CN109647371A - A kind of heterojunction composite photocatalyst and its preparation method and application - Google Patents
A kind of heterojunction composite photocatalyst and its preparation method and application Download PDFInfo
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- CN109647371A CN109647371A CN201910109989.2A CN201910109989A CN109647371A CN 109647371 A CN109647371 A CN 109647371A CN 201910109989 A CN201910109989 A CN 201910109989A CN 109647371 A CN109647371 A CN 109647371A
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 79
- 239000002131 composite material Substances 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000003054 catalyst Substances 0.000 claims abstract description 48
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000013078 crystal Substances 0.000 claims abstract description 28
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 12
- 239000001257 hydrogen Substances 0.000 claims abstract description 12
- 230000001699 photocatalysis Effects 0.000 claims abstract description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 18
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000011148 porous material Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 claims description 5
- 229960005147 calcium acetate Drugs 0.000 claims description 5
- 235000011092 calcium acetate Nutrition 0.000 claims description 5
- 239000001639 calcium acetate Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 235000011187 glycerol Nutrition 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 150000003608 titanium Chemical class 0.000 claims description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 3
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical group [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000002351 wastewater Substances 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims 1
- 229920001223 polyethylene glycol Polymers 0.000 claims 1
- 229910002971 CaTiO3 Inorganic materials 0.000 abstract description 14
- 238000007146 photocatalysis Methods 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 4
- 230000009467 reduction Effects 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 abstract description 2
- 238000010348 incorporation Methods 0.000 abstract description 2
- 230000005764 inhibitory process Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 13
- 238000012360 testing method Methods 0.000 description 12
- 238000013019 agitation Methods 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 230000005540 biological transmission Effects 0.000 description 5
- 239000011575 calcium Substances 0.000 description 5
- 238000005119 centrifugation Methods 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 229910052593 corundum Inorganic materials 0.000 description 5
- 239000010431 corundum Substances 0.000 description 5
- 229960000935 dehydrated alcohol Drugs 0.000 description 5
- 239000004570 mortar (masonry) Substances 0.000 description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- 206010070834 Sensitisation Diseases 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910000510 noble metal 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
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000000452 restraining effect Effects 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
-
- 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
- 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
- C02F1/70—Treatment of water, waste water, or sewage by reduction
-
- 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
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- 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
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
-
- 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
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- 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
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Hydrology & Water Resources (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to photocatalysis technology field, a kind of heterojunction composite photocatalyst and its preparation method and application is disclosed, the catalyst includes the rutile TiO of special ratios2, hexagonal crystal system CaTi4O9And hexagonal crystal system CaTiO3, the present invention passes through in TiO2Middle incorporation CaTi4O9And hexagonal crystal system CaTiO3, effectively inhibition photohole and electronics is compound, quantum efficiency is improved, meanwhile, heterojunction composite photocatalyst of the invention makes the TiO with broad stopband2、CaTiO3The advantage of quality fine paper potential is shown, provides the light induced electron with stronger reducing power for light-catalyzed reaction, effectively increases photocatalytic hydrogen production by water decomposition rate and reduction removal Cr (VI) efficiency.
Description
Technical field
The present invention relates to photocatalysis technology fields, and in particular to a kind of heterojunction composite photocatalyst and preparation method thereof and
Using.
Background technique
Energy and environment problem is to restrict the principal element of human social development.The development of current world economy still relies on
Fossil energy, with being constantly progressive for human society, the consumption of the energy increases increasingly.It was predicted that the year two thousand fifty world energy sources demand
2 times of 2000 are up to, but fossil energy is just petered out, while fossil energy also brings such as greenhouse effects, atmosphere
The a series of environmental problems such as pollution, water pollution.Develop the clean reproducible energies such as solar energy, water energy, wind energy, nuclear energy come substitution
The stone energy is the key that solve energy crisis and environmental pollution.
