CN105854863A - Method for preparing C/ZnO/TiO2 composite nano photocatalytic material - Google Patents
Method for preparing C/ZnO/TiO2 composite nano photocatalytic material Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 66
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 20
- 239000002131 composite material Substances 0.000 title abstract description 29
- 239000013132 MOF-5 Substances 0.000 claims abstract description 35
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 16
- 239000002243 precursor Substances 0.000 claims abstract description 13
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 12
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 9
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 4
- 239000000843 powder Substances 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 3
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 239000004094 surface-active agent Substances 0.000 claims abstract description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 35
- 239000002114 nanocomposite Substances 0.000 claims description 25
- 238000001914 filtration Methods 0.000 claims description 17
- 238000002360 preparation method Methods 0.000 claims description 17
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000012153 distilled water Substances 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 8
- 230000007062 hydrolysis Effects 0.000 claims description 7
- 238000006460 hydrolysis reaction Methods 0.000 claims description 7
- 238000003760 magnetic stirring Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000004567 concrete Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- 230000000593 degrading effect Effects 0.000 abstract description 2
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 abstract 3
- 238000010335 hydrothermal treatment Methods 0.000 abstract 2
- 238000000967 suction filtration Methods 0.000 abstract 1
- 238000001132 ultrasonic dispersion Methods 0.000 abstract 1
- 239000011941 photocatalyst Substances 0.000 description 20
- 238000007146 photocatalysis Methods 0.000 description 19
- 238000006731 degradation reaction Methods 0.000 description 15
- 230000015556 catabolic process Effects 0.000 description 14
- 238000006555 catalytic reaction Methods 0.000 description 5
- 239000000356 contaminant Substances 0.000 description 5
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000012621 metal-organic framework Substances 0.000 description 4
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 3
- 229940012189 methyl orange Drugs 0.000 description 3
- 239000002071 nanotube Substances 0.000 description 3
- 239000013110 organic ligand Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000007857 degradation product Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000005297 material degradation process Methods 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 239000013066 combination product Substances 0.000 description 1
- 229940127555 combination product Drugs 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 229920001795 coordination polymer Polymers 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000009432 framing Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 125000001905 inorganic group Chemical group 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000001455 metallic ions Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000007783 nanoporous material Substances 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002096 quantum dot Substances 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- 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
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
-
- B01J35/39—
-
- 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
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
-
- 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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The invention discloses a method for preparing a C/ZnO/TiO2 composite nano photocatalytic material. The method comprises the steps that 1, a hydrothermal method is adopted, tetra-n-butyl titanate is adopted as a raw material, cetyl trimethyl ammonium bromide is adopted as a surface active agent, tetra-n-butyl titanate is hydrolyzed and subjected to a stirring reaction at room temperature, and a titanium dioxide precursor is obtained through hydrothermal treatment, suction filtration and drying; 2, soluble zinc nitrate and terephthalic acid are dissolved in N,N-dimethylformamide, and MOF-5 is obtained through hydrothermal treatment after ultrasonic dispersion; 3, finally, obtained MOF-5 and titanium dioxide powder are mixed, and the C/ZnO/TiO2 composite nano photocatalytic material is obtained through high temperature treatment. The method for preparing the C/ZnO/TiO2 composite nano photocatalytic material for catalytically degrading organic pollutants has the advantages of being simple easy to operate and control, low in preparing cost and free of environmental pollution.
Description
Technical field
The present invention relates to a kind of photocatalyst for catalytic degradation organic pollution and preparation method thereof, particularly relate to hydro-thermal method and prepare C/ZnO/TiO2The method of nano composite material；Metal nanometer material preparation and photocatalysis field.
