CN108465477A - The Preparation method and use of Three-element composite photocatalyst - Google Patents
The Preparation method and use of Three-element composite photocatalyst Download PDFInfo
- Publication number
- CN108465477A CN108465477A CN201810290771.7A CN201810290771A CN108465477A CN 108465477 A CN108465477 A CN 108465477A CN 201810290771 A CN201810290771 A CN 201810290771A CN 108465477 A CN108465477 A CN 108465477A
- Authority
- CN
- China
- Prior art keywords
- tio
- preparation
- composite photocatalyst
- dispersion liquid
- element composite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 66
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 229910003081 TiO2−x Inorganic materials 0.000 claims abstract description 41
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 38
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000000463 material Substances 0.000 claims abstract description 37
- 239000006185 dispersion Substances 0.000 claims abstract description 34
- 239000007788 liquid Substances 0.000 claims abstract description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 22
- 230000001699 photocatalysis Effects 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 claims abstract description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 10
- 239000001257 hydrogen Substances 0.000 claims abstract description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 9
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000007864 aqueous solution Substances 0.000 claims abstract description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 7
- 238000000151 deposition Methods 0.000 claims abstract description 5
- LINPIYWFGCPVIE-UHFFFAOYSA-N 2,4,6-trichlorophenol Chemical compound OC1=C(Cl)C=C(Cl)C=C1Cl LINPIYWFGCPVIE-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 16
- 239000012498 ultrapure water Substances 0.000 claims description 16
- 229910001220 stainless steel Inorganic materials 0.000 claims description 10
- 239000010935 stainless steel Substances 0.000 claims description 10
- 238000006555 catalytic reaction Methods 0.000 claims description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 7
- 239000004202 carbamide Substances 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- SPFMQWBKVUQXJV-BTVCFUMJSA-N (2r,3s,4r,5r)-2,3,4,5,6-pentahydroxyhexanal;hydrate Chemical class O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O SPFMQWBKVUQXJV-BTVCFUMJSA-N 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 4
- 239000004005 microsphere Substances 0.000 claims description 4
- 229910021392 nanocarbon Inorganic materials 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000000354 decomposition reaction Methods 0.000 claims description 3
- 238000003837 high-temperature calcination Methods 0.000 claims description 3
- 238000010189 synthetic method Methods 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 2
- 230000008021 deposition Effects 0.000 claims description 2
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 claims description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical group CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims 1
- 238000007146 photocatalysis Methods 0.000 abstract description 9
- 239000003643 water by type Substances 0.000 abstract description 3
- 230000000593 degrading effect Effects 0.000 abstract 1
- 239000002906 medical waste Substances 0.000 abstract 1
- 238000001782 photodegradation Methods 0.000 abstract 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 68
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 30
- 239000003054 catalyst Substances 0.000 description 15
- 239000004408 titanium dioxide Substances 0.000 description 14
- 230000004044 response Effects 0.000 description 13
- 230000015572 biosynthetic process Effects 0.000 description 7
- 235000019441 ethanol Nutrition 0.000 description 7
- 238000001228 spectrum Methods 0.000 description 7
- 238000001291 vacuum drying Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 125000005909 ethyl alcohol group Chemical group 0.000 description 6
- 238000001237 Raman spectrum Methods 0.000 description 5
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- 230000003301 hydrolyzing effect Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 241000143432 Daldinia concentrica Species 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- 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 3
- 230000005540 biological transmission Effects 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000005242 forging Methods 0.000 description 3
- 229960001031 glucose Drugs 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 230000006798 recombination Effects 0.000 description 3
- 238000005215 recombination Methods 0.000 description 3
- 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 2
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000003738 black carbon Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000000840 electrochemical analysis Methods 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- 239000011165 3D composite Substances 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 230000002153 concerted effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002096 quantum dot Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Classifications
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
- C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The preparation method of Three-element composite photocatalyst of the present invention, includes the following steps：Carbon ball is slowly added in the aqueous solution containing absolute ethyl alcohol, dispersion liquid A is stirred to get；Butyl titanate is slowly added in absolute ethyl alcohol, dispersion liquid B is obtained after being sufficiently stirred；Dispersion liquid B is slowly added in dispersion liquid A, then by solvent-thermal method in one layer of reduced form TiO of carbon ball surface uniform deposition2‑x, obtain C@TiO2‑xComposite material；By g C3N4It is scattered in pure water, obtains mixed liquor F；By C@TiO2‑xComposite material is scattered in mixed liquor F, then obtains ternary C@TiO by hydrothermal synthesis method2‑x/g‑C3N4Heterojunction material.Three-element composite photocatalyst prepared by the present invention is ternary heterojunction material, and the medical waste waters such as 2,4,6 trichlorophenol, 2,4,6,-Ts that can be used under visible light degrading, photodegradation water hydrogen manufacturing have good photocatalysis performance.
Description
Technical field
The invention belongs to a kind of visible light-responded C@TiO2-x/g-C3N4 hetero-junctions materials of nano material synthesis technical field
The preparation method of material more particularly to a kind of Preparation method and use of Three-element composite photocatalyst.