Solar radiation reaches the far super necessary for human of energy of the earth every year, and with semiconductor catalyst photocatalysis Decomposition aquatic products
Raw hydrogen is one of the method for efficiently using solar energy and being translated into hydrogen energy source.Early in 1972, Fujishima and
Honda TiO2Make electrode with Pt, by applying a drift potential, realizes photocatalysis Decomposition for the first time under ultraviolet light irradiation
Aquatic products hydrogen.Continuous research and probe through many decades, the photochemical catalyst as photochemical catalyzing have reached hundreds of, wherein TiO2With
The advantages that its catalytic activity is high, performance is stable, cheap, harmless is favored by people, becomes most valued one
Kind photochemical catalyst.However, TiO2As photocatalyst applications in the presence of cannot be relatively low using visible light and quantum efficiency when practical
Two biggish restraining factors.For this purpose, people in depth have studied the semiconductor material for having different level structures extensively
The reaction principle of photochemical catalyzing, and pass through noble metal loading, transition cations doping, dye sensitization, composite semiconductor etc.
Method improves TiO2Quantum efficiency and the visible light utilization efficiency of raising, but effect is not very significant.Therefore, a kind of photoresponse is found
Range is wide, and the high novel photocatalyst of quantum efficiency is an important research topic.
Summary of the invention
Therefore, the present invention is intended to provide the novel heterojunction composite photocatalyst that a kind of optical response range is wide, quantum efficiency is high
Agent；Meanwhile the present invention also provides the preparation method and applications of the photochemical catalyst.
For this purpose, the present invention provides a kind of heterojunction composite photocatalyst, the rutile TiO including 31~90wt%2、
The hexagonal crystal system CaTi of 4~28wt%4O9And the rhombic system CaTiO of 6~41wt%3。
Further, the partial size of the photochemical catalyst is 30~40nm, and specific surface area is 20~25m2/ g, pore volume are
0.07~0.16cm3/ g, aperture are 12~38nm, and band-gap energy is 3.0~3.47eV.
The present invention also provides a kind of preparation methods of above-mentioned heterojunction composite photocatalyst, include the following steps:
Calcium acetate is well-dispersed in organic solvent, TiO is added2Presoma, after mixing by mixed liquor 150~
18~30h of solvent thermal reaction is carried out at 200 DEG C, and products therefrom cool down, separate, wash and dry to get described heterogeneous
Tie the presoma of composite photo-catalyst；
To the presoma with the heating rate constant-speed heating of 4~6 DEG C/min to 650~750 DEG C, then keep the temperature at least
1.8h is to get the heterojunction composite photocatalyst.
Further, the calcium acetate and the TiO2The mass ratio of the material of presoma is 1:(1~20).
Further, the TiO2Presoma is organic titanium salt；The organic solvent is ethylene glycol, glycerine, poly- second two
At least one of alcohol.
Further, the organic titanium salt is butyl titanate and/or titanium tetraisopropylate.
Further, further include the steps that carrying out mechanical lapping to it before heating the presoma.
Further, the time of the mechanical lapping is 25~35min.
The present invention also provides above-mentioned heterojunction composite photocatalyst or the hetero-junctions according to made from above-mentioned preparation method are multiple
Application of the light combination catalyst in photocatalytic hydrogen production by water decomposition.
The present invention also provides above-mentioned heterojunction composite photocatalyst or the hetero-junctions according to made from above-mentioned preparation method are multiple
The application of light combination catalyst in the treatment of waste water.
Technical solution of the present invention has the advantages that
1. heterojunction composite photocatalyst provided by the invention, the rutile TiO including special ratios2, hexagonal crystal system
CaTi4O9And hexagonal crystal system CaTiO3, the present invention passes through in TiO2Middle incorporation CaTi4O9And hexagonal crystal system CaTiO3, effectively inhibit
Photohole and electronics it is compound, improve quantum efficiency, meanwhile, heterojunction composite photocatalyst of the invention to have
The TiO of broad stopband2、CaTiO3The advantage of quality fine paper potential is shown, provides the light with stronger reducing power for light-catalyzed reaction
Raw electronics effectively increases photocatalytic hydrogen production by water decomposition rate and reduction removal Cr (VI) efficiency.
2. heterojunction composite photocatalyst provided by the invention further limits the pattern and partial size, ratio of the catalyst
Surface area etc., to improve the photocatalysis efficiency of the catalyst.
