CN108906131A - A kind of preparation method of composite photocatalyst material - Google Patents
A kind of preparation method of composite photocatalyst material Download PDFInfo
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- CN108906131A CN108906131A CN201810692890.5A CN201810692890A CN108906131A CN 108906131 A CN108906131 A CN 108906131A CN 201810692890 A CN201810692890 A CN 201810692890A CN 108906131 A CN108906131 A CN 108906131A
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- 239000000463 material Substances 0.000 title claims abstract description 43
- 239000002131 composite material Substances 0.000 title claims abstract description 26
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 87
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 36
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 31
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 31
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 31
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000000243 solution Substances 0.000 claims abstract description 30
- 239000001913 cellulose Substances 0.000 claims abstract description 27
- 229920002678 cellulose Polymers 0.000 claims abstract description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 24
- 238000010790 dilution Methods 0.000 claims abstract description 24
- 239000012895 dilution Substances 0.000 claims abstract description 24
- 241000219315 Spinacia Species 0.000 claims abstract description 23
- 235000009337 Spinacia oleracea Nutrition 0.000 claims abstract description 23
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 23
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 20
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000725 suspension Substances 0.000 claims abstract description 15
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 14
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 11
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 9
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 claims abstract description 8
- 239000004317 sodium nitrate Substances 0.000 claims abstract description 8
- 235000010344 sodium nitrate Nutrition 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 239000007788 liquid Substances 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 239000012065 filter cake Substances 0.000 claims description 19
- 239000005457 ice water Substances 0.000 claims description 17
- 239000006185 dispersion Substances 0.000 claims description 15
- 238000000227 grinding Methods 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 239000003292 glue Substances 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 239000012530 fluid Substances 0.000 claims description 9
- 230000032683 aging Effects 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 6
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000011010 flushing procedure Methods 0.000 claims description 6
- 239000004570 mortar (masonry) Substances 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 5
- 238000002604 ultrasonography Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 3
- 240000007594 Oryza sativa Species 0.000 claims description 2
- 235000007164 Oryza sativa Nutrition 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 235000009566 rice Nutrition 0.000 claims description 2
- 238000007873 sieving Methods 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 20
- 238000006555 catalytic reaction Methods 0.000 abstract description 15
- 238000007146 photocatalysis Methods 0.000 abstract description 13
- 239000000499 gel Substances 0.000 abstract description 7
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 abstract description 4
- 239000003963 antioxidant agent Substances 0.000 abstract description 2
- 230000003078 antioxidant effect Effects 0.000 abstract description 2
- 239000000741 silica gel Substances 0.000 abstract description 2
- 229910002027 silica gel Inorganic materials 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 238000003915 air pollution Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 229910003849 O-Si Inorganic materials 0.000 description 1
- 229910003872 O—Si Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- BLALBRWEAJQIIL-UHFFFAOYSA-N [Cl].CC(O)=O Chemical compound [Cl].CC(O)=O BLALBRWEAJQIIL-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- -1 iron ion Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002086 nanomaterial Substances 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
- 239000005416 organic matter Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 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 1
- 239000000758 substrate Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000003911 water pollution 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
-
- B01J35/396—
-
- 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
- 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
- C01B2203/1047—Group VIII metal catalysts
-
- 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 invention belongs to catalysis material preparation technical fields, and in particular to a kind of preparation method of composite photocatalyst material.Wooden nano-cellulose suspension is added in tetraethyl titanate, acetic acid is added dropwise again, silicon dioxide gel, obtain mesoporous TiO 2, to graphite powder, sulfuric acid solution is added in sodium nitrate, hydrogen peroxide obtains the titanium dioxide of load graphene oxide, sodium hydroxide will be added after its ultrasonic disperse, spinach dilution etc. obtains composite photocatalyst material, the specific surface area of graphene oxide raising mesoporous TiO 2, improve the photocatalysis efficiency of titanium dioxide, ethyl orthosilicate coats one layer of silica gel in titanium dioxide surface, increase the dispersibility of titanium dioxide, improve light-catalyzed reaction rate, pass through monoxone carboxylated graphene oxide, generate stronger bonding force, in addition antioxidant can protect the three-dimensional structure of graphene oxide not to be destroyed containing there are many in spinach dilution, with wide prospect of the application.