Background technology
With industrialized fast development, energy shortage and environmental pollution already become threat human society and earth life
Two big critical problems of life.Based on having the special performances such as solar energy conversion and pollutant removing, photocatalysis technology is by conduct
Environmental improvement and the regenerated Critical policies of clean energy resource.The semiconductor anatase titanium dioxide of great market prospects
(TiO2), due to low cost, chemical stability is good, pollution-free, has been obtained extensively in fields such as production hydrogen, photocatalysis and photoelectricities
General application.However, TiO2There are two big defects：(1) broad-band gap (3.0-3.2eV) TiO2The UV light region of response only accounts for too
5% or so of sunlight；(2) a large amount of of electrons and holes compound cause its whole photocatalysis efficiency relatively low in photo-generated carrier.Cause
This, promotes TiO2Sun light utilization efficiency solve TiO2It is particularly important in the practical application of photocatalysis technology.It in recent years, pair can
Light-exposed response includes a large amount of auto-dope Ti3+Reduced form titanium dioxide (TiO2-x) attract wide attention.However, most of
Researcher is prepared by the methods of more by step, condition harshness chemical vapor deposition, high-temperature heating and high-energy particle bombardment
TiO2-x.TiO that is more bad, being reported2-xSerious agglomeration all has occurred in nano particle.Therefore, it designs and opens
Send out simple and the TiO of the response of economic method synthesizing visible light, high dispersive2-xCatalysis material still has extremely important meaning
Justice.
As good support carrier, three-dimensional (3D) carbon ball can significantly promote wide bandgap semiconductor materials in visible light
The absorbability in region.Therefore, reduced form titanium dioxide/carbon ball composite material can organically combine titanium dioxide quantum dot with
The advantages of carbon ball, there are concerted catalysis functions between two kinds of components.On the one hand, due to the introducing of black carbon ball, C TiO2-xLight inhale
It receives performance to be greatly enhanced, this effectively enhances TiO2-xSun light utilization efficiency；On the other hand, TiO2-xEquably divide
It is distributed in the surface of carbon ball, both solves TiO2-xThe phenomenon that nano particle is easily reunited improves TiO again2-xSpecific surface area, this has
Help adsorb pollutant macromolecular and generates more reactivity sites.But C@TiO2-xThe light induced electron of photocatalytic system
The recombination rate in hole does not obtain promotion largely.Two-dimentional (2D) carbonitride (g-C3N4) it is used as non-metal optical catalyst
Due to its chemical stability, electronic structure, easily prepare and the performances such as visible light-responded receive the concerns of Many researchers.Pass through
g-C3N4The recombination rate of photo-generate electron-hole pair can be effectively reduced by coupling other catalyst formation heterojunction structure, be into one
Step promotes the active effective way of its photocatalysis performance.However, up to the present there are no C@TiO2-x/g-C3N4The system of hetero-junctions
Standby and photocatalytic applications reports.Therefore, the present invention provides a kind of visible light-responded C@TiO2-x/g-C3N4Heterojunction material
Preparation method, it is therefore an objective to promote specific surface area of catalyst by building excellent 3D/2D heterojunction structures, extend photoproduction current-carrying
The service life of son, and then promote the quick separating of light induced electron and hole, to enhance the photocatalytic activity of heterojunction material.
Invention content
Present invention aims at provide a kind of simple C@TiO2-x/g-C3N4The synthesis side of ternary heterojunction photochemical catalyst
Method, the synthetic method of ternary heterojunction photochemical catalyst of the present invention are raw material by urea, glucose, butyl titanate, utilize hydro-thermal
Synthetic method and solvent-thermal method carry out synthesis of ternary heterojunction photocatalyst, have good wide spectrum photocatalytic activity.
To realize the above-mentioned technical purpose, the present invention take technical solution is：The preparation method of Three-element composite photocatalyst,
Include the following steps：
(1) carbon ball is slowly added in the aqueous solution containing absolute ethyl alcohol, stirs to get dispersion liquid A；
(2) butyl titanate is slowly added in absolute ethyl alcohol, dispersion liquid B is obtained after being sufficiently stirred；
(3) dispersion liquid B is slowly added in dispersion liquid A, then is gone back for one layer in carbon ball surface uniform deposition by solvent-thermal method
Prototype TiO2-x, obtain C@TiO2-xComposite material；
(4) by g-C3N4It is scattered in pure water, obtains mixed liquor F；
(5) by C@TiO2-xComposite material is scattered in mixed liquor F, then obtains ternary C@TiO by hydrothermal synthesis method2-x/
g-C3N4Heterojunction material.
Further, the preparation method of the carbon ball is as follows：
It takes mono- glucose monohydrates of 4.0g to be dissolved in 40ml distilled water and obtains solution C；
Then solution C is placed in 50ml stainless steel autoclaves, is heated to 180 DEG C of reaction 6h；
It waits for being washed with ultra-pure water and absolute ethyl alcohol respectively after reaction, dry 10h under 60 DEG C of vacuum environments is obtained big
Small uniform nano carbon microsphere.
Further, the mass volume ratio of the carbon ball in the dispersion liquid A, absolute ethyl alcohol and pure water is 0.2g：35ml：
0.1ml；The volume ratio of four butyl ester of carbonic acid and absolute ethyl alcohol in the dispersion liquid B is 2ml：40ml, the g-C3N4Quality be
0.06g。
Further, it is described by solvent-thermal method in one layer of reduced form TiO of carbon ball surface uniform deposition2-x(C@TiO2-xMaterial
Material) refer to：By carbon ball be dispersed in comprising absolute ethyl alcohol, butyl titanate aqueous solution in, be sufficiently stirred, be placed in 180 DEG C of perseverances
10h is reacted in warm environment, centrifugation, washing are dried to obtain C@TiO2-xComposite photocatalyst material.