3. TiO is added in the solution of calcium acetate in the preparation method of heterojunction composite photocatalyst provided by the invention2Before
Drive body, the TiO2Hydrolysis, condensation reaction occur for presoma, to avoid TiO2Group caused by inorganic nano-particle is directly added into
Problem poly- and that uniform mixed liquor cannot be obtained, and then the uniformity of catalyst components combination is improved, improve photocatalysis
The performance of agent.It is preparation method simple process of the invention, easy to operate, it is convenient for large-scale promotion application.
4. the preparation method of heterojunction composite photocatalyst provided by the invention selects ethylene glycol, glycerine or poly- second two
Alcohol is solvent, and the nontoxic solvent is environmentally protective and at low cost, and without using other surfaces activating agent, so that it may which preparation is high
The heterojunction composite photocatalyst of stability.
Detailed description of the invention
It, below will be to specific in order to illustrate more clearly of the specific embodiment of the invention or technical solution in the prior art
Embodiment or attached drawing needed to be used in the description of the prior art be briefly described, it should be apparent that, it is described below
Attached drawing is some embodiments of the present invention, for those of ordinary skill in the art, before not making the creative labor
It puts, is also possible to obtain other drawings based on these drawings.
Fig. 1 is X-ray diffraction (XRD) figure of heterojunction composite photocatalyst in the embodiment of the present invention 1；
Fig. 2 is rutile TiO2X-ray diffraction (XRD) figure of standard substance；
Fig. 3 is hexagonal crystal system CaTi4O9X-ray diffraction (XRD) figure of standard substance；
Fig. 4 is rhombic system CaTiO3X-ray diffraction (XRD) figure of standard substance.
Specific embodiment
There is provided following embodiments is to preferably further understand the present invention, it is not limited to the best embodiment party
Formula is not construed as limiting the contents of the present invention and protection scope, anyone under the inspiration of the present invention or by the present invention and its
The feature of his prior art is combined and any and identical or similar product of the present invention for obtaining, all falls within of the invention
Within protection scope.
Specific experiment step or condition person are not specified in embodiment, according to the literature in the art described routine experiment
The operation of step or condition can carry out.Reagents or instruments used without specified manufacturer, being can be by commercially available acquisition
Conventional reagent product.
Embodiment 1
A kind of heterojunction composite photocatalyst is present embodiments provided, preparation method is as follows:
(1) presoma of heterojunction composite photocatalyst is prepared
Weigh 1.58g Ca (CH3COO)2(0.01mol) is added in 60mL ethylene glycol solution, and magnetic agitation is to complete overnight
Dissolution, then positive four butyl ester (0.01mol) of 3.40g metatitanic acid is taken to be slowly added in solution, after magnetic agitation 30min, it is transferred to 100mL
It is kept the temperature for 24 hours at 160 DEG C in ptfe autoclave.Room temperature is naturally cooled to after reaction, and centrifugation obtains product, is used in combination
Three times, dry 10h obtains white powder to dehydrated alcohol centrifuge washing in 60 DEG C of vacuum ovens, and the as described hetero-junctions is compound
The presoma of photochemical catalyst.