Description
Technical field
The invention belongs to catalysis material preparation technical fields, and in particular to a kind of preparation side of composite photocatalyst material
Method.
Background technique
The air pollution to occur frequently in recent years, water pollution and haze weather, the room air pollution especially got worse, allow
People have experienced the Disadvantages of Developing of the modern society based on fossil energy conscientiously, also have stimulated people to the depollution of environment and
The demand of clean energy technology.Under this social status quo, based on the photocatalysis technology of solar energy, with it, low energy consumption, source is steady
The features such as fixed, environmental-friendly, has been to be concerned by more and more people.
Photocatalysis technology is a kind of technology that can directly convert light energy into chemical energy, in the air that can be used for degrading or
Organic pollutant in person's water can be used for photocatalytic water hydrogen making to solve energy problem.In recent years, it is led in environmental protection and energy saving
Domain is widely used.And basis of the catalysis material as photocatalysis technology, also by extensive concern.
In the prior art, it is titanium dioxide that catalysis material is most widely used（TiO2）.TiO2It is that one kind is important partly to lead
Body catalysis material, it has, and photocatalytic degradation of organic matter activity is high, chemical property is stable, chemically-resistant and photochemical corrosion and
The characteristics such as nontoxic, thus sewage treatment and in terms of have great potential using value.However, due to TiO2
Forbidden bandwidth it is larger, it is only active in ultra-violet (UV) band, and ultraviolet light only accounts for the 4% of sunshine gross energy, this is just greatly limited
TiO2In the application of photocatalysis field.It, can be at present by noble-metal-supported, ion doping or the addition means such as light-sensitive coloring agent
Improve the catalytic performance of titanium dioxide and the response to visible light.
At least there are the following problems in the prior art：Existing visible-light photocatalysis material, photo-generate electron-hole it is compound
Probability is higher, causes the quantum efficiency of visible-light photocatalysis material lower, and broad-band gap is low to solar energy utilization ratio, and eventually leading to can
The photocatalytic activity of light-exposed catalysis material is poor etc., is restricted its application.
Therefore, it is necessary to provide it is a kind of prepare simple, catalysis material that stability is high and preparation method thereof, to promote light
The photocatalytic activity and practical value of catalysis material.
Summary of the invention
Present invention mainly solves the technical issues of, for current existing visible-light photocatalysis material, photo-generate electron-hole
Recombination probability it is higher, cause the quantum efficiency of visible-light photocatalysis material lower, since broad stopband energy gap is to Solar use
Rate is low, and the photocatalytic activity for eventually leading to visible-light photocatalysis material is poor, and the defect for being restricted its application provides one
The preparation method of kind composite photocatalyst material.
