CN109865514A - A kind of preparation method of copper/titanic oxide composite photochemical catalyst material - Google Patents
A kind of preparation method of copper/titanic oxide composite photochemical catalyst material Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 109
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 58
- 239000010949 copper Substances 0.000 title claims abstract description 58
- 239000000463 material Substances 0.000 title claims abstract description 53
- 239000002131 composite material Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000003054 catalyst Substances 0.000 title description 34
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 53
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 24
- 230000001699 photocatalysis Effects 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 12
- 239000005751 Copper oxide Substances 0.000 claims abstract description 11
- 229910000431 copper oxide Inorganic materials 0.000 claims abstract description 11
- 229960004643 cupric oxide Drugs 0.000 claims abstract description 11
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 claims abstract description 10
- UHWHMHPXHWHWPX-UHFFFAOYSA-J dipotassium;oxalate;oxotitanium(2+) Chemical compound [K+].[K+].[Ti+2]=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O UHWHMHPXHWHWPX-UHFFFAOYSA-J 0.000 claims abstract 6
- 239000000243 solution Substances 0.000 claims description 24
- 239000000725 suspension Substances 0.000 claims description 20
- 239000011259 mixed solution Substances 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- 230000015572 biosynthetic process Effects 0.000 abstract description 8
- 238000003786 synthesis reaction Methods 0.000 abstract description 8
- 239000003638 chemical reducing agent Substances 0.000 abstract description 7
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract description 4
- 239000010936 titanium Substances 0.000 abstract description 4
- 229910052719 titanium Inorganic materials 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 3
- 229910001431 copper ion Inorganic materials 0.000 abstract description 2
- 239000007810 chemical reaction solvent Substances 0.000 abstract 2
- 231100000331 toxic Toxicity 0.000 abstract 1
- 230000002588 toxic effect Effects 0.000 abstract 1
- HHDOORYZQSEMGM-UHFFFAOYSA-L potassium;oxalate;titanium(4+) Chemical compound [K+].[Ti+4].[O-]C(=O)C([O-])=O HHDOORYZQSEMGM-UHFFFAOYSA-L 0.000 description 22
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 description 20
- 239000000178 monomer Substances 0.000 description 14
- 238000006731 degradation reaction Methods 0.000 description 12
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 12
- 239000004810 polytetrafluoroethylene Substances 0.000 description 12
- 230000015556 catabolic process Effects 0.000 description 11
- 238000000926 separation method Methods 0.000 description 11
- 238000004090 dissolution Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 238000010521 absorption reaction Methods 0.000 description 8
- 230000008859 change Effects 0.000 description 7
- 239000012535 impurity Substances 0.000 description 7
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 7
- 230000001376 precipitating effect Effects 0.000 description 7
- 238000006555 catalytic reaction Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 229910000510 noble metal Inorganic materials 0.000 description 6
- 238000007146 photocatalysis Methods 0.000 description 6
- -1 polytetrafluoroethylene Polymers 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 4
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 230000001988 toxicity Effects 0.000 description 4
- 231100000419 toxicity Toxicity 0.000 description 4
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- 230000003197 catalytic effect Effects 0.000 description 3
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- 239000007787 solid Substances 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 229910052724 xenon Inorganic materials 0.000 description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- 241000790917 Dioxys <bee> Species 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
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- 229910052739 hydrogen Inorganic materials 0.000 description 2
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- 150000002500 ions Chemical class 0.000 description 2
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- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
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- 150000001875 compounds Chemical class 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- PTVDYARBVCBHSL-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu] PTVDYARBVCBHSL-UHFFFAOYSA-N 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
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- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
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- 231100000252 nontoxic Toxicity 0.000 description 1
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- 231100000614 poison Toxicity 0.000 description 1
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明提供一种铜/二氧化钛复合光催化材料的制备方法，该铜/二氧化钛复合光催化材料的制备方法以草酸钛钾作为钛源，以三水合硝酸铜为铜源，以乙二醇和水作为反应溶剂，通过水热反应制得由立方相的铜和锐钛矿二氧化钛复合而成的铜/二氧化钛复合光催化材料，其中，乙二醇既可作为反应溶剂，使整个反应体系均匀分散，同时又可作为还原剂，提供电子用于将铜离子还原为单质铜，合成过程简单，成本低，未引入任何毒性还原剂，生产过程绿色环保，符合实际生产需要，有较大的应用潜力。The invention provides a preparation method of a copper/titanium dioxide composite photocatalytic material. The preparation method of the copper/titanium dioxide composite photocatalytic material uses potassium titanium oxalate as the titanium source, copper nitrate trihydrate as the copper source, and ethylene glycol and water as the Reaction solvent, a copper/titanium dioxide composite photocatalytic material composed of cubic phase copper and anatase titanium dioxide is prepared by hydrothermal reaction, wherein ethylene glycol can be used as a reaction solvent to make the whole reaction system evenly dispersed, and at the same time It can also be used as a reducing agent to provide electrons for reducing copper ions to elemental copper, the synthesis process is simple, the cost is low, no toxic reducing agent is introduced, the production process is green and environmentally friendly, meets the actual production needs, and has great application potential.