(2) heterojunction composite photocatalyst is prepared
The presoma of above-mentioned photochemical catalyst is placed in mortar uniformly grind 30min be placed in corundum crucible with 5 DEG C/
Min heating rate heats the lower 700 DEG C of roastings 2h of certain temperature to get the heterojunction composite photocatalyst comprising 31wt%
Rutile TiO2, 28wt% hexagonal crystal system CaTi4O9And the rhombic system CaTiO of 41wt%3。
With X-ray diffractometer to above-mentioned heterojunction composite photocatalyst and rutile TiO2, hexagonal crystal system CaTi4O9With
Rhombic system CaTiO3Standard substance carries out crystal phase test respectively, as a result respectively as shown in Fig. 1-4.As seen from Figure 1,2 θ exist
23.2 °, 27.4 °, 31.0 °, 32.5 °, 33.1 °, 36.1 °, 39.1 °, 40.7 °, 41.2 °, 42.6 °, 44.0 °, 47.4 °,
Feature is shown at 48.3 °, 49.1 °, 53.5 °, 54.3 °, 56.6 °, 59.0 °, 62.7 °, 64.0 °, 69.5 °, 73.0 °, 79.1 °
Diffraction maximum, comparison diagram 2, Fig. 3 and Fig. 4 it is found that 2 θ at 23.2 °, 33.1 °, 39.1 °, 40.7 °, 42.6 °, 47.4 °, 49.1 °,
Belong to CaTiO at 53.5 °, 59.0 °, 69.5 °, 73.0 °, 79.1 °3(110) of (JCPDS No.01-082-0228), (112),
(103), (022), (113), (220), (221), (222), (024), (224), (233), (332) crystal face, at 27.4 °
Diffraction maximum belongs to TiO at 36.1 °, 41.2 °, 44.0 °, 54.3 °, 56.6 °, 62.7 °, 64.0 °2(JCPDS No.00-004-
0551) (110), (101), (111), (210), (211), (220), (002), (310) crystal face, at 27.4 °, 31.0 °,
32.5 °, 48.3 ° belong to hexagonal phase CaTi4O9(301) of (JCPDS NO.00-026-0333), (220), (310), (216)
Crystal face.That is the heterojunction composite photocatalyst of the present embodiment contains three-phase, respectively rutile crystal type TiO2, hexagonal phase CaTi4O9
With rhombic system CaTiO3。
Above-mentioned heterojunction composite photocatalyst is tested with specific surface area measuring instrument device, obtains the photochemical catalyst
Specific surface area is 20.54m2/ g, pore volume 0.14cm3/ g, aperture 27nm；
Above-mentioned heterojunction composite photocatalyst is tested with UV-vis DRS instrument, obtains the photochemical catalyst
Band-gap energy be 3.2eV.
Above-mentioned heterojunction composite photocatalyst is tested using transmission electron microscope (TEM), obtains the photochemical catalyst
Partial size is about 30nm.
Embodiment 2
A kind of heterojunction composite photocatalyst is present embodiments provided, preparation method is as follows:
(1) presoma of heterojunction composite photocatalyst is prepared
Weigh 1.58g Ca (CH3COO)2(0.01mol) is added in 60mL ethylene glycol solution, and magnetic agitation is to complete overnight
Dissolution, then positive four butyl ester (0.09mol) of 30.63g metatitanic acid is taken to be slowly added in solution, after magnetic agitation 30min, it is transferred to
18h is kept the temperature at 200 DEG C in 100mL ptfe autoclave.Room temperature is naturally cooled to after reaction, and centrifugation is produced
Product, and three times with dehydrated alcohol centrifuge washing, dry 10h obtains white powder in 60 DEG C of vacuum ovens, as described different
The presoma of matter knot composite photo-catalyst.
(2) heterojunction composite photocatalyst is prepared
The presoma of above-mentioned photochemical catalyst is placed in mortar uniformly grind 35min be placed in corundum crucible with 4 DEG C/
Min heating rate heats the lower 750 DEG C of roastings 1.8h of certain temperature to get the heterojunction composite photocatalyst comprising
The rutile TiO of 79.6wt%2, 8.4wt% hexagonal crystal system CaTi4O9And the rhombic system CaTiO of 12wt%3。
Crystal phase test is carried out to above-mentioned heterojunction composite photocatalyst with X-ray diffractometer, according to test result it is found that originally
The heterojunction composite photocatalyst of embodiment contains three-phase, respectively rutile crystal type TiO2, hexagonal phase CaTi4O9And orthorhombic
It is CaTiO3。
Above-mentioned heterojunction composite photocatalyst is tested with specific surface area measuring instrument device, obtains the photochemical catalyst
Specific surface area is 21.72m2/ g, pore volume 0.15cm3/ g, aperture 29nm；
Above-mentioned heterojunction composite photocatalyst is tested with UV-vis DRS instrument, obtains the photochemical catalyst
Band-gap energy be 3.3eV.
Above-mentioned heterojunction composite photocatalyst is tested using transmission electron microscope (TEM), obtains the photochemical catalyst
Partial size is about 34nm.