Further, described that ternary C@TiO are obtained by hydrothermal synthesis method2-x/g-C3N4Heterojunction material refers to：Take 0.2g
C@TiO2-xComposite material and 0.06g g-C3N4It is dispersed in 40ml aqueous solutions, after being sufficiently stirred, is placed in 180 DEG C of constant temperature rings
10h is reacted in border, centrifugation, washing are dried to obtain C@TiO2-x/g-C3N4Tri compound catalysis material.
Further, the g-C3N4Preparation method it is as follows：
It takes 10g urea to be placed at high-temperature calcination 4h under 600 DEG C of environment, to the end of calcination, g-C is obtained after cooling room temperature3N4Sample
Product.
Further, Three-element composite photocatalyst is degraded the purposes of 2,4,6- trichlorophenol, 2,4,6,-Ts under visible light conditions.
Further, the purposes of Three-element composite photocatalyst photocatalytic hydrogen production by water decomposition under visible light.
The present invention uses high-temperature calcination to prepare two dimension g-C first3N4Material, then it is equal using hydrothermal synthesis method synthesis size
One nano carbon microsphere.And then quantitative carbon ball is dispersed in the mixed solution containing butyl titanate, passes through solvent-thermal method
It prepares by TiO2-xThe nano carbon microsphere uniformly coated, i.e. C@TiO2-xThree-dimensional composite material, finally again by hydrothermal synthesis method
Obtain C@TiO2-x/g-C3N4Ternary heterojunction catalysis material.
The present invention includes the following steps：
One, g-C3N4The preparation of photochemical catalyst
Urea is placed in hot environment and is calcined, product g-C is obtained after cooling3N4Photochemical catalyst is retained spare.
The hot environment refers to 3~4h of calcining in 550~650 DEG C of air atmospheres.
Two, the preparation of carbon ball
1. a glucose monohydrate is slowly added into distilled water, it is fitted into reaction kettle after being sufficiently stirred, constant temperature thermal response.
The glucose is 1g with distilled water mass volume ratio：10ml, the reaction temperature of the constant temperature thermal response is 160~
180 DEG C, the isothermal reaction time is 4~8h.
2. waiting for cooled to room temperature after reaction, washed respectively with ultra-pure water and absolute ethyl alcohol, is dried in vacuo, that is, makes
Obtain uniform carbon ball.
The vacuum drying temperature condition is 50~60 DEG C, and drying time is 6~12h.
Three, C@TiO2-xThe preparation of catalysis material
1. carbon ball prepared by step (2) is dispersed in the mixed solution of absolute ethyl alcohol and ultra-pure water, dispersion is stirred to get
Liquid A.
The dosage of the carbon ball, absolute ethyl alcohol and ultra-pure water is respectively 0.2g, 35mL and 0.1mL.
2. butyl titanate is slowly added in absolute ethyl alcohol, dispersion liquid B is stirred to get.
The dosage of the butyl titanate is 2mL, and the dosage of the absolute ethyl alcohol is 40mL.
3. dispersion liquid B is slowly dropped into dispersion liquid A, stirring is placed in stainless steel autoclave, constant temperature thermal response, reaction
After washed with absolute ethyl alcohol, be dried in vacuo, obtain C@TiO2-xComposite material.
The reaction temperature of the constant temperature thermal response is 160~180 DEG C, and constant temperature time is 10~12h；The absolute ethyl alcohol is washed
It is 5 times to wash number；Vacuum drying temperature condition is 50~60 DEG C, and drying time is 5~10h.
Four, C@TiO2-x/g-C3N4The preparation of heterojunction material
1. g-C prepared by step (1)3N4It is scattered in ultra-pure water, ultrasonic disperse is uniform, obtains dispersion liquid F.
The g-C3N4Amount ratio with ultra-pure water is 0.06g：40mL.
2. C@TiO prepared by step (3)2-xIt is scattered in mixed liquor F, constant temperature thermal response under stirring condition, reaction terminates
It stands, centrifuge afterwards, alternately being washed with deionized water and ethyl alcohol, vacuum drying obtains sample C TiO2-x/g-C3N4Ternary heterojunction
Photochemical catalyst.
The C@TiO2-xDosage be：0.05~0.2g；The stirring is 0.5~1h, and the temperature of constant temperature thermal response is
160~180 DEG C, constant temperature time is 8~12h；The ultra-pure water and absolute ethyl alcohol washing times are 3 times；Vacuum drying temperature item
Part is 50~60 DEG C, and drying time is 5~10h.
Using X-ray diffraction (XRD) to C@TiO in the present invention2-x/g-C3N4The success of Three-element composite photocatalyst prepare into
Shown in 1b, there is TiO such as Fig. 1 a in determination of having gone in XRD spectrum2-xWith g-C3N4Characteristic peak, with standard card PDF#76-
0318 coincide, and shows the formation of trielement composite material.
Reduced form titanium dioxide (TiO is demonstrated using Raman spectrum (Raman Spectrum)2-x) successful preparation, such as
Fig. 1 c, shown in 1d, TiO2-xRaman peaks relative to TiO2Apparent offset has occurred, shows Lacking oxygen TiO2Generation (reduced form
Titanium dioxide (TiO2-x)；The present invention further demonstrates reproducibility titanium dioxide TiO using x-ray photoelectron spectroscopy (XPS)2-x
Formation, such as Fig. 2A, shown in 2B, xps energy spectrum is shown, there are a large amount of Ti in the ternary catalysis material3+, O element power spectrums
Apparent offset has occurred, this shows the TiO in three-way catalyst2It is with reduced form TiO2-xForm exists.