Description
Technical field
The present invention relates to catalysis material technical field, in particular to a kind of copper/titanic oxide composite photochemical catalyst material
Preparation method.
Background technique
With the fast development of industrial civilization, the demand to the energy linearly increases, adjoint and next serious energy shortage
With problem of environmental pollution.The fast development of photocatalysis technology provides possibility to solve this two big global problems, and design is efficient, can
It makes full use of the photochemical catalyst of solar energy and has been developed into domestic and international research applied to environmental improvement and fungible energy source
The hot spot of person's concern.In the flow of research of photocatalysis nano material, nano-titanium dioxide has redox due to itself
Ability is strong, high catalytic efficiency and it is nontoxic, stability is good, valence band and conduction band positions low in cost and special are available
In the degradation of photocatalytic hydrogen production by water decomposition and organic pollutant many advantages, such as, it is considered to be the currently most light of application potential
Catalysis material.But due to titanium dioxide greater band gap (anatase=3.2eV), model only is utilized to ultraviolet light response spectrum
Enclose it is narrow, in addition, its electron hole easily quickly it is compound lead to carrier low efficiency, limit the application of titanium dioxide in practice.
Researcher is modified titanium dioxide by different methods, such as ion doping, semiconductors coupling, noble metal
Load, the regulation of pattern crystal face etc., main purpose is the hair for widening light abstraction width, promoting quantum efficiency, promoting surface reaction
It is raw.Based on to nano-titanium dioxide photo electric Quality Research, nano-titanium dioxide is carried out by above-mentioned means of different
It is modified, so that titanium dioxide base nano material has well in photocatalysis degradation organic contaminant and photodissociation aquatic products hydrogen field
Application prospect.Wherein, by noble metal loading, it can effectively capture light induced electron and then improve semiconductor catalytic activity, noble metal
It is deposited on semiconductor surface and is usually expressed as two aspect effects: first is that being conducive to photo-generate electron-hole to efficiently separating；Second is that
Improve photocatalytic activity by reducing the overpotential of reduction reaction, but noble metal is rare and expensive, hinder its into
The practical application of one step.In view of effect and its own limitation of the noble metal in Photocatalyst, for alternative
Non-noble metal exploration is of great significance, and in the selection of non-noble metallic materials, metallic copper is high, cheap due to natural abundance
Being easy to get becomes potential candidate.However, the synthesis of copper at present usually requires addition sodium borohydride, ascorbic acid, glucose, water
It closes hydrazine etc. and is used as reducing agent, it is unfriendly that the introducing of these reducing agents increases the toxicity of reaction system, environment, such as sodium borohydride
It is explosive, hydrazine hydrate toxicity is big, therefore, need to carry out close supervision to its dosage and usage mode in use, carry out
Safeguard procedures, this increases the complexity of experimentation to a certain extent.
Therefore, developing the catalysis material preparation method that a kind of synthesis is simple, raw material is green non-poisonous, synthesis cost is low has
Highly important meaning.
Summary of the invention
In view of this, the present invention is directed to propose a kind of preparation method of copper/titanic oxide composite photochemical catalyst material, to solve
The problem that existing catalysis material synthesis process is complicated, toxicity is high and synthesis cost is high.
In order to achieve the above objectives, the technical scheme of the present invention is realized as follows:
A kind of preparation method of copper/titanic oxide composite photochemical catalyst material, comprising the following steps:
1) titanium potassium oxalate is dissolved in water, obtains titanium potassium oxalate solution；
2) Gerhardite is dissolved in the titanium potassium oxalate solution, obtains mixed solution A；
3) it disperses ethylene glycol in the mixed solution A, obtains suspension B；
4) by the suspension B heat carry out hydro-thermal reaction, to the hydro-thermal reaction after, be cooled to room temperature, then,
Centrifuge separation, washing, vacuum drying, cooling, obtained copper/titanic oxide composite photochemical catalyst material.
