellent electrical conductivity.
  • the metal oxide catalytic material may be TiO 2 or WO 3 or the like.
  • the step S102 may specifically include:
  • the metal foam-loaded graphene is immersed in a metal salt solution to form a first sample.
  • the metal foam-loaded graphene prepared in S101 was immersed in a metal salt solution for about 15 minutes.
  • the ambient temperature is maintained at 15-40 ° C and the humidity is 10-30%.
  • the metal solution may be a titanium salt solution or a tungsten salt solution.
  • the first sample is dried to obtain a second sample.
  • the first sample after the immersion is taken out to keep the humidity of the environment unchanged, and air-dried for about 12H.
  • the second sample is placed in an electric resistance furnace for sintering, and the sintering condition is 1H at 400 ° C - 500 ° C.
  • a surface of a metal or the like is plated with a TiO 2 film, that is, the metal is immersed in a TiO 2 alcohol or an aqueous solution, and then heated to form a TiO 2 film.
  • the TiO 2 film particles produced by the method have poor adhesion on the metal.
  • a large amount of particles are peeled off, resulting in few effective TiO 2 film nanoparticles on the metal surface.
  • any wind blown vibration, etc. will cause more TiO 2 particles to peel off, and the photocatalytic efficiency will continue to decrease.
  • the present invention provides a method for preparing a nanocomposite photocatalytic material having the following characteristics: (1) preparing a graphene to form a three-dimensional structure-supported composite material on a metal foam; 2) Make full use of foam metal-loaded graphene to form a three-dimensional structure to increase its specific surface area and extremely high electron conductivity of graphene to improve the photocatalytic performance of the composite; (3)
  • the composite prepared by the invention combines graphene and The properties of metal oxide catalytic materials have good application prospects and economic benefits in the fields of environment and catalysis.
  • the foamed nickel was used as the anode and the copper foil was used as the cathode.
  • the two poles were simultaneously immersed in the electrolytic cell and passed through a direct current (8 V) ionization reaction for 5 min to end the removal of the surface burrs and the increase in brightness.
  • the polished foamed nickel was removed and washed with deionized water for 50 s, then with absolute ethanol for 80 s, and finally purged with high purity nitrogen.
  • the electrolyte in the electrolytic cell is 12 g of urea, 150 g of ammonium persulfate, 800 ml of phosphoric acid, 500 ml of ethanol, 150 ml of isopropanol, and then poured into 800 ml of deionized water solution, and the mixture is uniformly stirred to complete the preparation of the electrolyte.
  • the S201 treated foamed nickel was laid flat on the feeding table of the CVD equipment, and the foamed nickel was sequentially vacuumed into the vacuum chamber (about 8 minutes); the preheating chamber was heated for 12 minutes, and the temperature of the preheating chamber was 500 °C. And preheating chamber through 1500sccm argon-oxygen mixture gas (80% argon, 20% oxygen), pressure 80Pa; into the high temperature processing chamber for 900 °C heat treatment for 15min, and the annealing chamber through 2000sccm of hydrogen and 500sccm of argon, pressure 130Pa;
  • the order is first heated to 1100 ° C and 2500 sccm of hydrogen and 2500 sccm of methane / ethylene / acetylene for 18 min; secondly 1500 sccm of hydrogen and 1500 sccm of methane / ethylene / acetylene for 15 min; then 1800 sccm of hydrogen And 800sccm methane / ethylene / acetylene, time is 18min; finally heated to 1000 ° C and passed 800sccm of hydrogen and 500sccm methane / ethylene / acetylene for 8min; enter the cooling chamber for about 15min rapid cooling and cooling chamber into 3000sccm Hydrogen and 800 sccm methane / ethylene / acetylene; into the discharge chamber, that is, complete foamed nickel growth graphene.
  • a preferred four-step growth allows for the growth of uniform and complete graphene.
  • the SEM of the prepared foamed nickel-loaded graphene is shown in Fig. 3.
  • the graphene is uniformly and completely supported on the foamed nickel, and the prepared graphene is transparent to clearly see the morphology of the foamed nickel, indicating that the graphene is relatively thin.
  • the number of layers is small.
  • the Raman spectrum of Figure 6 shows that the value of G peak ( ⁇ 1580 cm -1 ) is about 140, and the value of 2D peak ( ⁇ 2700 cm -1 ) is about 440, that is, the value of IG/I2D is 0.318 ⁇ 0.4, that is, graphene. It is a single layer.
  • Figure 7 shows that the value of the G peak ( ⁇ 1580 cm -1 ) is about 88, and the value of the 2D peak ( ⁇ 2700 cm -1 ) is about 80, that is, the value of IG/I2D is 1.1 (close to 1.25), that is, graphene is Double layer; while the peak intensity of D peak ( ⁇ 1350 cm -1 ) is very weak, it indicates that the graphene structure is intact.
  • Figures 6, 7 further illustrate the complete uniform loading of graphene on foamed nickel.