C@TiO in the present invention2-x/g-C3N4The pattern of Three-element composite photocatalyst is determining by transmission electron microscope (TEM),
Fig. 3 A are carbon balls, and the carbon ball surface as can be seen from the figure prepared is smooth；Fig. 3 B are C@TiO2-xComposite material, can be with from figure
Find out TiO2-xNano particle is evenly coated at carbon ball surface；Fig. 3 C are C@TiO2-x/g-C3N4Three-element composite photocatalyst material,
As can be seen from the figure g-C3N4With C@TiO2-xIt combines closely, is evenly distributed, Fig. 3 D are then composite material element distribution maps.
Fig. 4 is C@TiO2-x/g-C3N4Ultraviolet-visible absorption spectra of trielement composite material, as seen from the figure, black carbon ball
Introducing, TiO2-xAbsorbing properties be greatly enhanced, effectively enhance TiO2-xSun light utilization efficiency；Fig. 5's
Electro-chemical test then shows that carbon ball conductive capability is extremely strong, can accelerate the conduction of electronics, greatly reduce light induced electron and hole
Recombination rate, to improve its photocatalytic activity；TiO2-xIt is distributed evenly in the surface of carbon ball, both solves TiO2-xNanometer
The phenomenon that grain is easily reunited improves TiO again2-xSpecific surface area, this helps to adsorb pollutant macromolecular and generate more anti-
Answer active site.
On the other hand, pass through two-dimentional (2D) carbonitride (g-C3N4) coupling C@TiO2-xIt is in order into one to form heterojunction structure
Step inhibits the compound of photo-generate electron-hole pair, to greatly promote the service life of light induced electron, further improves its light and urges
Change performance activity.
Another object of the present invention：One, it provides and prepares C@TiO2-x/g-C3N4The experiment side of Three-element composite photocatalyst
Method；Two, the C@TiO2-x/g-C3N4Three-element composite photocatalyst is used for photocatalytic degradation medical sewage and light under simulated solar irradiation and urges
Change hydrolytic hydrogen production.
Advantageous effect：The C@TiO prepared using simple and quick hydrothermal synthesis method and solvent-thermal method2-x/g-C3N4Tri compound
Photochemical catalyst shows excellent photocatalytic hydrogen production by water decomposition ability and photocatalytic pollutant degradation under visible light illumination
Ability.Present invention process is simple, and raw material is easy to get, and considerably reduces energy consumption and manufacturing cost, and the introducing of carbon ball solves TiO2
The problems such as being easy to reunite, also improves the absorption rate of its specific surface area and sunlight, while the method for the invention is convenient for
Batch production, it is nontoxic, meet environmental-friendly demand.
Description of the drawings
Fig. 1 is C@TiO2-x/g-C3N4The X ray diffracting spectrum (XRD) and Raman spectrum (Raman) of trielement composite material are said
C@TiO are illustrated2-x/g-C3N4Successful preparation, Ti in Raman spectrum3+, O elements power spectrum apparent offset also has occurred, show TiO2
There are a large amount of O defects and Ti3+The presence of particle, it was demonstrated that and C@TiO2-x/g-C3N4TiO in composite material2For reduction
Type TiO2-x。
Fig. 2 is x-ray photoelectron spectroscopy (XPS), and which demonstrate there are a large amount of Ti in the ternary catalysis material3+, O member
Apparent offset also has occurred in plain power spectrum, this has further demonstrated that the TiO in three-way catalyst2It is with reduced form TiO2-xForm is deposited
.
Fig. 3 is C@TiO2-x/g-C3N4The transmission electron microscope of trielement composite material, wherein (A) is the transmission electron microscope of pure carbon ball,
(B) it is C@TiO2-xTransmission electron microscope, reduced form TiO as we know from the figure2-xIt is evenly distributed on carbon ball surface, soilless sticking phenomenon；(C)
Figure is C@TiO2-x/g-C3N4Transmission electron microscope, close structure are evenly distributed；(D) figure is distribution diagram of element, shows composite material
In there are tetra- kinds of elements of C, Ti, O, N, and be evenly distributed.
Fig. 4 is C@TiO2-x/g-C3N4Ultraviolet-visible absorption spectra of tri compound catalysis material shows C@TiO2-x/
g-C3N4The visible absorption of trielement composite material is remarkably reinforced.
Fig. 5 is Three-element composite photocatalyst C@TiO2-x/g-C3N4Photoelectric current (A) and impedance diagram (B), as seen from the figure, respectively
The sequence of the photoelectric current of composite material from high to low is：IC@TiO2-x/g-C3N4＞ ITiO2-x/g-C3N4＞ IC@TiO2-x＞ Ig-C3N4＞
I TiO2-x＞ ITiO2, and impedance magnitude and photoelectric current sequence completely on the contrary, itself the result shows that, trielement composite material C@TiO2-x/
g-C3N4With best photo-generate electron-hole separative efficiency, electron lifetime is best, has more preferably photocatalytic degradation efficiency.
Fig. 6 is trielement composite material C@TiO2-x/g-C3N4Under visible light illumination to the 2,4,6- tri- of a concentration of 10mg/L
Chlorophenol photocatalytic degradation effect figure, the result shows that C@TiO2-x/g-C3N4With best photocatalytic degradation efficiency, result
It is consistent with the photochemistry test result of Fig. 3.