Background technology
Along with people's concern to environmental conservation, curbing environmental pollution and have become as the Important Problems of countries in the world scientific researcher joint research, catalysis material was always material science, the focus of catalytic science research in recent years.Semi-conducting material application in terms of photocatalysis degradation organic contaminant obtains extensive concern, in order to improve the photocatalysis efficiency of semi-conducting material, improve service life, the stability ensureing materials'use and safety, continually develops new material most important.Nano titanium oxide is high because having catalysis activity, stable chemical nature, uses safe, cheap and easy to get, non-secondary pollution, has broad application prospects in field of environment pollution control.But TiO2Spectral region is narrow, needs the most just to excite generation electronics, and under sunlight, ultraviolet content is less than 5%.So will be by TiO2Photocatalyst really applies in productive life, it is achieved large-scale industrial production, and primary improves TiO exactly2Spectral response range and photocatalysis efficiency, and shorten reaction needed for time.Correlational study shows, by the semiconductors coupling of different band gap, can effectively strengthen light induced electron and separate with hole, and then improve photocatalytic activity.Li Li et al. CTAB auxiliary has synthesized nano composite material Ag/ZnO-TiO2, it is achieved that the raising of catalysis activity, but this material cost is high, and environment also results in bigger pollution.Duan Xuechen et al. uses chemical deposition, with ZnO to TiO2Nanotube is modified, and is prepared for ZnO/TiO2-nanotube composite semiconductor material, ZnO particle surface is modified and is enhanced TiO2The photocatalytic activity of-nanotube, but this composite require preparation process each step will strict control condition, the repeatability of synthetic material is poor.Liu Yang et al. utilizes electrochemical synthesis technology to prepare nano level carbon quantum dot, and devises complex catalyst system (CQDs/TiO based on carbon quantum dot2), this system can the utilization of effective experiment catalyst spectrum complete to sunlight, but experiment condition is required higher by this method, technical sophistication, relatively costly.
Metal-organic framework materials (Metal-Organic Frameworks, MOFs) it is a kind of novel multifunctional nano porous material, it is to be connected by independently pretending by the organic ligand at inorganic metal center with bridging, forming a class and have the crystalline state porous material of periodic network structure, MOF-5 is one of Typical Representative of MOFs series organic frame compound.MOF-5 refers to Zn2+With p-phthalic acid (H2BDC) it is respectively central metallic ions and organic ligand, is formed by connecting by octahedral form between them, there is the three-dimensional skeleton of microcellular structure.Its secondary structure unit is Zn4O(-CO2)6, it is by centered by 1 oxygen atom, formed by the carboxyl bridging of 6 band phenyl ring, forms the crystalline state porous material with periodic network structure.MOF-5 is different from molecular sieve, and its duct is to be collectively formed by metal and organic component, and organic molecule and organic reaction are had bigger activity and selectivity.The electrochemical method for synthesizing that normal temperature and pressure is clean such as Yang Huimin synthesizes zinc metal organic coordination polymer, has good heat stability and catalytic water decomposes the ability producing hydrogen.MOF-5 is applied to electrode material by Wang Xianyou seminar, shows good chemical property.The MOF-5 material of the synthesis such as the Yaghi of Univ Michigan-Ann Arbor USA is the most typical material of structure in a series of MOF-n material, and it is to have four Zn2+With an O2-Composition
[ZnO] 6+Inorganic group, this group and [O2C-C6H4-C
O2 ]2-Connect with octahedral form, form the framing structure of 3 D stereo, there is higher specific surface area, regular pore passage structure.Scholars is extensive to the MOF-5 applied research in the field such as gas, biochemistry of storage, but by itself and TiO2Compound discussion after a series of processes process for photocatalysis degradation organic contaminant this respect is few.
Summary of the invention
For the deficiencies in the prior art, it is an object of the invention to provide a kind of simple to operate easily-controllable, cost of manufacture is low, the C/ZnO/TiO for photocatalysis degradation organic contaminant of non-environmental-pollution2The preparation method of nano composite photocatalytic material.