  • the foamed nickel loaded with graphene in step S202 was immersed in 200 ml of TiCl 4 solution for about 15 minutes.
  • the ambient temperature is maintained at 25 ° C and the humidity is 20%.
  • the sample after soaking was taken out and placed in a jig to keep the humidity of the environment constant, and the natural air was ventilated at 12H.
  • the dried sample was placed in an electric resistance furnace for sintering.
  • the sintering conditions were 1H sintered at 450 °C.
  • graphene can form a plurality of dangling bonds on the surface of the metal foam to effectively bond the TiO 2 nanoparticles.
  • more TiO 2 particles can be attached to the surface of the graphene, and the adhesion of these TiO 2 particles is also good, so that not only the photocatalytic efficiency is high, but also the graphene has an excessively large specific surface area and a large number of active sites.
  • the amount of TiO 2 particles is more and the adhesion is stronger.
  • graphene has a high electron mobility, which can effectively prolong the lifetime of carriers generated by photocatalysis, prevent the recombination of holes and electrons, and greatly improve the high catalytic efficiency.
  • Figure 8 is an SEM image of foamed nickel-loaded graphene-TiO 2 , from which it is seen that TiO 2 is uniformly and completely supported on graphene. It is indicated that this method produces high quality foamed nickel-loaded graphene-TiO 2 composite visible light catalytic material.
  • Embodiments of the present invention provide a nanocomposite photocatalytic material, including a metal foam, graphene supported on the metal foam, and a metal oxide catalytic material grown on the graphene.
  • the metal foam may be nickel foam or copper foam.
  • the metal oxide catalytic material may be TiO 2 or WO 3 .
  • the graphene is a single layer or a double layer structure and is uniformly supported on the metal foam. The metal oxide catalytic material is uniformly supported on the graphene.
  • the present invention provides a nanocomposite photocatalytic material that fully utilizes foamed nickel to load a plurality of graphenes to form a three-dimensional structure, and increases the specific surface area and the extremely high electron conductivity of the graphene to thereby improve the light of the composite material.
  • Catalytic properties combined with the properties of graphene and metal oxide catalytic materials, can have good application prospects and economic benefits in the fields of environment, catalysis and so on.

Abstract

A nanometer composite photocatalytic material and preparation method thereof. The nanometer composite photocatalytic material comprises a porous foam metal, a plurality of graphenes growing on the foam metal and catalytic materials of metallic oxide growing on the graphenes. The plurality of graphenes grow on a porous wall surface of the porous foam metal and form a three-dimensional structure.

Description

一种纳米复合光催化材料及其制备方法  Nano composite photocatalytic material and preparation method thereof 技术领域Technical field
本发明属于纳米复合材料和光催化技术领域，特别涉及一种纳米复合光催化材料及其制备方法。 The invention belongs to the field of nano composite materials and photocatalysis technology, and particularly relates to a nano composite photocatalytic material and a preparation method thereof.
背景技术Background technique
TiO2及WO3等金属氧化物因其化学性质稳定、抗光腐蚀能力强、难溶、无毒、成本低、对环境友好，已成为最具有开发前途的绿色环保型催化剂。但纯TiO2和WO3的光催化效率很低，且对太阳光的吸收仅限于紫外波段，大大影响了其对太阳能的利用率，降低了实际应用价值，通过复合掺杂TiO2或者WO3形成复合材料，可以有效提高光催化金属氧化物的光催化活性。因此，有必要提供一种含有光催化材料TiO2等的纳米复合光催化材料及其制备方法，以提升光催化材料的光催化活性，提升光催化材料的实用价值。 Metal oxides such as TiO 2 and WO 3 have become the most promising green environmentally friendly catalysts due to their stable chemical properties, strong resistance to photo-corrosion, poor solubility, non-toxicity, low cost and environmental friendliness. However, the photocatalytic efficiency of pure TiO 2 and WO 3 is very low, and the absorption of sunlight is limited to the ultraviolet band, which greatly affects the utilization of solar energy and reduces the practical application value by composite doping of TiO 2 or WO 3 . The formation of a composite material can effectively improve the photocatalytic activity of the photocatalytic metal oxide. Therefore, it is necessary to provide a nanocomposite photocatalytic material containing a photocatalytic material such as TiO 2 and a preparation method thereof to enhance the photocatalytic activity of the photocatalytic material and enhance the practical value of the photocatalytic material.
技术问题technical problem
本发明所要解决的技术问题在于提供一种纳米复合光催化材料及其制备方法，旨在提升光催化材料的光催化活性，增加对太阳能的利用率，提升光催化材料的实用价值。 The technical problem to be solved by the present invention is to provide a nanocomposite photocatalytic material and a preparation method thereof, aiming at improving the photocatalytic activity of the photocatalytic material, increasing the utilization rate of the solar energy, and improving the practical value of the photocatalytic material.