Optionally, the molar concentration of titanium potassium oxalate solution described in the step 1) is 0.03~0.3mol/L.
Optionally, Gerhardite described in the step 2) and the titanium potassium oxalate molar ratio are 1: 20~4: 1.
Optionally, the volume ratio of ethylene glycol described in the step 3) and water described in the step 1) is 1: 3~3: 1.
Optionally, the heating temperature of heating described in the step 4) be 120 DEG C~180 DEG C, heating time be 6h~
18h。
Copper/titanic oxide composite photochemical catalyst material synthesis mechanism of the invention are as follows:
Firstly, in water and glycol system, titanium potassium oxalate issues unboiled water and depolymerize in high temperature hydrothermal condition generates dioxy
Change titanium, the titanium dioxide surface of synthesis is adsorbed with a large amount of ethylene glycol, and the bivalent cupric ion in ethylene glycol and reaction system is complexed,
So that bivalent cupric ion is uniformly adsorbed on the surface of titanium dioxide；Finally, as reaction dissolvent ethylene glycol in high temperature hydro-thermal
Under the conditions of simultaneously be used as reducing agent, the bivalent cupric ion for being adsorbed on titanium dioxide surface is reduced to elemental copper, be made copper/dioxy
Change titanium composite photocatalyst material.
Compared with the existing technology, the preparation method of copper/titanic oxide composite photochemical catalyst material of the present invention have with
Lower advantage:
1, copper/titanic oxide composite photochemical catalyst material preparation method of the invention is using titanium potassium oxalate as titanium source, with three
Nitric hydrate copper is copper source, and using ethylene glycol and water as reaction dissolvent, the copper and rutile titania by cubic phase is made by hydro-thermal reaction
Copper/titanic oxide composite photochemical catalyst material that mine titanium dioxide is combined, wherein ethylene glycol can not only be used for reaction dissolvent, make
Entire reaction system is evenly dispersed, while but also as reducing agent, providing electronics for copper ion to be reduced to elemental copper, synthesizing
Process is simple, at low cost, is not introduced into any toxicity reducing agent, and production process is environmentally protective, meets needs of production, has larger
Application potential.
2, copper/titanic oxide composite photochemical catalyst material produced by the present invention makes titanium dioxide surface due to the introducing of elemental copper
Property changes, to be conducive to the absorption of organic pollutant, in addition, the introducing of copper promotes the transfer of electronics, realizes
Photo-generated carrier efficiently separates, and since the surface ion resonance effects (SPR) of nano copper particle urges the complex light
Change material and show high photocatalysis performance under visible light illumination, absorption and photocatalytic degradation efficiency are substantially better than monomer
Titanium dioxide.
Detailed description of the invention
The attached drawing for constituting a part of the invention is used to provide further understanding of the present invention, schematic reality of the invention
It applies example and its explanation is used to explain the present invention, do not constitute improper limitations of the present invention.In the accompanying drawings:
Fig. 1 is copper/titanic oxide composite photochemical catalyst material X-ray diffraction analysis instrument described in the embodiment of the present invention 1
(XRD) map；
Fig. 2 is monomer titanium dioxide (a) described in the embodiment of the present invention 1, elemental copper (b) and copper/titanium dioxide complex light
The SEM scanned photograph of catalysis material (c)；
Fig. 3 is copper/titanic oxide composite photochemical catalyst material described in the embodiment of the present invention 1 and monomer titanium dioxide to dyestuff
The performance comparison figure of Congo red absorption；
Fig. 4 is copper/titanic oxide composite photochemical catalyst material described in the embodiment of the present invention 1 and monomer titanium dioxide to dyestuff
Congo red Photocatalytic Activity for Degradation performance comparison figure；
Fig. 5 is copper/titanic oxide composite photochemical catalyst material described in the embodiment of the present invention 1 and monomer titanium dioxide to dyestuff
Congo red absorption-Photocatalytic Activity for Degradation circulation absorption degradation figure.
Specific embodiment
It should be noted that in the absence of conflict, the feature in embodiment and embodiment in the present invention can phase
Mutually combination.