In order to solve the above-mentioned technical problem, the technical scheme adopted by the invention is that：
A kind of preparation method of composite photocatalyst material, it is characterised in that specifically preparation step is：
（1）40~50mL dehydrated alcohol is added into ultrasonic disperse instrument and the wooden nano-cellulose of 2~3g, ultrasonic disperse obtain
Cellulose suspension is placed in the conical flask with blender by cellulose suspension, is added with dropping funel into conical flask
18~20mL butyl titanate, while starting blender, 10~15min of stirring is started with the revolving speed of 200~300r/min and is obtained
Mixed liquor；
（2）4~5mL acetic acid solution is added into above-mentioned mixed liquor, 20~30mL silicon dioxide gel stirs 1~2h, received
Rice cellulose/TiO 2 sol, it is still aging, dry colloidal sol is obtained, by dry colloidal sol Muffle furnace, is put into mortar and grinds after calcining
30~35min is ground, sieving obtains mesoporous TiO 2；
（3）0.2~0.3g graphite powder and 0.12~0.13g sodium nitrate are added to the beaker equipped with 10~12mL concentrated sulfuric acid solution
In, it places the beaker in ice-water bath, is stirred to react, remove and be stirred to react under ice-water bath room temperature, 10~15mL is added into beaker
Deionized water and 20~25mL hydrogen peroxide continue to be stirred to react until bubble-free generates；
（4）It continues up to state and 20~25mL sulfuric acid solution and 10~15mL hydrogen peroxide is added in beaker, it is mesoporous to add 40~50g
Titanium dioxide is removed by suction filtration under vacuum filtrate and obtains filter cake after being stirred to react, and rinses gained filter cake until washing with deionized water
Liquid is neutrality, and the filter cake after flushing is placed in oven and dried, and obtains the titanium dioxide of load graphene oxide；
（5）The titanium dioxide of the load graphene oxide of above-mentioned preparation is placed in ultrasonic disperse machine, distilled water ultrasound point is added
It dissipates, obtains dispersion liquid, filtering removal filter residue obtains lapping liquid after spinach is ground, and grinding fluid dilution is obtained spinach dilution；
（6）By 1.0~1.2g sodium hydroxide, 0.8~1.0g monoxone, 10~12mL dispersion liquid, 20~25mL spinach dilution
It with 40~50mL ethyl orthosilicate, is placed in ultrasonic reaction machine, ultrasonic reaction, obtains reaction glue, reaction glue is placed in baking
In case, it is dried to obtain composite photocatalyst material.
Step（1）The control ultrasonic power is 150~200W, and the ultrasonic disperse time is 4~6min, dropping funel drop
Rate of acceleration is 2~3mL/min.
Step（2）The mass fraction of the acetic acid solution is 20%, and the mass fraction of silicon dioxide gel is 20%, is stood
Digestion time is 2~3 days, sets muffle furnace as 400~500 DEG C, calcination time is 4~5h, and be sieved specification is 200
Mesh.
Step（3）The mass fraction of the concentrated sulfuric acid solution is 85%, be stirred to react under ice-water bath the time be 30~
45min is removed and is stirred to react the time under ice-water bath room temperature as 1~2h, and the mass fraction of hydrogen peroxide is 10%.
Step（4）The mass fraction of the sulfuric acid solution is 8%, and the mass fraction 5% of hydrogen peroxide, being stirred to react the time is
45~50min, drying temperature be 60~70 DEG C, drying time be 20~for 24 hours.
Step（5）The ultrasonic disperse time is 10~15min, and control supersonic frequency is 30~35kHz, dispersion liquid matter
Amount concentration is 2~3mg/L, and grinding fluid dilution is 5 times of original volume.
Step（6）The ultrasonic reaction time is 1~2h, and control supersonic frequency is 30~33kHz, baking oven set temperature
It is 50~55 DEG C, drying time is 3~4h.