技术解决方案Technical solution
本发明是这样实现的，一种纳米复合光催化材料的制备方法，包括：The present invention is achieved by the method for preparing a nanocomposite photocatalytic material, comprising:
在泡沫金属上生长多个石墨烯；所述泡沫金属为多孔结构，所述石墨烯生长于所述泡沫金属孔壁表面形成三维结构；以及Growing a plurality of graphene on the metal foam; the metal foam is a porous structure, and the graphene is grown on a surface of the metal foam wall to form a three-dimensional structure;
在所述石墨烯上生长纳米金属氧化物催化材料。A nano metal oxide catalytic material is grown on the graphene.
本发明还提供一种纳米复合光催化材料，所述纳米复合光催化材料包括多孔的泡沫金属、生长于所述泡沫金属上的多个石墨烯以及生长于所述石墨烯上的金属氧化物催化材料，所述多个石墨烯生长于多孔的泡沫金属孔壁表面形成三维结构。The present invention also provides a nanocomposite photocatalytic material comprising a porous metal foam, a plurality of graphenes grown on the metal foam, and a metal oxide catalyzed on the graphene. The material, the plurality of graphenes are grown on the surface of the porous metal foam wall to form a three-dimensional structure.
有益效果Beneficial effect
本发明与现有技术相比，有益效果在于：本实施方式提供纳米复合光催化材料的制备方法具有如下特点（1）制备方法上，在泡沫金属上制备石墨烯形成三维结构负载型的复合材料；（2）充分利用泡沫金属负载石墨烯形成三维结构增大其比表面积和石墨烯极高的电子传导率从而提高复合材料的光催化性能。（3）本发明制备的复合物，结合了石墨烯和金属氧化物催化材料的性质，可在环境、催化等领域有着较好的应用前景和经济效益。 Compared with the prior art, the present invention has the beneficial effects that the preparation method of the nano composite photocatalytic material has the following characteristics: (1) preparing a graphene to form a three-dimensional structure-supported composite material on a metal foam. (2) Make full use of foam metal-loaded graphene to form a three-dimensional structure to increase its specific surface area and the extremely high electron conductivity of graphene to improve the photocatalytic performance of the composite. (3) The composite prepared by the invention combines the properties of graphene and metal oxide catalytic materials, and has good application prospects and economic benefits in the fields of environment, catalysis and the like.
附图说明DRAWINGS
图1是本发明提供的纳米复合光催化材料的制备方法的流程图；1 is a flow chart of a method for preparing a nanocomposite photocatalytic material provided by the present invention;
图2是本发明一个具体实施提供的纳米复合光催化材料的制备方法的流程图；2 is a flow chart of a method for preparing a nanocomposite photocatalytic material provided by one embodiment of the present invention;
图3是图2提供的制备方法制备的泡沫镍负载石墨烯的扫描电镜照片；Figure 3 is a scanning electron micrograph of foamed nickel-loaded graphene prepared by the preparation method provided in Figure 2;
图4为泡沫金属负载石墨烯后形成的三维结构的立体示意图;4 is a schematic perspective view of a three-dimensional structure formed by foam metal-loaded graphene;
图5为形成的纳米复合光催化材料的立体示意图；5 is a schematic perspective view of a nanocomposite photocatalytic material formed;
图6为泡沫镍负载单层石墨烯的拉曼光谱图；Figure 6 is a Raman spectrum of a nickel-supported single-layer graphene;
图7为泡沫镍负载双层石墨烯的拉曼光谱图；Figure 7 is a Raman spectrum of foamed nickel-loaded double-layer graphene;
图8为泡沫镍负载石墨烯—TiO2的扫描电镜照片。Figure 8 is a scanning electron micrograph of a nickel-supported graphene-TiO 2 foam.
本发明的实施方式Embodiments of the invention
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合附图及实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。The present invention will be further described in detail below with reference to the accompanying drawings and embodiments. It is understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
请参阅图1，本技术方案实施方式提供一种纳米复合光催化材料的制备方法，所述纳米复合光催化材料的制备方法包括步骤：Referring to FIG. 1 , an embodiment of the present technical solution provides a method for preparing a nano composite photocatalytic material, and the method for preparing the nano composite photocatalytic material includes the steps of:
S101，在泡沫金属上生长多个石墨烯。S101, growing a plurality of graphene on the metal foam.
本实施方式中，泡沫金属可以为泡沫镍或者泡沫铜等。其中，在生长之前，还可通过电解法对泡沫金属的表面进行抛光处理，处理过程包括对泡沫金属进行电离反应及高温处理杂质。In this embodiment, the metal foam may be nickel foam or copper foam or the like. Among them, before the growth, the surface of the metal foam can be polished by electrolysis, and the treatment process includes ionization reaction of the metal foam and high temperature treatment of impurities.
