WO2012142829A1 - 光催化法制备光催化剂/石墨烯一维核壳复合结构的方法 - Google Patents

光催化法制备光催化剂/石墨烯一维核壳复合结构的方法 Download PDF

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WO2012142829A1
WO2012142829A1 PCT/CN2011/082360 CN2011082360W WO2012142829A1 WO 2012142829 A1 WO2012142829 A1 WO 2012142829A1 CN 2011082360 W CN2011082360 W CN 2011082360W WO 2012142829 A1 WO2012142829 A1 WO 2012142829A1
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graphene
photocatalyst
preparing
composite structure
shell composite
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孙岳明
代云茜
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东南大学
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    • 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
    • B01J21/18—Carbon
    • 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
    • B01J21/063—Titanium; 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
    • 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
    • B01J21/066—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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/18—Carbon
    • B01J21/185—Carbon nanotubes
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    • 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
    • B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
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    • 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
    • B01J23/14—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of germanium, tin or lead
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
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    • 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
    • B01J27/24—Nitrogen compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • 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
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    • 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
    • B01J37/04—Mixing
    • 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

Definitions

  • the invention belongs to the technical field of photocatalyst / graphene composite nano material, in particular to a preparation photocatalyst / A method for preparing a graphene one-dimensional core-shell composite structure.
  • Graphene is a two-dimensional planar material composed of a carbon atom and a sp 2 hybrid orbital hexagonal honeycomb lattice.
  • the basic repeating structural unit is the most stable benzene six-membered ring in organic materials.
  • the single-layer graphene theoretical specific surface area is as high as 2630 m 2 /g.
  • the most common preparation method is the chemical reduction method.
  • the inorganic materials are dispersed into graphene to prepare graphene/inorganic nanocomposites. Due to the presence of inorganic nanoparticles, the interaction between graphene sheets can be greatly reduced, and graphite is prevented to some extent. Agglomeration of alkenes. Therefore, the use of inorganic nanoparticles to modify graphene sheets is a method to effectively prevent graphene agglomeration.
  • graphene/inorganic oxides have been prepared (GE/TiO 2 , GE/Li 4 Ti 5 O 12 , GE/SnO 2 , GE/Co 3 O 4 , GE/ZnO, GE/Fe 3 O 4 , GE/Al 2 O 3 , GE/LiFePO 4 , etc.), graphene/metal (GE/Ag, GE/Au, GE/Pt, GE/Pd, GE/Co, etc.), graphene/polymer (GE/poly Composite nanoparticles of styrene, GE/polyvinyl acetate.
  • metals and metal oxides are three-dimensional nanoparticles ([1] Bai Wei, Shen Xiaoping. Graphene-based inorganic nanocomposites. Chemical Progress 2010, 22, 2010-2118).
  • the invention provides a photocatalytic method for preparing a photocatalyst/graphene one-dimensional core-shell composite structure,
  • the photocatalytic properties of one-dimensional photocatalysts were used to reduce graphene oxide to graphene to form a novel photocatalyst/graphene one-dimensional core-shell composite nanomaterial with core-shell structure.
  • Photocatalytic preparation of photocatalyst / The method for preparing a graphene one-dimensional core-shell composite structure is prepared by dispersing graphene oxide in a solvent at a concentration of 0.01-10 mg/mL. a graphene oxide colloid; a one-dimensional photocatalyst is dispersed in a solvent, and a photocatalyst suspension having a concentration of 0.01-1000 mg/mL is disposed; and the solution is mass ratio 100: 1-1 : 100, mixed and stirred, placed in an open container for 0.5-1000 h of light; after the reaction is finished, the product is centrifuged and dried.
  • the graphene oxide dispersion solvent is water or ethanol.