Fig. 7 is trielement composite material C@TiO2-x/g-C3N4Photocatalysis hydrolytic hydrogen production figure under visible light illumination, result
Show to invent the trielement composite material C@TiO of preparation according to the present invention2-x/g-C3N4With best photocatalytic hydrogen production activity.
Specific implementation mode
The present invention is further explained in the light of specific embodiments.
Embodiment 1：
The preparation method of this Three-element composite photocatalyst, includes the following steps：
Prepare g-C3N4Photochemical catalyst：
It weighs 10g urea to be put into crucible, covers crucible cover, be horizontally placed in Muffle furnace, the high warm forging under 600 DEG C of environment
4h is burnt, to the end of calcination, is cooled to room temperature to obtain g-C3N4Sample.
Embodiment 2：
The preparation method of this Three-element composite photocatalyst, includes the following steps：
Prepare monomer carbon ball：
At ambient temperature, ground mono- glucose monohydrates of 4.0g are slowly added into 40mL ultra-pure waters, are fully stirred
It is placed it in after mixing in 50mL stainless steel autoclaves, is heated to 180 DEG C of reaction 6h；It waits for using ultra-pure water and nothing respectively after reaction
Water-ethanol washs 6 times, and 60 DEG C of vacuum drying 10h obtain uniform carbon ball material.
Embodiment 3：
The preparation method of this Three-element composite photocatalyst, includes the following steps：
Prepare C@TiO2-xComposite material：
One, monomer carbon ball is prepared
1. mono- glucose monohydrates of 4.5g under room temperature, is taken to be slowly added into 45ml pure water, set after being sufficiently stirred
In 50mL stainless steel autoclaves, it is heated to 180 DEG C of reaction 6h；
2. after reaction, being washed 6 times with ultra-pure water and absolute ethyl alcohol respectively, 60 DEG C of vacuum drying 10h obtain size
Uniform carbon ball material.
Two, C@TiO are prepared2-xComposite material
1. 0.2g carbon balls is taken to be added in 35mL absolute ethyl alcohols and the ultrapure water mixed solutions of 0.1mL, ultrasonic 0.5h is divided
Dispersion liquid A；
2. 2mL butyl titanates is taken to be slowly added in 40mL absolute ethyl alcohols, it is thoroughly mixed uniformly, obtains dispersion liquid B；
3. dispersion liquid B is slowly dropped into dropwise in dispersion liquid A, it is sufficiently stirred, waits for reactant after mixing by reaction solution
It is transferred in 100mL stainless steel autoclaves, 180 DEG C of constant temperature thermal response 10h, cooled to room temperature after reaction is washed with absolute ethyl alcohol
It washs 5 times, dry 5h is to get to the C@TiO under the conditions of 60 DEG C of vacuum2-xMaterial.
Embodiment 4：
The preparation method of this Three-element composite photocatalyst, includes the following steps：
Prepare TiO2-x/g-C3N4Composite material
One, g-C is prepared3N4
It weighs 10g urea to be put into crucible, covers crucible cover, be horizontally placed in Muffle furnace, the high warm forging under 600 DEG C of environment
4h is burnt, to the end of calcination, is cooled to room temperature to obtain g-C3N4Sample.
Two, TiO is prepared2-x/g-C3N4Composite material
1. 2mL butyl titanates is taken to be slowly dropped into 10mL absolute ethyl alcohols, it is thoroughly mixed uniformly, obtains dispersion liquid D；
2. taking the g-C that 0.06g is ground3N4It is scattered in 35mL absolute ethyl alcohols and the ultrapure water mixed solutions of 0.1mL, ultrasound
Disperse 1h, obtains dispersion liquid E；
3. dispersion liquid E is slowly dropped into dispersion liquid D, 100mL stainless steel autoclaves are placed reaction liquid into after mixing
In, 180 DEG C of constant temperature thermal responses react cooled to room temperature after 10h, wash 3 times with ultra-pure water and absolute ethyl alcohol respectively, vacuum
Dry 6h is to get to the TiO under the conditions of 60 DEG C2-x/g-C3N4Composite material.
Embodiment 5：
The preparation method of this Three-element composite photocatalyst, includes the following steps：
Prepare C@TiO2-x/g-C3N4Heterojunction material
One, monomer carbon ball is prepared
1. mono- glucose monohydrates of 4.0g under room temperature, is taken to be slowly added into 45ml pure water, set after being sufficiently stirred
In 50mL stainless steel autoclaves, it is heated to 180 DEG C of reaction 6h；
2. after reaction, being washed 6 times with ultra-pure water and absolute ethyl alcohol respectively, 60 DEG C of vacuum drying 10h obtain size
The carbon ball pattern of uniform carbon ball material, preparation is as shown in Figure 3A.
Two, g-C is prepared3N4
It weighs 10g urea to be put into crucible, covers crucible cover, be horizontally placed in Muffle furnace, the high warm forging under 600 DEG C of environment
4h is burnt, to the end of calcination, is cooled to room temperature to obtain g-C3N4Sample.
Three, C@TiO are prepared2-xComposite material
1. 0.2g carbon balls is taken to be added in 35mL absolute ethyl alcohols and the ultrapure water mixed solutions of 0.1mL, ultrasonic 0.5h is divided
Dispersion liquid A；
2. 2mL butyl titanates is taken to be slowly added in 40mL absolute ethyl alcohols, it is thoroughly mixed uniformly, obtains dispersion liquid B；
3. dispersion liquid B is slowly dropped into dropwise in dispersion liquid A, it is sufficiently stirred, waits for reactant after mixing by reaction solution
It is transferred in 100mL stainless steel autoclaves, 180 DEG C of constant temperature thermal response 10h, cooled to room temperature after reaction is washed with absolute ethyl alcohol
It washs 5 times, dry 5h is to get to the C@TiO under the conditions of 60 DEG C of vacuum2-xMaterial, pattern are as shown in Figure 3B.