电离反应过程为：对泡沫金属进行电离反应。具体的，将泡沫镍（或铜）作为阳极，同样尺寸的铜箔作为阴极，两极同时浸入到电解槽中，通以5-10V的直流电压进行电离反应3-8min，从而达到泡沫金属表面除去细微毛刺和光亮度增大。然后，对电离反应后的泡沫金属进行清洗干燥。具体的，取出泡沫金属用去离子水清洗30- 60s，再用无水乙醇清洗60- 120s，最后使用高纯氮气进行吹扫干净。The ionization reaction process is: ionization reaction of the metal foam. Specifically, the nickel (or copper) foam is used as the anode, and the copper foil of the same size is used as the cathode. The two poles are simultaneously immersed in the electrolytic cell, and the ionization reaction is performed for 5-8 minutes with a direct current voltage of 5-10 V, thereby removing the surface of the foam metal. Fine burrs and increased brightness. Then, the metal foam after the ionization reaction is washed and dried. Specifically, remove the foam metal and wash it with deionized water 30- After 60s, it was washed with anhydrous ethanol for 60-120s, and finally purged with high-purity nitrogen.
高温处理杂质过程为：将表面处理过的泡沫金属进入真空室抽真空（约5-10min）。接着，样品缓慢进入预热室进行10-15min的加热处理，预热室的温度为400-600℃且预热室内通1000-2000sccm的氩氧混合气（70-90%氩气10-30%氧气），压力60-90Pa。接着，样品进入高温处理室进行800-950℃加热处理10-20min，且高温处理室通入1000-3000sccm的氢气和300-700sccm的氩气，压力为90-140Pa。The high temperature processing of impurities is as follows: the surface treated foam metal is evacuated into the vacuum chamber (about 5-10 min). Then, the sample slowly enters the preheating chamber for heat treatment for 10-15 minutes, the temperature of the preheating chamber is 400-600 ° C, and the argon-oxygen mixed gas (70-90% argon gas 10-30%) is passed through the preheating chamber through 1000-2000 sccm. Oxygen), pressure 60-90Pa. Next, the sample enters the high temperature processing chamber for heat treatment at 800-950 ° C for 10-20 min, and the high temperature processing chamber is passed through 1000-3000 sccm of hydrogen and 300-700 sccm of argon gas at a pressure of 90-140 Pa.
生长过程具体如下：The growth process is as follows:
样品进入生长室，在生长室内进行四步生长。顺序依次为：首先，加热到1000-1100℃且通入2000-3000sccm的氢气和1000-2000sccm甲烷/乙烯/乙炔，时间为15-20min；其次，通入1000-2000sccm的氢气和1300-1800sccm甲烷/乙烯/乙炔，时间为10-20min；然后，通入1200-2200sccm的氢气和500-1200sccm甲烷/乙烯/乙炔，时间为15-20min；再加热到1000-1050℃且通入500-1000sccm的氢气和300-700sccm甲烷/乙烯/乙炔，时间为5-10min。最后，样品进入冷却室进行约10-20min的快速冷却且冷却室内通入2000-4000sccm的氢气和500-1000sccm甲烷/乙烯/乙炔。即完成在泡沫金属孔壁上生长多个石墨烯，得到三维结构。The sample enters the growth chamber and is grown in four steps in the growth chamber. The order is as follows: first, heating to 1000-1100 ° C and introducing 2000-3000 sccm of hydrogen and 1000-2000 sccm of methane / ethylene / acetylene for 15-20 min; secondly, introducing 1000-2000 sccm of hydrogen and 1300-1800 sccm of methane / ethylene / acetylene, time 10-20min; then, pass 1200-2200sccm of hydrogen and 500-1200sccm methane / ethylene / acetylene for 15-20min; reheat to 1000-1050 ° C and pass 500-1000sccm Hydrogen and 300-700 sccm methane/ethylene/acetylene for 5-10 min. Finally, the sample enters the cooling chamber for rapid cooling for about 10-20 min and the chamber is passed through 2000-4000 sccm of hydrogen and 500-1000 sccm of methane/ethylene/acetylene. That is, a plurality of graphenes are grown on the pore walls of the metal foam to obtain a three-dimensional structure.
由图4可看出，石墨烯生长于多孔结构的泡沫金属孔壁上所形成的三维结构，具有高的比表面积、优异的导电性。As can be seen from Fig. 4, the three-dimensional structure formed by the growth of graphene on the porous metal foam wall has a high specific surface area and excellent electrical conductivity.
S102，在石墨烯上生长金属氧化物催化材料。S102, growing a metal oxide catalytic material on the graphene.
所述金属氧化物催化材料可以为TiO2或者WO3等。S102步骤可以具体包括：The metal oxide catalytic material may be TiO 2 or WO 3 or the like. The step S102 may specifically include:
第一步，将所述泡沫金属负载石墨烯浸泡于金属盐溶液中，形成第一样品。In a first step, the metal foam-loaded graphene is immersed in a metal salt solution to form a first sample.