The beneficial effects of the invention are as follows：
（1）Wooden nano-cellulose suspension is added in tetraethyl titanate, mixed liquor is obtained, acetic acid, two are added dropwise into mixed liquor
Silica sol stirs to get nano-cellulose/TiO 2 sol, and process is still aging, calcine, grinding obtains mesoporous dioxy
Change titanium, graphite powder, sodium nitrate sequentially added into sulfuric acid solution, hydrogen peroxide under the conditions of ice-water bath, are filtered by vacuum after being stirred to react,
Filter cake is obtained, the titanium dioxide of load graphene oxide is obtained after washing is dry, the titanium dioxide of graphene oxide will be loaded
Reaction glue is obtained after sodium hydroxide, monoxone, dispersion liquid, spinach dilution, ethyl orthosilicate are added after titanium ultrasonic disperse, is done
Dry to obtain composite photocatalyst material, titanic oxide composite photochemical catalyst material of the invention is by mesoporous TiO 2 and graphene oxide
It constituting, graphene oxide can form three-dimensional structure in titanium dioxide hole, improve the specific surface area of mesoporous TiO 2, this
Light induced electron in iron ion and titanium dioxide and hole in invention in spinach dilution react, due to Fe3+/Fe4+'s
Being closer between energy level and rutile titanium dioxide conduction band, and titanium dioxide prepared by the present invention is nanometer rutile titania structure, by
It is greater than Rutile Type in the band-gap energy of Anatase itself, influences Fe2+/Fe3+Energy level and conduction band between relative position,
The capturing agent of light induced electron is become, so that the photocatalysis efficiency of titanium dioxide be made to improve；
（2）The present invention finally utilizes ethyl orthosilicate to coat one layer of silica gel in titanium dioxide surface, due to silica surface area
It is larger, the dispersibility of titanium dioxide is increased after titanium dioxide surface load layer of silicon dioxide film, has also just spread titanium dioxide
The activated centre of titanium, since the addition of silicon increases the surface acidity of titanium dioxide, the raising of surface acidity not only can be two
Titania surface forms better adsorption potential, increases the absorption to organic pollutant, can also form stronger hydroxyl groups on surface,
Capture position of these hydroxyl groups as hole, prevents the merging of electron hole pair, generate the activity hydroxy of strong oxidizing property to
Light-catalyzed reaction is accelerated, light-catalyzed reaction rate is improved, in addition titanium dioxide and silica sections are compound, silica
Or Ti-O-Si key hinder it is intergranular contact with each other, crystal form and grain growth are suppressed, and titanium dioxide surface becomes to compare
Coarse, intercrystalline pore structure also increases, and defect increases and increases the specific surface area on surface, adsorption capacity enhancing, Er Qieneng
Relatively more Lacking oxygens are generated, so rapidly can be changed into hydrophilic and keep lesser from hydrophobic after by ultraviolet light
Contact angle, surface and inside are filled with hole configurations and hydroxyl, can with very effective fixed stannic oxide/graphene nano material,
By monoxone carboxylated graphene oxide, it can react with the hydroxyl of silica, generate stronger bonding force,
In addition antioxidant can protect the three-dimensional structure of graphene oxide not to be destroyed containing there are many in spinach dilution, and iron is golden
Belonging to salt makes titanium dioxide forbidden band energy gap narrow, and generates red shift, and the optical wavelength for making titanium dioxide that conversion can be absorbed is wider, so that
Titanium dioxide shows stronger catalytic activity under visible light, has broad application prospects.
Specific embodiment
40~50mL dehydrated alcohol and the wooden nano-cellulose of 2~3g are added into ultrasonic disperse instrument, controls ultrasonic power
Cellulose suspension is obtained for 150~200W, 4~6min of ultrasonic disperse, cellulose suspension is placed in the cone with blender
In shape bottle, 18~20mL butyl titanate is added into conical flask with the drop rate of 2~3mL/min with dropping funel, simultaneously
Start blender, 10~15min of stirring is started with the revolving speed of 200~300r/min and obtains mixed liquor；Add into above-mentioned mixed liquor
Enter 4~5mL mass fraction be 20% acetic acid solution, 20~30mL mass fraction be 20% silicon dioxide gel, stirring 1~
2h obtains nano-cellulose/TiO 2 sol, still aging 2~3 days, obtains dry colloidal sol, dry colloidal sol is placed in set temperature