Below in conjunction with drawings and examples, the present invention will be described in detail.
Embodiment 1
A kind of preparation method of copper/titanic oxide composite photochemical catalyst material, comprising the following steps:
1) 4mmol titanium potassium oxalate is dissolved in by 20mL water using the method for ultrasonic dissolution, without precipitating after being clarified and being placed
Titanium potassium oxalate solution；
2) 2mmol Gerhardite is dissolved in by titanium potassium oxalate solution using the method for ultrasonic dissolution, obtains mixed solution
A；
3) it is dispersed 60mL ethylene glycol in mixed solution A using the method for ultrasonic disperse, obtains suspension B；
4) suspension B is placed in the stainless steel cauldron that liner is polytetrafluoroethylene (PTFE), hydro-thermal is anti-under conditions of 180 DEG C
12h is answered, after hydro-thermal reaction, cooled to room temperature, then, centrifuge separation, washing, to remove impurity, then, 60
It is dried in vacuo under the conditions of DEG C, it is cooling after sufficiently drying, copper/titanic oxide composite photochemical catalyst material is made.
It is urged using copper/titanium dioxide complex light of the BrukeraxsD8 type X-ray diffraction analysis instrument (XRD) to the present embodiment
Change material and carry out material phase analysis, and it is compared with monomer titanium dioxide, elemental copper, test results are shown in figure 1.
Wherein, the preparation method of monomer titanium dioxide, includes the following steps:
4mmol titanium potassium oxalate is dissolved in by 20mL water using the method for ultrasonic dissolution, without precipitating after being clarified and being placed
Titanium potassium oxalate solution；
Titanium potassium oxalate solution is dispersed for 60mL ethylene glycol using the method for ultrasonic disperse, obtains suspension C；
Suspension C is placed in the stainless steel autoclave that liner is polytetrafluoroethylene (PTFE), hydro-thermal under conditions of 180 DEG C
12h is reacted, after hydro-thermal reaction, cooled to room temperature, then, and centrifuge separation, washing, to remove impurity, then,
It is dried under the conditions of 60 DEG C, it is cooling after sufficiently drying, obtain monomer titanium dioxide.
The preparation method of elemental copper, includes the following steps:
5mmol Gerhardite is dissolved in by 20mL water using the method for ultrasonic dissolution, obtains copper nitrate solution；
Copper nitrate solution is dispersed for 60mL ethylene glycol using the method for ultrasonic disperse, obtains suspension D；
Suspension D is placed in the stainless steel autoclave that liner is polytetrafluoroethylene (PTFE), hydro-thermal under conditions of 180 DEG C
12h is reacted, after hydro-thermal reaction, cooled to room temperature, then, and centrifuge separation, washing, to remove impurity, then,
It is dried in vacuo under the conditions of 60 DEG C, it is cooling after sufficiently drying, obtain elemental copper.
As shown in Figure 1, the characteristic peak of the elemental copper of cubic phase and anatase monomer titanium dioxide and standard diagram JCPDS
1-1241 and JCPDS 1-562 is consistent, not the appearance of other impurity peaks, and the copper of the present embodiment/titanium dioxide complex light is urged
Change and have diffraction maximum identical with elemental copper and monomer titanium dioxide in material, and occur without mixed and disorderly peak, illustrates this implementation
Copper/titanic oxide composite photochemical catalyst material purity of example is higher.
Using JEOL JSM-5510LV type scanning electron microscope (SEM) to the copper/titanium dioxide complex light of the present embodiment
Catalysis material (2c) carries out morphology analysis, and it is compared with monomer titanium dioxide (2a), elemental copper (2b), test result
As shown in Figure 2.
As shown in Figure 2, TiO in the copper/titanic oxide composite photochemical catalyst material of the present embodiment2For the aggregation of nanometer little particle
At ball, rough surface, copper is little particle.
To copper/titanic oxide composite photochemical catalyst material absorption of the present embodiment, photocatalytic degradation, absorption-visible light light
The Congo red performance of catalytic degradation is tested, and it is compared with monomer titanium dioxide.Test result such as Fig. 3, Fig. 4 and figure
Shown in 5.