将S101制备的所述泡沫金属负载石墨烯浸入到金属盐溶液中浸泡约15min。环境的温度保持15-40℃，湿度为10-30%。所述金属溶液可以为钛盐溶液或钨盐溶液。所述钛盐溶液可以为TiCl4溶液、钛酸四丁酯溶液或钛酸四丁酯：乙醇（体积比）=1:2-1:4的混合溶液。The metal foam-loaded graphene prepared in S101 was immersed in a metal salt solution for about 15 minutes. The ambient temperature is maintained at 15-40 ° C and the humidity is 10-30%. The metal solution may be a titanium salt solution or a tungsten salt solution. The titanium salt solution may be a mixed solution of a TiCl 4 solution, a tetrabutyl titanate solution or a tetrabutyl titanate:ethanol (volume ratio)=1:2-1:4.
第二步，晾干第一样品，得到第二样品。具体的，将浸泡后的第一样品取出保持环境的湿度不变，自然通风晾干约12H。In the second step, the first sample is dried to obtain a second sample. Specifically, the first sample after the immersion is taken out to keep the humidity of the environment unchanged, and air-dried for about 12H.
第三步，将第二样品放入电阻炉内烧结，烧结条件为400℃-500℃下烧结1H。In the third step, the second sample is placed in an electric resistance furnace for sintering, and the sintering condition is 1H at 400 ° C - 500 ° C.
传统做法是在金属等表面镀上TiO2薄膜，即将金属浸泡在TiO2醇或水溶液中，再拿出加热，形成TiO2薄膜。该方法产生的TiO2薄膜颗粒在金属上的粘结性很差，在高温加热形成TiO2薄膜的过程中，大量颗粒会剥落，造成金属表面的有效TiO2薄膜纳米颗粒很少。在之后的使用过程中，任何风吹振动等都会造成更多TiO2颗粒剥落，光催化效率会不断下降。Conventionally, a surface of a metal or the like is plated with a TiO 2 film, that is, the metal is immersed in a TiO 2 alcohol or an aqueous solution, and then heated to form a TiO 2 film. The TiO 2 film particles produced by the method have poor adhesion on the metal. During the high temperature heating to form the TiO 2 film, a large amount of particles are peeled off, resulting in few effective TiO 2 film nanoparticles on the metal surface. In the subsequent use, any wind blown vibration, etc. will cause more TiO 2 particles to peel off, and the photocatalytic efficiency will continue to decrease.
因此，本发明与现有技术相比，本实施方式提供纳米复合光催化材料的制备方法具有如下特点（1）制备方法上，在泡沫金属上制备石墨烯形成三维结构负载型的复合材料；（2）充分利用泡沫金属负载石墨烯形成三维结构增大其比表面积和石墨烯极高的电子传导率从而提高复合材料的光催化性能；（3）本发明制备的复合物，结合了石墨烯和金属氧化物催化材料的性质，可在环境、催化等领域有着较好的应用前景和经济效益。Therefore, compared with the prior art, the present invention provides a method for preparing a nanocomposite photocatalytic material having the following characteristics: (1) preparing a graphene to form a three-dimensional structure-supported composite material on a metal foam; 2) Make full use of foam metal-loaded graphene to form a three-dimensional structure to increase its specific surface area and extremely high electron conductivity of graphene to improve the photocatalytic performance of the composite; (3) The composite prepared by the invention combines graphene and The properties of metal oxide catalytic materials have good application prospects and economic benefits in the fields of environment and catalysis.
请参阅图2，下面以一个具体实施例来说明一种泡沫镍负载石墨烯—TiO2复合可见光催化材料的制备方法，具体包括：Referring to FIG. 2, a method for preparing a foamed nickel-loaded graphene-TiO 2 composite visible light catalytic material is described below by using a specific embodiment, which specifically includes:
S201，通过电解法对泡沫镍进行表面抛光处理。S201, surface-polishing the nickel foam by electrolysis.
将泡沫镍作为阳极，铜箔作为阴极，两极同时浸入到电解槽中，通以直流（8V）电离反应5min，以去除表面的毛刺和光亮度增加为结束。取出抛光后的泡沫镍用去离子水清洗50s，再用无水乙醇清洗80s，最后使用高纯氮气进行吹扫干净。The foamed nickel was used as the anode and the copper foil was used as the cathode. The two poles were simultaneously immersed in the electrolytic cell and passed through a direct current (8 V) ionization reaction for 5 min to end the removal of the surface burrs and the increase in brightness. The polished foamed nickel was removed and washed with deionized water for 50 s, then with absolute ethanol for 80 s, and finally purged with high purity nitrogen.
电解槽中的电解液为12g的尿素、150g的过硫酸铵、800ml的磷酸、500ml乙醇、150ml异丙醇，再一起倒入800ml的去离子水溶液中，均匀搅拌即可完成电解液的配制。The electrolyte in the electrolytic cell is 12 g of urea, 150 g of ammonium persulfate, 800 ml of phosphoric acid, 500 ml of ethanol, 150 ml of isopropanol, and then poured into 800 ml of deionized water solution, and the mixture is uniformly stirred to complete the preparation of the electrolyte.