For realizing object above, one C/ZnO/TiO of the present invention2The preparation method one of nano composite photocatalytic material is to use hydro-thermal method, with tetra-n-butyl titanate as raw material, cetyl trimethylammonium bromide is surfactant, at room temperature by tetra-n-butyl titanate hydrolysis stirring reaction, obtains TiO 2 precursor by hydro-thermal, sucking filtration, drying；Two is solubility zinc nitrate, p-phthalic acid to be dissolved in DMF, obtains MOF-5 through hydro-thermal after ultrasonic disperse；Finally obtained MOF-5 is mixed with titanium dioxide powder, obtain C/ZnO/TiO through high-temperature process2Nano composite photocatalytic material；Concrete operation step is as follows:
(1) take tetra-n-butyl titanate and add hydrolysis sucking filtration in distilled water, add distilled water and 0.05-1.00mol/l
Cetyl trimethylammonium bromide solution, with HCl:HNO3=1:
Solution, to pH value of solution=1～5, is placed in reactor by the proportion adjustment pH of 2～6, hydro-thermal reaction 8-24 hour in the constant temperature oven of 150 ° of C～200 ° of C, and sucking filtration obtains the TiO 2 precursor of white；
(2) zinc nitrate (ZnNO is taken3·4H2O, AR) and p-phthalic acid be 1:3～6 in mass ratio, add DMF dissolve, after magnetic stirring apparatus, ultrasonic disperse, 100 DEG C～160 DEG C of hydro-thermal reactions 18-36 hour in reactor, after natural cooling sucking filtration dry, obtain MOF-5；
(3) by the TiO 2 precursor prepared in (1) (2) and MOF-5 with MOF-5:TiO2The ratio that mass ratio is 1:1～15, grind non-homogeneous physical mixing, this mixture moved in crucible, process 1-3 hour in the Muffle furnace of 300～700 ° of C, obtain C/ZnO/TiO2Nano composite photocatalytic material.
Wherein: the pH of step (1) described solution is preferably 1～3.
Wherein: step (1) described hydrothermal temperature is preferably 160 DEG C～180 DEG C.
Wherein: step (2) described zinc nitrate (ZnNO3·4H2O, AR) and the matter of p-phthalic acid than preferably 1:4～1:5.5.
Wherein: step (2) described hydrothermal temperature is preferably 100 DEG C～130 DEG C.
Wherein: step (3) described MOF-5:TiO2Mass ratio be preferably 1:10～13.
Wherein: step (3) described high temperature is preferably 400～600 ° of C.
By one C/ZnO/TiO of the present invention2The C/ZnO/TiO that the preparation method of nano composite photocatalytic material prepares2Nano composite photocatalytic material be applied to photocatalysis degradation organic contaminant, application operating step is:
Take 100ml 15mg/L methyl orange solution, the methyl orange solution of another part of 100ml 15mg/L adds 20mg sample, in ultrasonic disperse instrument, ultrasonic 10 minutes magnetic stirring apparatuss in the dark stir after 40min reaches physical absorption and desorption equilibrium and in the dark place 30min, survey its absorbance, they are placed under Burdick lamp again and are irradiated, every 30min sampling, measure absorbance (maximum absorption wavelength: 464.8nm), calculate its degradation rate, result of the test is: after placing 120min under 300W ultra violet lamp, the methyl orange degradation rate not having sample is 7.80%, the sample degradation rate adding MOF-5 is 12.57%, the sample degradation rate adding titanium dioxide is 75.14%, add C/ZnO/TiO2The degradation rate of nano composite photocatalytic material can reach 92.39%.
The C/ZnO/TiO that the present invention is prepared2The analysis detection means that composite photocatalyst material uses is: with its crystal structure of XRD determining, observing the pattern of photocatalyst under scanning electron microscope, TG-DSC analyzes the structure of material, is that target degradation product checks its photocatalysis performance in methyl orange.
One C/ZnO/TiO of the present invention2The preparation method hydrothermal reaction at low temperature of nano composite photocatalytic material prepares MOF-5 nano material, it is mixed with the titanium dioxide powder after hydro-thermal, then obtains C/ZnO/TiO through high-temperature process2Composite, this composite has the following characteristics that
(1) C/ZnO/TiO after high-temperature process2Composite specific surface area is greatly increased, so that TiO2Disperseing evenly, the increase of composite specific surface area also makes the photocatalysis performance of material be improved；
(2) Zn2+Can strengthen the transmittability of light induced electron as electronics trap center, suppression photo-generate electron-hole, to being combined, improves the photocatalysis performance of material；
(3) existence of ZnO can make itself and TiO2The synergism of two kinds of materials is more notable, thus improves the composite photocatalyst material utilization rate to solar energy；
(4) C/ZnO/TiO prepared2The loose structure of composite can help Adsorption of Organic at TiO2Surface, makes degradation reaction more complete, thus improves photocatalysis efficiency.