Copper/titanic oxide composite photochemical catalyst material absorption of the present embodiment, photocatalytic degradation, absorption-visible light light are urged
The testing procedure for changing Congo red performance of degrading is respectively as follows:
1) the Congo red performance test of Adsorption
Copper/the titanic oxide composite photochemical catalyst material for weighing 0.01g the present embodiment is distributed in the Congo red solution of 40mL
(20mg/L) is placed in dark place magnetic agitation, takes out the suspension of 3mL at regular intervals, and centrifuge separation takes supernatant in quartz
In cuvette, Congo red absorbance change is analyzed in ultraviolet-visible spectrophotometer, the variation of its concentration is reacted, thus table
Levy its adsorption effect.Wherein, the calculation formula of adsorption rate is (C0-Ct)/C0× 100% (C0: Congo red initial concentration；Ct: absorption
Solution concentration when time t).
2) the Congo red performance test of photocatalytic degradation
Copper/the titanic oxide composite photochemical catalyst material for weighing 0.01g the present embodiment is distributed in the Congo red solution of 40mL
(20mg/L) is placed in and reaches within dark place magnetic agitation 2 hours adsorption-desorption balance, then, in the 500W xenon lamp Imitating sun
Light irradiates (400nm ultraviolet light below is filtered with optical filter), takes out the suspension of 3mL, centrifuge separation at regular intervals
It takes supernatant in quartz colorimetric utensil, Congo red absorbance change is analyzed in ultraviolet-visible spectrophotometer, it is dense to react its
Degree variation, to characterize its degradation effect.Wherein, the calculation formula of degradation rate is (C0-Ct)/C0× 100% (C0: Congo red
Beginning concentration；Ct: solution concentration when degradation time t).
3) the Congo red cycle performance test of adsorption-photocatalytic degradation
Copper/the titanic oxide composite photochemical catalyst material for weighing 0.01g the present embodiment is distributed in the Congo red solution of 40mL
(20mg/L) is placed in and reaches within dark place magnetic agitation 2 hours adsorption-desorption balance, take 3mL suspension, and centrifuge separation takes
Clear liquid surveys its absorbance value, and solid precipitating returns to reaction system；Then, it is irradiated in 500W xenon lamp Imitating sunlight (visible
Light), 3mL suspension is taken after irradiating 4h, centrifuge separation takes supernatant to survey its absorbance value, and solid precipitating returns to reaction system.Point
It Ji Suan not adsorption rate and photocatalytic activity；By the liquid centrifugation after absorption-Photocatalytic Activity for Degradation reaction, obtains solid light and urge
Agent continuously adds the Congo red solution of 40mL (20mg/L), repeats above-mentioned experiment 5 times.
Wherein, photo catalysis reactor is the golden source CEL-LB70 type photo catalysis reactor of middle religion, long arc in above-mentioned performance test
Xenon source is the golden source CEL-LAX500 type lamp source of middle religion.Ultraviolet specrophotometer model UV2800.
From the figure 3, it may be seen that in the copper/titanic oxide composite photochemical catalyst material of the present embodiment copper introducing, make it to Congo red
Absorption property be obviously improved, this is because the introducing of copper, so that monomer titanium dioxide surface property changes, be conducive to just
Arnotto molecule is in its adsorption.
As shown in Figure 4, monomer titanium dioxide is under visible light illumination to Congo red no obvious degradation effect, and the present embodiment
Copper/titanic oxide composite photochemical catalyst material have apparent degradation effect to Congo red, after 4h radiation of visible light, 80% or so
It is Congo red by photocatalytic degradation.
As shown in Figure 5, after 5 circulation experiments, the copper/titanic oxide composite photochemical catalyst material of the present embodiment is to the Congo
It is red that still there is excellent adsorption-photocatalytic degradation effect, illustrate that its stability, cyclicity are good, there is practical application value.
Embodiment 2
A kind of preparation method of copper/titanic oxide composite photochemical catalyst material, comprising the following steps:
1) 4mmol titanium potassium oxalate is dissolved in by 40mL water using the method for ultrasonic dissolution, without precipitating after being clarified and being placed
Titanium potassium oxalate solution；
2) 8mmol Gerhardite is dissolved in by titanium potassium oxalate solution using the method for ultrasonic dissolution, obtains mixed solution
A；
3) it is dispersed 40mL ethylene glycol in mixed solution A using the method for ultrasonic disperse, obtains suspension B；
4) suspension B is placed in the stainless steel cauldron that liner is polytetrafluoroethylene (PTFE), hydro-thermal is anti-under conditions of 180 DEG C
18h is answered, after hydro-thermal reaction, cooled to room temperature, then, centrifuge separation, washing, to remove impurity, then, 60
It is dried in vacuo under the conditions of DEG C, it is cooling after sufficiently drying, copper/titanic oxide composite photochemical catalyst material is made.