To be put into 30~35min of grinding in mortar after 4~5h of calcining in 400~500 DEG C of Muffle furnaces, crosses 200 meshes and obtain mesoporous two
Titanium oxide；It is 85% that 0.2~0.3g graphite powder and 0.12~0.13g sodium nitrate, which are added to equipped with 10~12mL mass fraction,
It in the beaker of concentrated sulfuric acid solution, places the beaker in ice-water bath, is stirred to react 30~45min, remove and stirred under ice-water bath room temperature
1~2h is reacted, 10~15mL deionized water and 20~25mL mass fraction is added into beaker as 10% hydrogen peroxide, continues to stir
Reaction is mixed until bubble-free generates；Continue up state in beaker be added 20~25mL mass fraction be 8% sulfuric acid solution and 10~
The hydrogen peroxide of 15mL mass fraction 5% adds 40~50g mesoporous TiO 2, is filtered by vacuum after being stirred to react 45~50min
Remove filtrate and obtain filter cake, and with deionized water rinse gained filter cake until cleaning solution be it is neutral, the filter cake after flushing is put into
Dry 20 in the baking oven that set temperature is 60~70 DEG C~for 24 hours, obtain the titanium dioxide of load graphene oxide；By above-mentioned preparation
The titanium dioxide of load graphene oxide be placed in ultrasonic disperse machine, 10~15min of distilled water ultrasonic disperse is added, control is super
Acoustic frequency is 30~35kHz, and gained dispersion liquid mass concentration is 2~3mg/L, and filtering removal filter residue is ground after spinach is ground
Grinding fluid obtains spinach dilution by grinding fluid dilution to 5 times of original volume；By 1.0~1.2g sodium hydroxide, 0.8~1.0g chlorine
Acetic acid, 10~12mL dispersion liquid, 20~25mL spinach dilution and 40~50mL ethyl orthosilicate, are placed in ultrasonic reaction machine,
1~2h of ultrasonic reaction, control supersonic frequency are 30~33kHz, obtain reaction glue, and it is 50 that reaction glue, which is placed in set temperature,
In~55 DEG C of baking ovens, dry 3~4h obtains composite photocatalyst material.
Example 1
40mL dehydrated alcohol and the wooden nano-cellulose of 2g are added into ultrasonic disperse instrument, control ultrasonic power is 150W, ultrasound
Disperse 4min, obtain cellulose suspension, cellulose suspension be placed in the conical flask with blender, with dropping funel with
18mL butyl titanate is added into conical flask for the drop rate of 2mL/min, while starting blender, with the revolving speed of 200r/min
Start stirring 10min and obtains mixed liquor；The acetic acid solution that 4mL mass fraction is 20%, 20mL mass are added into above-mentioned mixed liquor
The silicon dioxide gel that score is 20% stirs 1h, obtains nano-cellulose/TiO 2 sol, still aging 2 days, done
Dry colloidal sol is placed in the Muffle furnace that set temperature is 400 DEG C by colloidal sol, is put into mortar after calcining 4h and is ground 30min, crosses 200
Mesh obtains mesoporous TiO 2；By 0.2g graphite powder and 0.12g sodium nitrate be added to equipped with 10mL mass fraction be 85% it is dense
It in the beaker of sulfuric acid solution, places the beaker in ice-water bath, is stirred to react 30min, remove and be stirred to react 1h under ice-water bath room temperature,
10mL deionized water and 20mL mass fraction is added into beaker as 10% hydrogen peroxide, continues to be stirred to react until bubble-free produces
It is raw；The hydrogen peroxide stated and sulfuric acid solution and 10mL mass fraction 5% that 20mL mass fraction is 8% are added in beaker is continued up, then
40g mesoporous TiO 2 is added, is stirred to react after 45min and filtrate is removed by suction filtration under vacuum obtains filter cake, and rinsed with deionized water
Gained filter cake is neutrality up to cleaning solution, and the filter cake after flushing is put into dry 20h in the baking oven that set temperature is 60 DEG C, is obtained
Load the titanium dioxide of graphene oxide；The titanium dioxide of the load graphene oxide of above-mentioned preparation is placed in ultrasonic disperse machine
In, distilled water ultrasonic disperse 10min is added, control supersonic frequency is 30kHz, and gained dispersion liquid mass concentration is 2mg/L, by spinach
Filtering removal filter residue obtains lapping liquid after dish grinding, by grinding fluid dilution to 5 times of original volume, obtains spinach dilution；It will
1.0g sodium hydroxide, 0.8g monoxone, 10mL dispersion liquid, 20mL spinach dilution and 40mL ethyl orthosilicate are placed in ultrasonic anti-
It answers in machine, ultrasonic reaction 1h, control supersonic frequency is 30kHz, obtains reaction glue, and it is 50 that reaction glue, which is placed in set temperature,
In DEG C baking oven, dry 3h obtains composite photocatalyst material.