The present invention utilizes simple hydro-thermal method to be prepared for the C/ZnO/TiO that photocatalysis performance is ideal2Nano composite photocatalytic material, the porous carbon structure of material makes light induced electron transmittability strengthen, and specific surface area increases, and electron-hole recombination rate reduces, ZnO and TiO2Synergism extend the catalysis material utilization to solar energy；Have studied its photocatalysis performance as photocatalyst for degrading organic pollution, find its photocatalysis performance ratio be not optimised promote before bigger.The preparation manipulation of this composite is simple and easy to do, it is easy to large-scale production so that it is have potential application prospect in photocatalysis degradation organic contaminant field, and exploitation novel photocatalysis degradable organic pollutant material is had certain directive function.
Accompanying drawing explanation
Fig. 1 is TiO after MOF-5, high-temperature process2The C/ZnO/TiO prepared with the present invention2The XRD figure of composite photocatalyst material.
Fig. 2 is C/ZnO/TiO prepared by the present invention2The SEM figure of composite photocatalyst material.
Fig. 3 is C/ZnO/TiO prepared by the present invention2The thermogravimetric analysis figure of composite photocatalyst material.
Fig. 4 is C/ZnO/TiO prepared by the present invention2Composite photocatalyst material photocatalytic degradation efficiency figure.
Detailed description of the invention
Below in conjunction with the accompanying drawings with detailed description of the invention to one C/ZnO/TiO of the present invention2The preparation method of nano composite photocatalytic material is described in further detail.
The C/ZnO/TiO prepared by the XRD determining present invention2The crystal structure of composite photocatalyst material, such as Fig. 1；The C/ZnO/TiO that the present invention prepares is observed under scanning electron microscope2The pattern of composite photocatalyst material, such as Fig. 2；TG-DSC analyzes the C/ZnO/TiO that the present invention prepares2The structure of composite photocatalyst material, such as Fig. 3；It is the C/ZnO/TiO that the target degradation product inspection present invention prepares in methyl orange2The photocatalysis performance of composite photocatalyst material, such as Fig. 4.
From figure 1 it appears that each diffraction maximum peak shape is good, TiO2The C/ZnO/TiO prepared with the present invention22 θ positions of composite photocatalyst material all have 5 obvious diffraction maximums at 25.1 °, 37.7 °, 48.1 °, 55.1 ° and 62.8 °, and its peak position is consistent with the peak position of standard card (JCPDS 89-4921), illustrates that crystal is mainly Anatase structure；It addition, diffraction maximum does not occurs the characteristic peak of MOF-5, because doping is smaller.According to the data value in diffracting spectrum, Scherrer formula can obtain MOF-5, TiO2、C/ZnO/TiO2The average grain size of composite photocatalyst material is all nanoscale.
Fig. 2 is the C/ZnO/TiO that the present invention prepares2Shape appearance figure after composite photocatalyst material high-temperature process, figure shows the granular size of this composite at about 50nm, consistent with XRD figure result, material has certain pore space structure, can be effectively improved its photocatalysis performance.
Fig. 3 shows the C/ZnO/TiO that the present invention prepares2The weightlessness of composite photocatalyst material is main before 500 ° of C, and the weightlessness before 200 DEG C mainly loses the abjection of irreducible water weak between skeleton and solvent, to there being an endothermic peak.200～500 DEG C of weightlessness belong to pyrolysis carbonization formation C/ZnO combination product, the Zn of organic ligand2+The decomposition reaction of salt, therefore, after 500 DEG C of calcinings, MOF-5 can be pyrolyzed carbonization.
Fig. 4 shows, methyl orange, TiO2、C/ZnO/TiO2Composite photocatalyst material degradation rate under uviol lamp is respectively 7.88%, 75.71%, 92.39%, and the C/ZnO/TiO that the present invention prepares is described2The photocatalysis performance of composite photocatalyst material is enhanced, and shows good catalytic performance.
Embodiment
1
The present embodiment comprises the following steps:
(1) weighing zinc nitrate and p-phthalic acid for 1:3 in mass ratio, add DMF and dissolve, after magnetic stirring apparatus, ultrasonic disperse, 160 DEG C of hydro-thermal reactions 24 hours in reactor, after natural cooling, sucking filtration is dried, and obtains MOF-5.
(2) take 2ml tetra-n-butyl titanate and add hydrolysis sucking filtration in 40ml distilled water, add the distilled water of 60ml and the 0.1mol/l cetyl trimethylammonium bromide solution of 2ml, with HCl:HNO3Solution, to pH value of solution=3, is placed in reactor by the proportion adjustment pH of=1:2, hydro-thermal reaction 12 hours in the constant temperature oven of 180 ° of C, and sucking filtration obtains the TiO 2 precursor of white.