Embodiment 3
A kind of preparation method of copper/titanic oxide composite photochemical catalyst material, comprising the following steps:
1) 2mmol titanium potassium oxalate is dissolved in by 40mL water using the method for ultrasonic dissolution, without precipitating after being clarified and being placed
Titanium potassium oxalate solution；
2) 1mmol Gerhardite is dissolved in by titanium potassium oxalate solution using the method for ultrasonic dissolution, obtains mixed solution
A；
3) it is dispersed 40mL ethylene glycol in mixed solution A using the method for ultrasonic disperse, obtains suspension B；
4) suspension B is placed in the stainless steel cauldron that liner is polytetrafluoroethylene (PTFE), hydro-thermal is anti-under conditions of 120 DEG C
8h is answered, after hydro-thermal reaction, cooled to room temperature, then, centrifuge separation, washing, to remove impurity, then, 60
It is dried in vacuo under the conditions of DEG C, it is cooling after sufficiently drying, copper/titanic oxide composite photochemical catalyst material is made.
Embodiment 4
A kind of preparation method of copper/titanic oxide composite photochemical catalyst material, comprising the following steps:
1) 6mmol titanium potassium oxalate is dissolved in by 20mL water using the method for ultrasonic dissolution, without precipitating after being clarified and being placed
Titanium potassium oxalate solution；
2) 3mmol Gerhardite is dissolved in by titanium potassium oxalate solution using the method for ultrasonic dissolution, obtains mixed solution
A；
3) it is dispersed 60mL ethylene glycol in mixed solution A using the method for ultrasonic disperse, obtains suspension B；
4) suspension B is placed in the stainless steel cauldron that liner is polytetrafluoroethylene (PTFE), hydro-thermal is anti-under conditions of 180 DEG C
18h is answered, after hydro-thermal reaction, cooled to room temperature, then, centrifuge separation, washing, to remove impurity, then, 60
It is dried in vacuo under the conditions of DEG C, it is cooling after sufficiently drying, copper/titanic oxide composite photochemical catalyst material is made.
The above is merely preferred embodiments of the present invention, be not intended to limit the invention, it is all in spirit of the invention and
Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (5)
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| CN113492007A (en) * | 2021-06-30 | 2021-10-12 | 武汉工程大学 | Copper-titanium dioxide core-shell structure composite material and preparation method and application thereof |
| CN113996299A (en) * | 2021-11-30 | 2022-02-01 | 南京邮电大学 | Titanium-based copper nano heterogeneous catalyst material and preparation method and application thereof |
| CN115430411A (en) * | 2021-06-02 | 2022-12-06 | 长春理工大学 | A kind of aluminum-titanium dioxide composite photocatalytic material for treating VOC and its preparation method |
| CN115770572A (en) * | 2022-11-23 | 2023-03-10 | 浙江工业大学 | A kind of biochar coupling copper catalyst and its preparation method and application |
| CN115845856A (en) * | 2022-11-30 | 2023-03-28 | 化学与精细化工广东省实验室 | Ultraviolet light-assisted prepared nano composite material and preparation method thereof |
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| CN115770572A (en) * | 2022-11-23 | 2023-03-10 | 浙江工业大学 | A kind of biochar coupling copper catalyst and its preparation method and application |
| CN115845856A (en) * | 2022-11-30 | 2023-03-28 | 化学与精细化工广东省实验室 | Ultraviolet light-assisted prepared nano composite material and preparation method thereof |
| CN116351417A (en) * | 2023-03-17 | 2023-06-30 | 陕西净豹新材料有限公司 | Preparation method of composite nano catalytic material for removing nitrogen oxides in atmospheric environment |
| CN116351417B (en) * | 2023-03-17 | 2024-06-07 | 陕西净豹新材料有限公司 | Preparation method of composite nano catalytic material for removing nitrogen oxides in atmospheric environment |
| CN118165449A (en) * | 2024-05-14 | 2024-06-11 | 浙江悦腾信息科技有限公司 | Long-acting heat-insulating solar film and preparation method thereof |
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