S202，在泡沫镍上生长多个石墨烯。S202, growing a plurality of graphene on the foamed nickel.
将S201处理过的泡沫镍平整的铺在CVD设备的进料台上，泡沫镍依次进入真空室抽真空（约8min）；进入预热室进行12min的加热处理，预热室的温度为500℃且预热室内通1500sccm的氩氧混合气（80%氩气，20%氧气），压力80Pa；进入高温处理室进行900℃加热处理15min，且退火室通2000sccm的氢气和500sccm的氩气，压力130Pa；The S201 treated foamed nickel was laid flat on the feeding table of the CVD equipment, and the foamed nickel was sequentially vacuumed into the vacuum chamber (about 8 minutes); the preheating chamber was heated for 12 minutes, and the temperature of the preheating chamber was 500 °C. And preheating chamber through 1500sccm argon-oxygen mixture gas (80% argon, 20% oxygen), pressure 80Pa; into the high temperature processing chamber for 900 °C heat treatment for 15min, and the annealing chamber through 2000sccm of hydrogen and 500sccm of argon, pressure 130Pa;
进入生长室，在生长室内进行四步生长。顺序依次为首先加热到1100℃且通入2500sccm的氢气和2500sccm甲烷/乙烯/乙炔，时间为18min；其次通入1500sccm的氢气和1500sccm甲烷/乙烯/乙炔，时间为15min；然后通入1800sccm的氢气和800sccm甲烷/乙烯/乙炔，时间为18min；最后加热到1000℃且通入800sccm的氢气和500sccm甲烷/乙烯/乙炔，时间为8min；进入冷却室进行约15min的快速冷却且冷却室内通入3000sccm的氢气和800sccm甲烷/乙烯/乙炔；进入出料室，即完成泡沫镍生长石墨烯。优选的四步生长，可以生长均匀完整的石墨烯。Enter the growth chamber and grow in four steps in the growth chamber. The order is first heated to 1100 ° C and 2500 sccm of hydrogen and 2500 sccm of methane / ethylene / acetylene for 18 min; secondly 1500 sccm of hydrogen and 1500 sccm of methane / ethylene / acetylene for 15 min; then 1800 sccm of hydrogen And 800sccm methane / ethylene / acetylene, time is 18min; finally heated to 1000 ° C and passed 800sccm of hydrogen and 500sccm methane / ethylene / acetylene for 8min; enter the cooling chamber for about 15min rapid cooling and cooling chamber into 3000sccm Hydrogen and 800 sccm methane / ethylene / acetylene; into the discharge chamber, that is, complete foamed nickel growth graphene. A preferred four-step growth allows for the growth of uniform and complete graphene.
制备得到的泡沫镍负载石墨烯的SEM如图3所示，石墨烯均匀完整的负载在泡沫镍上，且所制备的石墨烯透明可以清晰看到泡沫镍的形貌，说明石墨烯比较薄，层数较少。图6拉曼光谱发现G峰（～1580 cm-1）的值约为140，2D峰（～2700 cm-1）的值约为440，即IG/I2D的值为0.318<0.4，即石墨烯为单层。图7发现G峰（～1580 cm-1）的值约为88，2D峰（～2700 cm-1）的值约为80，即IG/I2D的值为1.1（接近1.25），即石墨烯为双层；同时D峰（～1350 cm-1）峰强非常弱，则说明石墨烯结构完整。图6，7进一步说明了石墨烯完整均匀的负载在泡沫镍上。The SEM of the prepared foamed nickel-loaded graphene is shown in Fig. 3. The graphene is uniformly and completely supported on the foamed nickel, and the prepared graphene is transparent to clearly see the morphology of the foamed nickel, indicating that the graphene is relatively thin. The number of layers is small. The Raman spectrum of Figure 6 shows that the value of G peak (~1580 cm -1 ) is about 140, and the value of 2D peak (~2700 cm -1 ) is about 440, that is, the value of IG/I2D is 0.318<0.4, that is, graphene. It is a single layer. Figure 7 shows that the value of the G peak (~1580 cm -1 ) is about 88, and the value of the 2D peak (~2700 cm -1 ) is about 80, that is, the value of IG/I2D is 1.1 (close to 1.25), that is, graphene is Double layer; while the peak intensity of D peak (~1350 cm -1 ) is very weak, it indicates that the graphene structure is intact. Figures 6, 7 further illustrate the complete uniform loading of graphene on foamed nickel.
S203，在石墨烯上生长纳米TiO2催化材料。S203, growing a nano TiO 2 catalytic material on the graphene.
将步骤S202负载石墨烯的泡沫镍浸入到200ml的TiCl4溶液中浸泡约15min。环境的温度保持25℃，湿度为20%。将浸泡后的样品取出放在治具中保持环境的湿度不变，自然通风12H晾干。将晾干后的样品放入电阻炉内烧结。烧结条件为450℃下烧结1H。The foamed nickel loaded with graphene in step S202 was immersed in 200 ml of TiCl 4 solution for about 15 minutes. The ambient temperature is maintained at 25 ° C and the humidity is 20%. The sample after soaking was taken out and placed in a jig to keep the humidity of the environment constant, and the natural air was ventilated at 12H. The dried sample was placed in an electric resistance furnace for sintering. The sintering conditions were 1H sintered at 450 °C.