Four, C@TiO are prepared2-x/g-C3N4Heterojunction material
1. taking the g-C that 0.06g is ground3N4It is scattered in 40mL ultra-pure waters, ultrasonic disperse 1h obtains dispersion liquid F；
2. taking 0.2g C@TiO2-xIt is scattered in mixed liquor F, stirs 0.5h, be subsequently placed in 50mL stainless steel autoclaves,
180 DEG C of constant temperature thermal responses are reacted cooled to room temperature after 10h, are washed 3 times with ultra-pure water and absolute ethyl alcohol respectively, vacuum item
Dry 8h, obtains C@TiO under part2-x/g-C3N4Heterojunction material photochemical catalyst, the C@TiO2-x/g-C3N4Heterojunction material
XRD diagram, Raman spectrum are as shown in Figure 1, show successful preparation and the reduced form TiO of trielement composite material2-xPresence；
XPS collection of illustrative plates is as shown in Fig. 2, further demonstrated that the TiO in three-way catalyst2It is with reduced form TiO2-xForm exist, pattern and
Distribution diagram of element is as shown in Fig. 3 C and D；Prepared Three-element composite photocatalyst purple-visible absorption spectra is as shown in figure 4, show
Its absorbance in visible light region is remarkably reinforced；5 be its electro-chemical test, shows prepared Three-element composite photocatalyst
With good photo-generate electron-hole to separative efficiency,；Fig. 6 is then that prepared Three-element composite photocatalyst drops under visible light
2,4,6- trichlorophenol, 2,4,6,-T photocatalytic degradation effect figures are solved, show that its photocatalysis effect is obviously improved relative to single catalyst；Fig. 7
It is the design sketch of prepared Three-element composite photocatalyst photocatalysis hydrolytic hydrogen production under visible light, shows its hydrolytic hydrogen production ability
It is promoted significantly, is had a good application prospect.
Claims (8)
1. a kind of preparation method of Three-element composite photocatalyst, it is characterised in that include the following steps：
(1) carbon ball is slowly added in the aqueous solution containing absolute ethyl alcohol, stirs to get dispersion liquid A；
(2) butyl titanate is slowly added in absolute ethyl alcohol, dispersion liquid B is obtained after being sufficiently stirred；
(3) dispersion liquid B is slowly added in dispersion liquid A, then by solvent-thermal method in one layer of reduced form of carbon ball surface uniform deposition
TiO2-x, obtain C@TiO2-xComposite material；
(4) by g-C3N4It is scattered in pure water, obtains mixed liquor F；
(5) by C@TiO2-xComposite material is scattered in mixed liquor F, then obtains ternary C@TiO by hydrothermal synthesis method2-x/g-C3N4
Heterojunction material.
2. the preparation method of Three-element composite photocatalyst as described in claim 1, it is characterised in that the preparation side of the carbon ball
Method is as follows：
It takes mono- glucose monohydrates of 4.0g to be dissolved in 40ml distilled water and obtains solution C；
Then solution C is placed in 50ml stainless steel autoclaves, is heated to 180 DEG C of reaction 6h；
It waits for being washed with ultra-pure water and absolute ethyl alcohol respectively after reaction, dry 10h, it is equal to obtain size under 60 DEG C of vacuum environments
One nano carbon microsphere.
3. the preparation method of Three-element composite photocatalyst as described in claim 1, it is characterised in that：In the dispersion liquid A
The mass volume ratio of carbon ball, absolute ethyl alcohol and pure water is 0.2g：35ml：0.1ml；Four butyl ester of carbonic acid in the dispersion liquid B and
The volume ratio of absolute ethyl alcohol is 2ml：40ml, the g-C3N4Quality be 0.06g.
4. the preparation method of Three-element composite photocatalyst as described in claim 1, it is characterised in that：It is described to pass through solvent-thermal method
In one layer of reduced form TiO of carbon ball surface uniform deposition2-x(C@TiO2-xMaterial) refer to：Carbon ball is dispersed in comprising anhydrous second
Alcohol, butyl titanate aqueous solution in, be sufficiently stirred, be placed in 180 DEG C of isoperibols and react 10h, centrifugation, washing be dried to obtain
C@TiO2-xComposite photocatalyst material.
5. a kind of preparation method of Three-element composite photocatalyst as described in claim 1, it is characterised in that：It is described to pass through hydro-thermal
Synthetic method obtains ternary C@TiO2-x/g-C3N4Heterojunction material refers to：Take 0.2g C@TiO2-xComposite material and 0.06g g-C3N4
Be dispersed in 40ml aqueous solutions, after being sufficiently stirred, be placed in 180 DEG C of isoperibols and react 10h, centrifuge, wash it is dry
To C@TiO2-x/g-C3N4Tri compound catalysis material.
6. the preparation method of Three-element composite photocatalyst as described in claim 1, it is characterised in that：The g-C3N4Preparation
Method is as follows：
It takes 10g urea to be placed at high-temperature calcination 4h under 600 DEG C of environment, to the end of calcination, g-C is obtained after cooling room temperature3N4Sample.
7. Three-element composite photocatalyst prepared by the preparation method of Three-element composite photocatalyst as described in claim 1 is in visible light
Under the conditions of degrade 2,4,6- trichlorophenol, 2,4,6,-Ts purposes.