(3) by ratio with the mass ratio of MOF-5:TiO2 as 1:1 of the MOF-5 prepared in (1) (2) and TiO 2 precursor, grinding non-homogeneous physical mixes, this mixture is moved in crucible, in the Muffle furnace of 400 ° of C, high-temperature process 2 hours, obtains C/ZnO/TiO2 nano composite photocatalytic material.
The methyl orange solution 60min of resulting materials photocatalytic degradation 15mg/L, obtaining degradation rate is 46.49%.
Embodiment
2
The present embodiment comprises the following steps:
(1) weighing zinc nitrate and p-phthalic acid for 1:5 in mass ratio, add DMF and dissolve, after magnetic stirring apparatus, ultrasonic disperse, 120 DEG C of hydro-thermal reactions 24 hours in reactor, after natural cooling, sucking filtration is dried, and obtains MOF-5.
(2) take 2ml tetra-n-butyl titanate and add hydrolysis sucking filtration in 40ml distilled water, add the distilled water of 50ml and the 0.1mol/l cetyl trimethylammonium bromide solution of 1ml, with the proportion adjustment pH of HCl:HNO3=1:4 to pH value of solution=2, solution is placed in reactor, hydro-thermal reaction 12 hours in the constant temperature oven of 160 ° of C, sucking filtration obtains the TiO 2 precursor of white.
(3) by ratio with the mass ratio of MOF-5:TiO2 as 1:11 of the MOF-5 prepared in (1) (2) and TiO 2 precursor, grinding non-homogeneous physical mixes, this mixture is moved in crucible, in the Muffle furnace of 500 ° of C, high-temperature process 2 hours, obtain C/ZnO/TiO2 nano composite photocatalytic material
The methyl orange solution 60min of resulting materials photocatalytic degradation 15mg/L, obtaining degradation rate is 92.39%.
Embodiment
3
The present embodiment comprises the following steps:
(1) weighing zinc nitrate and p-phthalic acid for 1:6 in mass ratio, add DMF and dissolve, after magnetic stirring apparatus, ultrasonic disperse, 100 DEG C of hydro-thermal reactions 24 hours in reactor, after natural cooling, sucking filtration is dried, and obtains MOF-5.
(2) take 2ml tetra-n-butyl titanate and add hydrolysis sucking filtration in 40ml distilled water, add the distilled water of 100ml and the 0.1mol/l cetyl trimethylammonium bromide solution of 5ml, with HCl:HNO3Solution, to pH value of solution=5, is placed in reactor by the proportion adjustment pH of=1:2～1:6, hydro-thermal reaction 12 hours in the constant temperature oven of 150 ° of C, and sucking filtration obtains the TiO 2 precursor of white.
(3) by ratio with the mass ratio of MOF-5:TiO2 as 1:15 of the MOF-5 prepared in (1) (2) and TiO 2 precursor, grinding non-homogeneous physical mixes, this mixture is moved in crucible, in the Muffle furnace of 500 ° of C, high-temperature process 2 hours, obtaining C/ZnO/TiO2 nano composite photocatalytic material, the methyl orange solution 60min of resulting materials photocatalytic degradation 15mg/L, obtaining degradation rate is 57.94%.
Contrast three above embodiment, embodiment 2 gained C/ZnO/TiO2 nano composite photocatalytic material degradation rate in the application is the highest, for most preferred embodiment.
The application of the present invention is not limited to above-mentioned citing; for those of ordinary skills; under the premise without departing from the principles of the invention, it is also possible to improved according to the above description or modify, in all these improvement or modification all should fall into the protection domain of the claims in the present invention.