请参阅图5，本发明中石墨烯可以在泡沫金属表面上形成很多悬挂键，有效键合住TiO2纳米颗粒。这样，在石墨烯表面可以附着更多的TiO2颗粒，而且这些TiO2颗粒的粘结性还很好，这样，不仅光催化效率高，石墨烯有超大的比表面积，超多的活性点位，TiO2颗粒数量更多，且附着力更强，同时，石墨烯由于电子迁移率高，可以有效延长光催化产生的载流子的寿命，防止空穴和电子复合，大幅提升高催化效率。Referring to FIG. 5, in the present invention, graphene can form a plurality of dangling bonds on the surface of the metal foam to effectively bond the TiO 2 nanoparticles. In this way, more TiO 2 particles can be attached to the surface of the graphene, and the adhesion of these TiO 2 particles is also good, so that not only the photocatalytic efficiency is high, but also the graphene has an excessively large specific surface area and a large number of active sites. The amount of TiO 2 particles is more and the adhesion is stronger. At the same time, graphene has a high electron mobility, which can effectively prolong the lifetime of carriers generated by photocatalysis, prevent the recombination of holes and electrons, and greatly improve the high catalytic efficiency.
图8为泡沫镍负载石墨烯—TiO2的SEM图，从图上看出TiO2均匀完整的负载在石墨烯上。说明此方法制备出了高质量的泡沫镍负载石墨烯—TiO2复合可见光催化材料。Figure 8 is an SEM image of foamed nickel-loaded graphene-TiO 2 , from which it is seen that TiO 2 is uniformly and completely supported on graphene. It is indicated that this method produces high quality foamed nickel-loaded graphene-TiO 2 composite visible light catalytic material.
本发明实施例提供一种纳米复合光催化材料，所述纳米复合光催化材料包括泡沫金属、负载于所述泡沫金属上的石墨烯以及生长于所述石墨烯上的金属氧化物催化材料。所述泡沫金属可以为泡沫镍或泡沫铜。所述金属氧化物催化材料可以为TiO2或者WO3。所述石墨烯为单层或者双层结构，且均匀负载于所述泡沫金属上。所述金属氧化物催化材料均匀负载于所述石墨烯上。Embodiments of the present invention provide a nanocomposite photocatalytic material, including a metal foam, graphene supported on the metal foam, and a metal oxide catalytic material grown on the graphene. The metal foam may be nickel foam or copper foam. The metal oxide catalytic material may be TiO 2 or WO 3 . The graphene is a single layer or a double layer structure and is uniformly supported on the metal foam. The metal oxide catalytic material is uniformly supported on the graphene.
本发明与现有技术相比，本实施方式提供纳米复合光催化材料充分利用泡沫镍负载多个石墨烯形成三维结构，增大其比表面积和石墨烯极高电子传导率从而提高复合材料的光催化性能，并且结合了石墨烯和金属氧化物催化材料的性质，可在环境、催化等领域有着较好的应用前景和经济效益。Compared with the prior art, the present invention provides a nanocomposite photocatalytic material that fully utilizes foamed nickel to load a plurality of graphenes to form a three-dimensional structure, and increases the specific surface area and the extremely high electron conductivity of the graphene to thereby improve the light of the composite material. Catalytic properties, combined with the properties of graphene and metal oxide catalytic materials, can have good application prospects and economic benefits in the fields of environment, catalysis and so on.
以上所述仅为本发明的较佳实施例，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。The above is only the preferred embodiment of the present invention, and is not intended to limit the present invention. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the scope of the present invention. within.

Claims (10)

  1. 一种纳米复合光催化材料，所述纳米复合光催化材料包括多孔的泡沫金属、生长于所述泡沫金属上的多个石墨烯以及生长于所述石墨烯上的金属氧化物催化材料，所述多个石墨烯生长于多孔的泡沫金属孔壁表面形成三维结构。 A nanocomposite photocatalytic material comprising a porous metal foam, a plurality of graphene grown on the metal foam, and a metal oxide catalytic material grown on the graphene, A plurality of graphenes are grown on the surface of the porous metal foam wall to form a three-dimensional structure.
  2. 如权利要求1所述的纳米复合光催化材料，其特征在于，所述泡沫金属为泡沫镍或泡沫铜，所述金属氧化物催化材料为TiO2或者WO3。The nanocomposite photocatalytic material according to claim 1, wherein the metal foam is nickel foam or copper foam, and the metal oxide catalytic material is TiO 2 or WO 3 .