Example 2
45mL dehydrated alcohol and the wooden nano-cellulose of 2g are added into ultrasonic disperse instrument, control ultrasonic power is 175W, ultrasound
Disperse 5min, obtain cellulose suspension, cellulose suspension be placed in the conical flask with blender, with dropping funel with
19mL butyl titanate is added into conical flask for the drop rate of 2mL/min, while starting blender, with the revolving speed of 250r/min
Start stirring 13min and obtains mixed liquor；The acetic acid solution that 4mL mass fraction is 20%, 25mL mass are added into above-mentioned mixed liquor
The silicon dioxide gel that score is 20% stirs 1h, obtains nano-cellulose/TiO 2 sol, still aging 2 days, done
Dry colloidal sol is placed in the Muffle furnace that set temperature is 450 DEG C by colloidal sol, is put into mortar after calcining 4h and is ground 33min, crosses 200
Mesh obtains mesoporous TiO 2；By 0.2g graphite powder and 0.12g sodium nitrate be added to equipped with 11mL mass fraction be 85% it is dense
It in the beaker of sulfuric acid solution, places the beaker in ice-water bath, is stirred to react 37min, remove and be stirred to react 1h under ice-water bath room temperature,
13mL deionized water and 23mL mass fraction is added into beaker as 10% hydrogen peroxide, continues to be stirred to react until bubble-free produces
It is raw；The hydrogen peroxide stated and sulfuric acid solution and 13mL mass fraction 5% that 23mL mass fraction is 8% are added in beaker is continued up, then
45g mesoporous TiO 2 is added, is stirred to react after 47min and filtrate is removed by suction filtration under vacuum obtains filter cake, and rinsed with deionized water
Gained filter cake is neutrality up to cleaning solution, and the filter cake after flushing is put into dry 22h in the baking oven that set temperature is 65 DEG C, is obtained
Load the titanium dioxide of graphene oxide；The titanium dioxide of the load graphene oxide of above-mentioned preparation is placed in ultrasonic disperse machine
In, distilled water ultrasonic disperse 13min is added, control supersonic frequency is 33kHz, and gained dispersion liquid mass concentration is 2mg/L, by spinach
Filtering removal filter residue obtains lapping liquid after dish grinding, by grinding fluid dilution to 5 times of original volume, obtains spinach dilution；It will
1.1g sodium hydroxide, 0.9g monoxone, 11mL dispersion liquid, 23mL spinach dilution and 45mL ethyl orthosilicate are placed in ultrasonic anti-
It answers in machine, ultrasonic reaction 1h, control supersonic frequency is 32kHz, obtains reaction glue, and it is 53 that reaction glue, which is placed in set temperature,
In DEG C baking oven, dry 3h obtains composite photocatalyst material.