  • the one-dimensional structure is a nanofiber, a nanotube or a nanorod.
  • the photocatalyst is TiO 2 , ZnO , ZrO 2 , SnO 2 , N-doped TiO 2 , S-doped TiO 2 , N and S co-doped TiO 2 or N-doped ZnO.
  • the photocatalyst dispersion solvent is water or ethanol.
  • the illumination is visible light or ultraviolet light.
  • the stirring speed is not more than 800 rpm/min.
  • the centrifugation speed is 500-13000 rpm/min, and the centrifugation time is 1-60 min. .
  • graphene oxide is reduced to graphene by photocatalyst.
  • the steric effect of photocatalyst can effectively prevent the agglomeration of graphene, and the two-dimensional sheet-like graphene oxide is curled and wrapped.
  • Preparation of one-dimensional semiconductor by photocatalytic reduction method / The method of graphene composite nanofibers is simple; the reduction of graphene oxide by photocatalytic reaction can overcome the phenomenon of irreversible agglomeration of graphene oxide during the reduction process, and the product has good dispersibility.
  • Prepared photocatalyst / Graphene product is a new composite material with novel nano-core shell structure and novel physicochemical properties.
  • the reaction system does not add any organic matter as a surfactant, the product is pure, no complicated separation and purification process is required;
  • ethanol has a wide range of sources and low price; it can be reacted under visible light and ultraviolet light conditions, so it can be produced by natural light; the production process is carried out under normal temperature and pressure, no sintering process, saving production energy consumption; No toxic and harmful reagents, environmentally friendly, no pollution; fast and convenient method, easy to learn, good reproducibility, low manufacturing cost, simple process and high efficiency.
  • Figure 1 shows the photocatalytic preparation of a semiconductor/graphene core-shell composite one-dimensional structure.
  • Figure 2 is a transmission electron microscopy (TEM) photograph of titanium dioxide/graphene core-shell composite nanofibers.
  • Figure 3 is a high-resolution transmission electron microscope (HRTEM) photograph of titanium dioxide/graphene core-shell composite nanofibers.
  • the above solution was mixed according to the mass ratio of graphene oxide/TiO 2 nanofibers to 1:4, placed in a beaker, magnetically stirred at a rotation speed of 50 rpm/min, and irradiated with an ultraviolet lamp for 21 hours.
  • the above solution was mixed according to the mass ratio of graphene oxide/TiO 2 nanotubes to 10:1, placed in a beaker, magnetically stirred at a rotation speed of 500 rpm/min, and irradiated with an ultraviolet lamp for 4 hours.
  • the composite fiber is centrifuged at 13,000 rpm/min. Min, the product was isolated and dried at room temperature.
  • the graphene oxide/ZnO nanofiber mass ratio is 100:1, placed in a beaker, magnetically stirred, rotating at 100 Rpm/min, irradiated with UV light for 1000 h.
  • the composite fiber is centrifuged at 15000 rpm/min. Min, the product was isolated and dried at room temperature.
  • the graphene oxide/ZnO nanorods mass ratio is 20:1, placed in a beaker, magnetically stirred, rotating at 800 Rpm/min, irradiated with UV light for 4 h.
  • the composite fiber is centrifuged at 15000 rpm/min. Min, the product was isolated and dried at room temperature.
  • the graphene oxide/ZrO 2 nanofibers have a mass ratio of 1:100, placed in a beaker at a rotation speed of 300 rpm/min, and continuously irradiated for 0.5 h under ultraviolet light.
  • the composite fiber is centrifuged at 1000 rpm/min for 5 min, and the product is separated and dried under vacuum at room temperature.
  • the composite fiber is centrifuged at 1000 rpm/min for 10 min and dried at room temperature.
  • the composite fiber is centrifuged at 1000 rpm/min for 10 min and dried at room temperature.
  • the composite fiber is centrifuged at 500 rpm/min. Min, the product was isolated and dried at room temperature.
  • the composite fiber was centrifuged at 8,000 rpm/min, and the product was separated and dried at room temperature.
  • the mass ratio of graphene oxide/N and S co-doped TiO 2 nanofibers is 1:10.
  • the above solution is mixed, placed in a beaker, magnetically stirred, rotating at 500 rpm / min, continuous illumination under visible light 120 h.
  • the composite fiber was centrifuged at 8,000 rpm/min, and the product was separated and dried at room temperature.
  • the mass ratio of graphene oxide/S doped ZnO nanorods is 20:1.