  3. 如权利要求1所述的纳米复合光催化材料，其特征在于，所述石墨烯为单层或者双层结构，且均匀生长于所述泡沫金属上。The nanocomposite photocatalytic material according to claim 1, wherein the graphene is a single layer or a double layer structure and is uniformly grown on the metal foam.
  4. 如权利要求3所述的纳米复合光催化材料，其特征在于，所述金属氧化物催化材料均匀负载于所述石墨烯上。The nanocomposite photocatalytic material according to claim 3, wherein the metal oxide catalytic material is uniformly supported on the graphene.
  5. 如权利要求3所述的纳米复合光催化材料，其特征在于，石墨烯呈连续状形成三维结构。The nanocomposite photocatalytic material according to claim 3, wherein the graphene is continuously formed into a three-dimensional structure.
  6. 一种纳米复合光催化材料的制备方法，包括步骤：A method for preparing a nano composite photocatalytic material, comprising the steps of:
    在泡沫金属上生长多个石墨烯；所述泡沫金属为多孔结构，所述石墨烯生长于所述泡沫金属孔壁表面形成三维结构；以及Growing a plurality of graphene on the metal foam; the metal foam is a porous structure, and the graphene is grown on a surface of the metal foam wall to form a three-dimensional structure;
    在所述石墨烯上生长纳米金属氧化物催化材料。A nano metal oxide catalytic material is grown on the graphene.
  7. 如权利要求6所述的纳米复合光催化材料的制备方法，其特征在于，在泡沫金属上生长多个石墨烯的步骤之前，还包括步骤：The method for preparing a nanocomposite photocatalytic material according to claim 6, wherein before the step of growing a plurality of graphene on the metal foam, the method further comprises the steps of:
    通过电解法将泡沫金属的表面进行抛光处理，处理过程包括对泡沫金属进行电离反应及高温处理杂质。The surface of the metal foam is polished by electrolysis, which involves ionization of the metal foam and high temperature treatment of impurities.
  8. 如权利要求6所述的纳米复合光催化材料的制备方法，其特征在于，在泡沫金属上生长多个石墨烯的步骤包括下述四步生长过程：The method of preparing a nanocomposite photocatalytic material according to claim 6, wherein the step of growing a plurality of graphene on the metal foam comprises the following four-step growth process:
    首先，加热到1000-1100℃且通入2000-3000sccm的氢气和1000-2000sccm甲烷/乙烯/乙炔，时间为15-20min；First, heating to 1000-1100 ° C and introducing 2000-3000 sccm of hydrogen and 1000-2000 sccm methane / ethylene / acetylene, time is 15-20min;
    其次，通入1000-2000sccm的氢气和1300-1800sccm甲烷/乙烯/乙炔，时间为10-20min；Next, 1000-2000 sccm of hydrogen and 1300-1800 sccm of methane/ethylene/acetylene are introduced for 10-20 min;
    然后，通入1200-2200sccm的氢气和500-1200sccm甲烷/乙烯/乙炔，时间为15-20min；再加热到1000-1050℃且通入500-1000sccm的氢气和300-700sccm甲烷/乙烯/乙炔，时间为5-10min；Then, pass 1200-2200 sccm of hydrogen and 500-1200 sccm of methane/ethylene/acetylene for 15-20 min; reheat to 1000-1050 ° C and pass 500-1000 sccm of hydrogen and 300-700 sccm of methane/ethylene/acetylene. The time is 5-10min;
    最后，进入冷却室进行约10-20min的快速冷却且冷却室内通入2000-4000sccm的氢气和500-1000sccm甲烷/乙烯/乙炔。Finally, the cooling chamber is introduced into the rapid cooling for about 10-20 min and the cooling chamber is passed through 2000-4000 sccm of hydrogen and 500-1000 sccm of methane/ethylene/acetylene.
  9. 如权利要求6所述的纳米复合光催化材料的制备方法，其特征在于，在所述石墨烯上生长纳米金属氧化物催化材料的步骤具体包括下述步骤：The method for preparing a nanocomposite photocatalytic material according to claim 6, wherein the step of growing the nano metal oxide catalytic material on the graphene comprises the following steps:
    第一步，将所述泡沫金属负载石墨烯浸入到金属盐溶液中浸泡约15min；环境温度保持15-40℃，湿度为10-30%，形成第一样品；In the first step, the foam metal-loaded graphene is immersed in the metal salt solution for about 15 minutes; the ambient temperature is maintained at 15-40 ° C, and the humidity is 10-30% to form a first sample;
    第二步，晾干第一样品，得到第二样品；以及In the second step, drying the first sample to obtain a second sample;
    第三步，对第二样品进行烧结，烧结条件为400-500℃下烧结1H。In the third step, the second sample is sintered under sintering conditions of 1H at 400-500 °C.
  10. 如权利要求9所述的纳米复合光催化材料的制备方法，其特征在于，所述金属溶液为钛盐溶液或钨盐溶液。The method for preparing a nanocomposite photocatalytic material according to claim 9, wherein the metal solution is a titanium salt solution or a tungsten salt solution.
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