Claims (7)
1. a C/ZnO/TiO2The preparation method of nano composite photocatalytic material, it is characterized in that: the method one is to use hydro-thermal method, with tetra-n-butyl titanate as raw material, cetyl trimethylammonium bromide is surfactant, at room temperature by tetra-n-butyl titanate hydrolysis stirring reaction, obtain TiO 2 precursor by hydro-thermal, sucking filtration, drying；Two is solubility zinc nitrate, p-phthalic acid to be dissolved in DMF, obtains MOF-5 through hydro-thermal after ultrasonic disperse；Finally obtained MOF-5 is mixed with titanium dioxide powder, obtain C/ZnO/TiO through high-temperature process2Nano composite photocatalytic material；Concrete operation step is as follows:
(1) take tetra-n-butyl titanate and add hydrolysis sucking filtration in distilled water, add distilled water and 0.05-1.00mol/l
Cetyl trimethylammonium bromide solution, with HCl:HNO3Solution, to pH value of solution=1～5, is placed in reactor by the proportion adjustment pH of=1:2～6, hydro-thermal reaction 8-24 hour in the constant temperature oven of 150 ° of C～200 ° of C, and sucking filtration obtains the TiO 2 precursor of white；
(2) zinc nitrate (ZnNO is taken3·4H2O, AR) and p-phthalic acid be 1:3～6 in mass ratio, add DMF dissolve, after magnetic stirring apparatus, ultrasonic disperse, 100 DEG C～160 DEG C of hydro-thermal reactions 18-36 hour in reactor, after natural cooling sucking filtration dry, obtain MOF-5；
(3) by the TiO 2 precursor prepared in (1) (2) and MOF-5 with MOF-5:TiO2The ratio that mass ratio is 1:1～15, grind non-homogeneous physical mixing, this mixture moved in crucible, process 1-3 hour in the Muffle furnace of 300～700 ° of C, obtain C/ZnO/TiO2Nano composite photocatalytic material.
2. C/ZnO/TiO as claimed in claim 12The preparation method of nano composite photocatalytic material, is characterized in that: the pH of step (1) described solution is preferably 1～3.
3. C/ZnO/TiO as claimed in claim 12The preparation method of nano composite photocatalytic material, is characterized in that: step (1) described hydrothermal temperature is preferably 160 DEG C～180 DEG C.
4. C/ZnO/TiO as claimed in claim 12The preparation method of nano composite photocatalytic material, is characterized in that: step (2) described zinc nitrate (ZnNO3·4H2O, AR) and the matter of p-phthalic acid than preferably 1:4～1:5.5.
5. C/ZnO/TiO as claimed in claim 12The preparation method of nano composite photocatalytic material, is characterized in that: step (2) described hydrothermal temperature is preferably 100 DEG C～130 DEG C.
6. C/ZnO/TiO as claimed in claim 12The preparation method of nano composite photocatalytic material, is characterized in that: step (3) described MOF-5:TiO2Mass ratio be preferably 1:10～13.
7. C/ZnO/TiO as claimed in claim 12The preparation method of nano composite photocatalytic material, is characterized in that: step (3) described high temperature is preferably 400～600 ° of C.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106423155A (en) * | 2016-11-03 | 2017-02-22 | 中国检验检疫科学研究院 | Preparation method of clavate Au@TiO2 composite photocatalytic nanometer material |
| CN107670664A (en) * | 2017-10-31 | 2018-02-09 | 云南健牛生物科技有限公司 | Titanic oxide composite photochemical catalyst system prepares and its application |
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| CN110665492A (en) * | 2019-09-24 | 2020-01-10 | 安徽工程大学 | TiO 22/Cr2O3/C nano material and preparation method thereof |
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| WO2022144043A1 (en) * | 2021-01-04 | 2022-07-07 | 江苏大学 | Preparation method for heterojunction of mof-derived zinc oxide and titanium dioxide composite, and use in photoelectric water splitting |
| CN114849692A (en) * | 2022-04-14 | 2022-08-05 | 三峡大学 | TiO 2 2 -C-MoO 2 Preparation method and application of nano composite material |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104492381A (en) * | 2014-11-28 | 2015-04-08 | 上海工程技术大学 | Heterogeneous TiO2/Co-metal organic framework (MOF) material as well as preparation method and application thereof |
-
2016
- 2016-04-14 CN CN201610229739.9A patent/CN105854863B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104492381A (en) * | 2014-11-28 | 2015-04-08 | 上海工程技术大学 | Heterogeneous TiO2/Co-metal organic framework (MOF) material as well as preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| 郭艳蓉等: ""MOF 衍生的多孔ZnO/C、Ag/ZnO/C复合材料光催化性能研究"", 《无机材料学报》 * |
| 顾逸凡等: ""原位负载纳米锐钛矿TiO2的制备研究"", 《中国化学会第29届学术年会摘要集-第27分会：多孔功能材料》 * |
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