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  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Nanotechnology (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
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Description

光催化法制备光催化剂 / 石墨烯一维核壳复合结构的方法 技术领域
本发明属于光催化剂 / 石墨烯复合纳米材料技术领域，尤其涉及一种制备光催化剂 / 石墨烯一维核壳复合结构的制备方法。
背景技术
现有技术：石墨烯（ GE ）是一种由碳原子以 sp2 杂化轨道组成六角型呈蜂巢晶格的二维平面材料，其基本重复结构单元为有机材料中最稳定的苯六元环，单层石墨烯理论比表面积高达 2630 m2/g 。最常用的制备方法是化学还原法。但是由氧化石墨烯还原为石墨烯的过程中，碳原子由 sp3 杂化转变为 sp2 杂化，导致石墨烯发生不可逆团聚，产物比表面积下降至仅有 1 m2/g （ [1] 柏嵩，沈小平 . 石墨烯基无机纳米复合材料 . 化学进展 2010, 22, 2010-2118; [2] 徐超，陈胜，汪信 . 基于石墨烯的材料化学进展 . 应用化学 2011, 28, 1-9. ）。
将无机材料（如金属和半导体纳米粒子）分散到石墨烯中制备石墨烯 / 无机纳米复合材料，由于无机纳米粒子的存在，可以大大减少石墨烯片层之间的相互作用，一定程度上防止石墨烯的团聚。因此，采用无机纳米粒子修饰石墨烯片是一种有效阻止石墨烯团聚的方法。目前，人们已经制备的石墨烯 / 无机氧化物（ GE/TiO2 、 GE/Li4Ti5O12 、 GE/SnO2 、 GE/Co3O4 、 GE/ZnO 、 GE/Fe3O4 、 GE/Al2O3 、 GE/LiFePO4 等）、石墨烯 / 金属（ GE/Ag 、 GE/Au 、 GE/Pt 、 GE/Pd 、 GE/Co 等）、石墨烯 / 高分子（ GE/ 聚苯乙烯、 GE/ 聚乙酸乙烯酯）的复合纳米颗粒。在已报道的文献、专利中，金属、金属氧化物均为三维的纳米颗粒 ([1] 柏嵩，沈小平 . 石墨烯基无机纳米复合材料 . 化学进展 2010, 22, 2010-2118) 。
 技术问题
本发明提供一种光催化法制备光催化剂 / 石墨烯一维核壳复合结构的方法 , 利用一维光催化剂光催化特性，将氧化石墨烯还原为石墨烯，生成新颖的具有核壳结构的光催化剂 / 石墨烯一维核壳复合纳米材料。
技术解决方案
光催化法制备光催化剂 / 石墨烯一维核壳复合结构的方法，制备步骤为：将氧化石墨烯分散在溶剂中，配制浓度为 0.01-10 mg/mL 的氧化石墨烯胶体；将一维结构的光催化剂分散在溶剂中，配置浓度为 0.01-1000 mg/mL 的光催化剂悬浮液；将上述溶液按质量比 100 ： 1-1 ： 100 混合搅拌，置于开口容器中光照 0.5-1000 h ；反应结束后，在将产物离心分离，干燥。
所述氧化石墨烯分散溶剂为水或者乙醇。
所述一维结构为纳米纤维、纳米管或纳米棒。
所述光催化剂为 TiO2 、 ZnO 、 ZrO2 、 SnO2 、 N 掺杂 TiO2 、 S 掺杂 TiO2 、 N 和 S 共掺杂 TiO2 或 N 掺杂 ZnO 。
所述光催化剂分散溶剂为水或者乙醇。
所述光照为可见光照或者紫外光照。
所述搅拌速度为不超过 800 rpm/min 。
所述离心速度为 500-13000 rpm/min ，离心时间为 1-60 min 。
在光照条件下，氧化石墨烯被光催化剂还原为石墨烯，在还原反应发生过程中，光催化剂的位阻效应可以有效防止石墨烯的团聚，并且二维的片状氧化石墨烯发生卷曲包裹在一维的光催化剂表面，形成新颖的光催化剂 / 石墨烯核壳结构。
 有益效果
利用光催化还原法制备一维半导体 / 石墨烯复合纳米纤维，方法简便；采用光催化反应法还原氧化石墨烯，可以克服氧化石墨烯在还原过程中出现不可逆团聚的现象，产物具有良好的分散性。制备出的光催化剂 / 石墨烯产物是一种新的复合材料，具有新颖的纳米核壳结构和新颖的物理化学性质；反应体系未添加任何有机物作为表面活性剂，产物纯净，无需复杂的分离、提纯过程；以水或乙醇作为反应溶剂，来源广泛、价格低廉；可以在可见光、紫外光照条件下进行反应，因此可以利用自然光进行生产；制作过程在常温常压下进行，无烧结工艺，节约生产能耗；制备方法中无任何有毒有害试剂，对环境友好，无污染；方法快速便捷、简单易学，重现性好，并且制造成本低，工艺简单，效率高。
附图说明
图 1 为光催化制备半导体 / 石墨烯核壳复合一维结构的设备。 1 、光源； 2 、容器； 3 、反应溶液； 4 、磁子； 5 、磁力搅拌器； 6 、载物台。