8. Three-element composite photocatalyst prepared by the preparation method of Three-element composite photocatalyst as described in claim 1 is in visible light
The purposes of lower photocatalytic hydrogen production by water decomposition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810290771.7A CN108465477A (en) | 2018-04-03 | 2018-04-03 | The Preparation method and use of Three-element composite photocatalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810290771.7A CN108465477A (en) | 2018-04-03 | 2018-04-03 | The Preparation method and use of Three-element composite photocatalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108465477A true CN108465477A (en) | 2018-08-31 |
Family
ID=63262664
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810290771.7A Pending CN108465477A (en) | 2018-04-03 | 2018-04-03 | The Preparation method and use of Three-element composite photocatalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108465477A (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109603888A (en) * | 2019-01-28 | 2019-04-12 | 华东交通大学 | Self assembly carbonitride-TiO2/ hollow structure biomass carbon degradation of ammonia nitrogen composite material and preparation method |
| CN110280313A (en) * | 2019-07-11 | 2019-09-27 | 哈尔滨工业大学 | A kind of three-dimensional structure load TiO2-xThe preparation method of material |
| CN111111727A (en) * | 2019-12-12 | 2020-05-08 | 西安建筑科技大学 | Ternary magnetic composite visible light catalytic nano material and preparation method and application thereof |
| CN111167498A (en) * | 2020-01-19 | 2020-05-19 | 河南师范大学 | Porous g-C3N4/Ti3C2Tx heterojunction photocatalyst and preparation method thereof |
| CN112774695A (en) * | 2021-01-28 | 2021-05-11 | 南京大学 | Direct Z-type heterojunction photocatalyst capable of being used for decomposing water and preparation method thereof |
| CN113634270A (en) * | 2021-07-20 | 2021-11-12 | 长春理工大学 | Janus nanofiber heterojunction photocatalyst modified by carbon nitride nanosheets |
| CN113926442A (en) * | 2021-10-25 | 2022-01-14 | 南通大学 | Spherical HCNs @ g-C3N4/TiO2Preparation method of photocatalyst and application of photocatalyst in dye wastewater |
| CN113941357A (en) * | 2021-12-02 | 2022-01-18 | 塔里木大学 | Si-TiO2/g-C3N4Ternary composite photocatalytic material and preparation method thereof |
| CN114068949A (en) * | 2021-11-19 | 2022-02-18 | 四川大学 | High-performance titanium-based low-platinum catalyst, preparation method thereof and application thereof in fuel cell |
| CN114570410A (en) * | 2022-03-31 | 2022-06-03 | 浙江大学 | g-C3N4/TiO2/C nano heterojunction photocatalyst and in-situ preparation method thereof |
| CN115318289A (en) * | 2022-07-04 | 2022-11-11 | 中南林业科技大学 | Preparation method of wood-based composite material, wood-based composite material and application thereof |
| CN116119875A (en) * | 2023-02-20 | 2023-05-16 | 纳琦绿能工程有限公司 | Medical wastewater treatment method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103143380A (en) * | 2013-03-21 | 2013-06-12 | 哈尔滨工业大学 | Solvent evaporation method for preparing graphite phase carbon nitride/{001} surface exposed anatase phase titanium dioxide nano composite material |
| CN103736513A (en) * | 2014-01-03 | 2014-04-23 | 北京工业大学 | Preparation method of TiO2(B)@g-C3N4 composite nano-sheet photocatalyst |
| CN107824174A (en) * | 2017-11-17 | 2018-03-23 | 南京大学 | A kind of titanium dioxide quantum dot/carbon ball composite and preparation method thereof |
-
2018
- 2018-04-03 CN CN201810290771.7A patent/CN108465477A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103143380A (en) * | 2013-03-21 | 2013-06-12 | 哈尔滨工业大学 | Solvent evaporation method for preparing graphite phase carbon nitride/{001} surface exposed anatase phase titanium dioxide nano composite material |
| CN103736513A (en) * | 2014-01-03 | 2014-04-23 | 北京工业大学 | Preparation method of TiO2(B)@g-C3N4 composite nano-sheet photocatalyst |
| CN107824174A (en) * | 2017-11-17 | 2018-03-23 | 南京大学 | A kind of titanium dioxide quantum dot/carbon ball composite and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| LIUAN GU ET AL.: ""Graphitic-C3N4-hybridized TiO2 nanosheets with reactive {0 0 1} facets to enhance the UV- and visible-light photocatalytic activity {0 0 1} facets to enhance the UV- and visible-light photocatalytic activity"", 《JOURNAL OF HAZARDOUS MATERIALS》 * |
| 卢丹: ""TiO2微球、g-C3N4/Ti3+-TiO2复合纳米片光催化剂的可控合成及其光催化降解污染物的研究"", 《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》 * |
| 郑佩等: ""TiO2@GCs纳米复合微球的制备及其吸附性能"", 《环境科学与技术》 * |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109603888A (en) * | 2019-01-28 | 2019-04-12 | 华东交通大学 | Self assembly carbonitride-TiO2/ hollow structure biomass carbon degradation of ammonia nitrogen composite material and preparation method |
| CN110280313A (en) * | 2019-07-11 | 2019-09-27 | 哈尔滨工业大学 | A kind of three-dimensional structure load TiO2-xThe preparation method of material |
| CN111111727A (en) * | 2019-12-12 | 2020-05-08 | 西安建筑科技大学 | Ternary magnetic composite visible light catalytic nano material and preparation method and application thereof |