Example 3
50mL dehydrated alcohol and the wooden nano-cellulose of 3g are added into ultrasonic disperse instrument, control ultrasonic power is 200W, ultrasound
Disperse 6min, obtain cellulose suspension, cellulose suspension be placed in the conical flask with blender, with dropping funel with
20mL butyl titanate is added into conical flask for the drop rate of 3mL/min, while starting blender, with the revolving speed of 300r/min
Start stirring 15min and obtains mixed liquor；The acetic acid solution that 5mL mass fraction is 20%, 30mL mass are added into above-mentioned mixed liquor
The silicon dioxide gel that score is 20% stirs 2h, obtains nano-cellulose/TiO 2 sol, still aging 3 days, done
Dry colloidal sol is placed in the Muffle furnace that set temperature is 500 DEG C by colloidal sol, is put into mortar after calcining 5h and is ground 35min, crosses 200
Mesh obtains mesoporous TiO 2；By 0.3g graphite powder and 0.13g sodium nitrate be added to equipped with 12mL mass fraction be 85% it is dense
It in the beaker of sulfuric acid solution, places the beaker in ice-water bath, is stirred to react 45min, remove and be stirred to react 2h under ice-water bath room temperature,
15mL deionized water and 25mL mass fraction is added into beaker as 10% hydrogen peroxide, continues to be stirred to react until bubble-free produces
It is raw；The hydrogen peroxide stated and sulfuric acid solution and 15mL mass fraction 5% that 25mL mass fraction is 8% are added in beaker is continued up, then
50g mesoporous TiO 2 is added, is stirred to react after 50min and filtrate is removed by suction filtration under vacuum obtains filter cake, and rinsed with deionized water
Gained filter cake is until the filter cake after flushing to be neutral, be put into drying in the baking oven that set temperature is 70 DEG C and for 24 hours, obtained by cleaning solution
Load the titanium dioxide of graphene oxide；The titanium dioxide of the load graphene oxide of above-mentioned preparation is placed in ultrasonic disperse machine
In, distilled water ultrasonic disperse 15min is added, control supersonic frequency is 35kHz, and gained dispersion liquid mass concentration is 3mg/L, by spinach
Filtering removal filter residue obtains lapping liquid after dish grinding, by grinding fluid dilution to 5 times of original volume, obtains spinach dilution；It will
1.2g sodium hydroxide, 1.0g monoxone, 12mL dispersion liquid, 25mL spinach dilution and 50mL ethyl orthosilicate are placed in ultrasonic anti-
It answers in machine, ultrasonic reaction 2h, control supersonic frequency is 33kHz, obtains reaction glue, and it is 55 that reaction glue, which is placed in set temperature,
In DEG C baking oven, dry 4h obtains composite photocatalyst material.
Comparative example
As a comparison case with the catalysis material of Yangzhou company production
Catalysis material in composite photocatalyst material produced by the present invention and comparative example is detected, testing result such as table 1
It is shown：
Photocatalysis efficiency test
Catalysis material in composite photocatalyst material produced by the present invention and comparative example is prepared applied to photocatalytic water splitting
Hydrogen tests the generating rate of hydrogen under ultraviolet light, visible light and natural lighting.
Photocatalytic activity test
Using Metal halogen lamp as light source, its launch wavelength range is in 300nm~2.5 μm.It is molten using the sodium nitrite of 2mol/L
Liquid excludes ultraviolet light as smoke agent for shielding.The 10mg/L methyl orange solution that 250mL is prepared in quartz reaction kettle, is separately added into
Catalysis material 100mg in composite photocatalyst material produced by the present invention and comparative example, is stirred in dark state at room temperature
30min makes photochemical catalyst reach adsorption equilibrium to degradation substrate.400W Metal halogen lamp is opened, every 20min takes out 10mL suspension,
7 samples are taken, separate sample under 10000r/min with supercentrifuge, after being centrifuged 20min twice, supernatant is taken, measures above-mentioned
Supernatant wavelength 464nm absorbance and find out the photocatalytic activity of each catalyst.
1 performance measurement result of table
From the data in table 1, it can be seen that by composite photocatalyst material produced by the present invention, stability with higher and wider extinction model
It encloses, and preparation method is simple, reaction condition is mild, it is environmental-friendly, photocatalysis, solar battery, photoelectricity can be widely applied to
All various aspects such as conversion, have broad application prospects.