图 2 为二氧化钛 / 石墨烯核壳复合纳米纤维透射电镜（ TEM ）照片。
图 3 为二氧化钛 / 石墨烯核壳复合纳米纤维高分辨率透射电镜（ HRTEM ）照片。
 本发明的实施方式
实施例1：
a、将氧化石墨分散在乙醇中，浓度为1 mg/mL。
b、将TiO2纳米纤维分散在水中，浓度为2 mg/mL。
c、将上述溶液按照氧化石墨烯/TiO2纳米纤维质量比为1：4进行混合，置于烧杯中，进行磁力搅拌，转速为50 rpm/min，用紫外灯照射21 h。
d、反应结束后，在8000 rpm/min转速下离心3 min，将产物分离出来，室温干燥。
反应产物见图2、3。
实施例2：
a、将氧化石墨烯分散在去离子水中，浓度为2 mg/mL。
b、将TiO2纳米管分散在乙醇中，配置浓度为0.01 mg/mL。
c、上述溶液按照氧化石墨烯/TiO2纳米管质量比为10：1进行混合，置于烧杯中，磁力搅拌，转速为500 rpm/min，用紫外灯照射4 h。
d、反应结束后，在将复合纤维在13000 rpm/min转速下进行离心1 min，将产物分离出来，室温干燥。
实施例3：
a、将氧化石墨烯分散在去离子水中，浓度为0.05 mg/mL。
b、将ZnO纳米纤维分散在去离子水中，浓度为100 mg/mL。
c、将上述溶液混合，氧化石墨烯/ZnO纳米纤维质量比为100：1，置于烧杯中，磁力搅拌，转速为100 rpm/min，用紫外灯照射1000 h。
d、反应结束后，在将复合纤维在15000 rpm/min转速下进行离心1 min，将产物分离出来，室温干燥。
实施例4：
a、将氧化石墨烯分散在去离子水中，配置浓度为10 mg/mL。
b、将ZnO纳米棒分散在乙醇中，配置浓度为100 mg/mL。
c、将上述溶液混合，氧化石墨烯/ZnO纳米棒质量比为20：1，置于烧杯中，磁力搅拌，转速为800 rpm/min，用紫外灯照射4 h。
d、反应结束后，在将复合纤维在15000 rpm/min转速下进行离心1 min，将产物分离出来，室温干燥。
实施例5：
a、将氧化石墨烯分散在蒸馏水中，配置浓度为5 mg/mL。
b、将ZrO2纳米纤维分散在乙醇中，配置浓度为0.1 mg/mL。
c、将上述溶液混合，氧化石墨烯/ZrO2纳米纤维质量比为1：100，置于烧杯中，转速为300 rpm/min，在紫外光下连续照射0.5 h。
d、反应结束后，将复合纤维在1000 rpm/min转速下离心5 min，将产物分离出来，室温真空干燥。
实施例6：
a、以氧化石墨烯作为碳源，超声分散在蒸馏水中，配置浓度为1 mg/mL。
b、将SnO2纳米纤维分散在水中，配置浓度为10 mg/mL。
c、将上述溶液混合，其中氧化石墨烯/SnO2纳米纤维质量比为2:1，置于烧杯中，磁力搅拌，转速为50 rpm/min，在紫外光下连续照射96 h。
d、反应结束后，在将复合纤维在1000 rpm/min转速下离心10 min，室温干燥。
实施例7：
a、以氧化石墨烯作为碳源，超声分散在蒸馏水中，配置浓度为1 mg/mL。
b、将静电纺丝制备的N掺杂TiO2纳米纤维分散在水中，配置浓度为0.1 mg/mL。
c、将上述溶液混合，其中氧化石墨烯/SnO2纳米纤维质量比为10:1置于烧杯中，在可见光下连续照射96 h。
d、反应结束后，在将复合纤维在1000 rpm/min转速下离心10 min，室温干燥。
实施例8：
a、以氧化石墨烯作为碳源，超声分散在蒸馏水中，配置浓度为1 mg/mL。
b、将静电纺丝制备的S掺杂TiO2纳米纤维分散在水中，配置浓度为0.1 mg/mL。
c、将上述溶液混合，其中氧化石墨烯/S掺杂TiO2纳米纤维质量比为5:1置于烧杯中，磁力搅拌，转速为400 rpm/min，在可见光下连续照射24 h。
d、反应结束后，在将复合纤维在500 rpm/min转速下离心60 min，将产物分离出来，室温干燥。
实施例9：
a、以氧化石墨烯作为碳源，超声分散在蒸馏水中，配置浓度为1 mg/mL。
b、将静电纺丝制备的N和S共掺杂TiO2纳米纤维分散在水中，配置浓度为0.1 mg/mL。
c、将上述溶液混合，置于烧杯中，在可见光下连续照射1 h。
d、反应结束后，在将复合纤维在8000 rpm/min转速下进行离心，将产物分离出来，室温干燥。
其中氧化石墨烯/N和S共掺杂TiO2纳米纤维质量比为1:10。
实施例10：
a、以氧化石墨烯作为碳源，超声分散在蒸馏水中，配置浓度为1 mg/mL。
b、将S掺杂的ZnO纳米棒分散在水中，配置浓度为0.1 mg/mL。
c、将上述溶液混合，置于烧杯中，磁力搅拌，转速为500 rpm/min，在可见光下连续照射120 h。
d、反应结束后，在将复合纤维在8000 rpm/min转速下进行离心，将产物分离出来，室温干燥。
其中氧化石墨烯/S掺杂的ZnO纳米棒质量比为20：1。