| CN111167498B (en) * | 2020-01-19 | 2023-08-25 | 河南师范大学 | Porous g-C 3 N 4 /Ti 3 C 2 Tx heterojunction photocatalyst and preparation method thereof |
| CN111167498A (en) * | 2020-01-19 | 2020-05-19 | 河南师范大学 | Porous g-C3N4/Ti3C2Tx heterojunction photocatalyst and preparation method thereof |
| CN112774695A (en) * | 2021-01-28 | 2021-05-11 | 南京大学 | Direct Z-type heterojunction photocatalyst capable of being used for decomposing water and preparation method thereof |
| CN112774695B (en) * | 2021-01-28 | 2021-12-17 | 南京大学 | Direct Z-type heterojunction photocatalyst capable of being used for decomposing water and preparation method thereof |
| CN113634270A (en) * | 2021-07-20 | 2021-11-12 | 长春理工大学 | Janus nanofiber heterojunction photocatalyst modified by carbon nitride nanosheets |
| CN113926442A (en) * | 2021-10-25 | 2022-01-14 | 南通大学 | Spherical HCNs @ g-C3N4/TiO2Preparation method of photocatalyst and application of photocatalyst in dye wastewater |
| CN114068949A (en) * | 2021-11-19 | 2022-02-18 | 四川大学 | High-performance titanium-based low-platinum catalyst, preparation method thereof and application thereof in fuel cell |
| CN113941357A (en) * | 2021-12-02 | 2022-01-18 | 塔里木大学 | Si-TiO2/g-C3N4Ternary composite photocatalytic material and preparation method thereof |
| CN114570410B (en) * | 2022-03-31 | 2023-02-03 | 浙江大学 | g-C 3 N 4 /TiO 2 /C nano heterojunction photocatalyst and in-situ preparation method thereof |
| CN114570410A (en) * | 2022-03-31 | 2022-06-03 | 浙江大学 | g-C3N4/TiO2/C nano heterojunction photocatalyst and in-situ preparation method thereof |
| CN115318289A (en) * | 2022-07-04 | 2022-11-11 | 中南林业科技大学 | Preparation method of wood-based composite material, wood-based composite material and application thereof |
| CN116119875A (en) * | 2023-02-20 | 2023-05-16 | 纳琦绿能工程有限公司 | Medical wastewater treatment method |
| CN116119875B (en) * | 2023-02-20 | 2023-07-07 | 纳琦绿能工程有限公司 | Medical wastewater treatment method |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108465477A (en) | The Preparation method and use of Three-element composite photocatalyst | |
| Hu et al. | Step-scheme NiO/BiOI heterojunction photocatalyst for rhodamine photodegradation | |
| CN110180548A (en) | Empty nanotube/two dimension zinc ferrite nanometer sheet heterojunction composite and its application in removal water pollutant in one-dimensional indium oxide | |
| CN103480399B (en) | Micronano-structured and silver phosphate based composite visible light catalytic material and preparing method thereof | |
| CN108479810A (en) | A kind of WS2/ZnIn2S4Composite visible light catalyst and preparation method thereof | |
| CN103801284B (en) | A kind of preparation method of pucherite-graphene composite photocatalyst | |
| CN106944074B (en) | A kind of visible-light response type composite photo-catalyst and its preparation method and application | |
| CN106732527B (en) | A kind of bismuth/composite bismuth vanadium photocatalyst and preparation method thereof and the application in photocatalytic degradation of organic matter | |
| CN105688899B (en) | The preparation method and purposes of a kind of Three-element composite photocatalyst | |
| CN103599802A (en) | Preparation method of silver phosphate/graphene nanocomposite | |
| CN109847786A (en) | A kind of preparation method and application of Z-type photochemical catalyst MgAlLDH/CN-H | |
| CN107020143A (en) | A kind of preparation method and purposes of visible light-responded Three-element composite photocatalyst | |
| CN102580714A (en) | Graphene oxide/silver phosphate composite visible light catalyst and preparation method thereof | |
| CN108940332B (en) | High-activity MoS2/g-C3N4/Bi24O31Cl10Preparation method of composite photocatalyst | |
| CN108262054A (en) | A kind of preparation method of silver vanadate/nitride porous carbon heterojunction composite photocatalyst | |
| CN106378160B (en) | It is a kind of to prepare CdS/MoS2The method of composite hollow square photochemical catalyst | |
| CN110252326A (en) | A kind of copper tungstate@zinc oxide composite photocatalyst and the preparation method and application thereof | |
| CN107824174A (en) | A kind of titanium dioxide quantum dot/carbon ball composite and preparation method thereof | |
| CN109847780A (en) | A kind of AgBr/BiOI/g-C3N4The preparation method and applications of tri compound catalysis material | |
| CN104801292A (en) | Preparation method for zinc oxide hollow nanosphere/graphene composite material | |
| CN113134381B (en) | Bi 4 O 5 I 2 Carbon nitride boron quantum dot photocatalytic material and preparation method and application thereof | |
| CN110589886A (en) | Preparation method of bismuth oxycarbonate | |
| CN107790129A (en) | Preparation method of cuprous oxide/graphene visible-light photocatalyst and products thereof and application | |
| CN110721698A (en) | Bismuth vanadate/copper vanadate composite photocatalyst and preparation method and application thereof | |
| CN110433847A (en) | A kind of two dimension composite photo-catalyst h-BN/Ti3C2/TiO2And the preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180831 |