Claims (7)
1. a kind of preparation method of composite photocatalyst material, it is characterised in that specifically preparation step is：
（1）40~50mL dehydrated alcohol is added into ultrasonic disperse instrument and the wooden nano-cellulose of 2~3g, ultrasonic disperse obtain
Cellulose suspension is placed in the conical flask with blender by cellulose suspension, is added with dropping funel into conical flask
18~20mL butyl titanate, while starting blender, 10~15min of stirring is started with the revolving speed of 200~300r/min and is obtained
Mixed liquor；
（2）4~5mL acetic acid solution is added into above-mentioned mixed liquor, 20~30mL silicon dioxide gel stirs 1~2h, received
Rice cellulose/TiO 2 sol, it is still aging, dry colloidal sol is obtained, by dry colloidal sol Muffle furnace, is put into mortar and grinds after calcining
30~35min is ground, sieving obtains mesoporous TiO 2；
（3）0.2~0.3g graphite powder and 0.12~0.13g sodium nitrate are added to the beaker equipped with 10~12mL concentrated sulfuric acid solution
In, it places the beaker in ice-water bath, is stirred to react, remove and be stirred to react under ice-water bath room temperature, 10~15mL is added into beaker
Deionized water and 20~25mL hydrogen peroxide continue to be stirred to react until bubble-free generates；
（4）It continues up to state and 20~25mL sulfuric acid solution and 10~15mL hydrogen peroxide is added in beaker, it is mesoporous to add 40~50g
Titanium dioxide is removed by suction filtration under vacuum filtrate and obtains filter cake after being stirred to react, and rinses gained filter cake until washing with deionized water
Liquid is neutrality, and the filter cake after flushing is placed in oven and dried, and obtains the titanium dioxide of load graphene oxide；
（5）The titanium dioxide of the load graphene oxide of above-mentioned preparation is placed in ultrasonic disperse machine, distilled water ultrasound point is added
It dissipates, obtains dispersion liquid, filtering removal filter residue obtains lapping liquid after spinach is ground, and grinding fluid dilution is obtained spinach dilution；
（6）By 1.0~1.2g sodium hydroxide, 0.8~1.0g monoxone, 10~12mL dispersion liquid, 20~25mL spinach dilution
It with 40~50mL ethyl orthosilicate, is placed in ultrasonic reaction machine, ultrasonic reaction, obtains reaction glue, reaction glue is placed in baking
In case, it is dried to obtain composite photocatalyst material.
2. a kind of preparation method of composite photocatalyst material according to claim 1, it is characterised in that：Step（1）It is described
Control ultrasonic power be 150~200W, the ultrasonic disperse time be 4~6min, dropping funel drop rate be 2~3mL/min.
3. a kind of preparation method of composite photocatalyst material according to claim 1, it is characterised in that：Step（2）It is described
The mass fraction of acetic acid solution be 20%, the mass fraction of silicon dioxide gel is 20%, and the still aging time is 2~3 days, if
Determining muffle furnace is 400~500 DEG C, and calcination time is 4~5h, and be sieved specification is 200 mesh.
4. a kind of preparation method of composite photocatalyst material according to claim 1, it is characterised in that：Step（3）It is described
The mass fraction of concentrated sulfuric acid solution be 85%, it is 30~45min that the time is stirred to react under ice-water bath, is removed under ice-water bath room temperature
Being stirred to react the time is 1~2h, and the mass fraction of hydrogen peroxide is 10%.
5. a kind of preparation method of composite photocatalyst material according to claim 1, it is characterised in that：Step（4）It is described
The mass fraction of sulfuric acid solution be 8%, the mass fraction of hydrogen peroxide is 5%, and being stirred to react the time is 45~50min, dry temperature
Degree be 60~70 DEG C, drying time be 20~for 24 hours.
6. a kind of preparation method of composite photocatalyst material according to claim 1, it is characterised in that：Step（5）It is described
The ultrasonic disperse time be 10~15min, control supersonic frequency be 30~35kHz, dispersion liquid mass concentration be 2~3mg/L, grind
Grinding fluid is diluted to 5 times of original volume.
7. a kind of preparation method of composite photocatalyst material according to claim 1, it is characterised in that：Step（6）It is described
The ultrasonic reaction time be 1~2h, control supersonic frequency be 30~33kHz, baking oven set temperature be 50~55 DEG C, drying time
For 3~4h.
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| CN115582110A (en) * | 2022-10-18 | 2023-01-10 | 江苏和合环保集团有限公司 | Photocatalytic adsorption material prepared by recycling titanium-containing blast furnace slag and preparation method thereof |
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