Claims (8)

  1. 光催化法制备光催化剂/石墨烯一维核壳复合结构的方法，其特征在于制备步骤为： a.将氧化石墨烯分散在溶剂中，配制浓度为0.01-10 mg/mL的氧化石墨烯胶体； b.将一维结构的光催化剂分散在溶剂中，配置浓度为0.01-1000 mg/mL的光催化剂悬浮液； c.将上述溶液按质量比100：1-1：100混合搅拌，置于开口容器中光照0.5-1000 h； d.反应结束后，在将产物离心分离，干燥。
  2. 根据权利要求1所述的光催化法制备光催化剂/石墨烯一维核壳复合结构的方法，其特征在于所述氧化石墨烯分散溶剂为水或者乙醇。
  3. 根据权利要求1所述的光催化法制备光催化剂/石墨烯一维核壳复合结构的方法，其特征在于所述一维结构为纳米纤维、纳米管或纳米棒。
  4. 根据权利要求1所述的光催化法制备光催化剂/石墨烯一维核壳复合结构的方法，其特征在于所述光催化剂为TiO2、ZnO、ZrO2、SnO2、N掺杂TiO2、S掺杂TiO2、N和S共掺杂TiO2或N掺杂ZnO。
  5. 根据权利要求1所述的光催化法制备光催化剂/石墨烯一维核壳复合结构的方法，其特征在于所述光催化剂分散溶剂为水或者乙醇。
  6. 根据权利要求1所述的光催化法制备光催化剂/石墨烯一维核壳复合结构的方法，其特征在于所述光照为可见光照或者紫外光照。
  7. 根据权利要求1所述的光催化法制备光催化剂/石墨烯一维核壳复合结构的方法，其特征在于所述搅拌速度为不超过800 rpm/min。
  8. 根据权利要求1所述的光催化法制备光催化剂/石墨烯一维核壳复合结构的方法，其特征在于所述离心速度为500-13000 rpm/min，离心时间为1-60 min。
PCT/CN2011/082360 2011-04-20 2011-11-17 光催化法制备光催化剂/石墨烯一维核壳复合结构的方法 WO2012142829A1 (zh)

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