Embodiment 3
A kind of heterojunction composite photocatalyst is present embodiments provided, preparation method is as follows:
(1) presoma of heterojunction composite photocatalyst is prepared
Weigh 1.58g Ca (CH3COO)2(0.01mol) is added in 60mL ethylene glycol solution, and magnetic agitation is to complete overnight
Dissolution, then positive four butyl ester (0.15mol) of 51.05g metatitanic acid is taken to be slowly added in solution, after magnetic agitation 30min, it is transferred to
30h is kept the temperature at 150 DEG C in 100mL ptfe autoclave.Room temperature is naturally cooled to after reaction, and centrifugation is produced
Product, and three times with dehydrated alcohol centrifuge washing, dry 10h obtains white powder in 60 DEG C of vacuum ovens, as described different
The presoma of matter knot composite photo-catalyst.
(2) heterojunction composite photocatalyst is prepared
The presoma of above-mentioned photochemical catalyst is placed in mortar uniformly grind 25min be placed in corundum crucible with 6 DEG C/
Min heating rate heats the lower 650 DEG C of roastings 3h of certain temperature to get the heterojunction composite photocatalyst comprising
The rutile TiO of 86.7wt%2, 5.4wt% hexagonal crystal system CaTi4O9And the rhombic system CaTiO of 7.9wt%3。
Crystal phase test is carried out to above-mentioned heterojunction composite photocatalyst with X-ray diffractometer, according to test result it is found that originally
The heterojunction composite photocatalyst of embodiment contains three-phase, respectively rutile crystal type TiO2, hexagonal phase CaTi4O9And orthorhombic
It is CaTiO3。
Above-mentioned heterojunction composite photocatalyst is tested with specific surface area measuring instrument device, obtains the photochemical catalyst
Specific surface area is 24.72m2/ g, pore volume 0.13cm3/ g, aperture 24nm；
Above-mentioned heterojunction composite photocatalyst is tested with UV-vis DRS instrument, obtains the photochemical catalyst
Band-gap energy be 3.3eV.
Above-mentioned heterojunction composite photocatalyst is tested using transmission electron microscope (TEM), obtains the photochemical catalyst
Partial size is about 38nm.
Embodiment 4
A kind of heterojunction composite photocatalyst is present embodiments provided, preparation method is as follows:
(1) presoma of heterojunction composite photocatalyst is prepared
Weigh 1.58g Ca (CH3COO)2(0.01mol) is added in 60mL glycerin solution, and magnetic agitation is to complete overnight
Dissolution, then positive four butyl ester (0.20mol) of 68.06g metatitanic acid is taken to be slowly added in solution, after magnetic agitation 30min, it is transferred to
240h is kept the temperature at 160 DEG C in 100mL ptfe autoclave.Room temperature is naturally cooled to after reaction, and centrifugation is produced
Product, and three times with dehydrated alcohol centrifuge washing, dry 10h obtains white powder in 60 DEG C of vacuum ovens, as described different
The presoma of matter knot composite photo-catalyst.
(2) heterojunction composite photocatalyst is prepared
The presoma of above-mentioned photochemical catalyst is placed in mortar uniformly grind 30min be placed in corundum crucible with 5 DEG C/
Min heating rate heats the lower 700 DEG C of roastings 2h of certain temperature to get the heterojunction composite photocatalyst comprising
The rutile TiO of 89.7wt%2, 4.2wt% hexagonal crystal system CaTi4O9And the rhombic system CaTiO of 6.1wt%3。
Crystal phase test is carried out to above-mentioned heterojunction composite photocatalyst with X-ray diffractometer, according to test result it is found that originally
The heterojunction composite photocatalyst of embodiment contains three-phase, respectively rutile crystal type TiO2, hexagonal phase CaTi4O9And orthorhombic
It is CaTiO3。
Above-mentioned heterojunction composite photocatalyst is tested with specific surface area measuring instrument device, obtains the photochemical catalyst
Specific surface area is 22.52m2/ g, pore volume 0.07cm3/ g, aperture 38nm；
Above-mentioned heterojunction composite photocatalyst is tested with UV-vis DRS instrument, obtains the photochemical catalyst
Band-gap energy be 3.47eV.
Above-mentioned heterojunction composite photocatalyst is tested using transmission electron microscope (TEM), obtains the photochemical catalyst
Partial size is about 40nm.
Embodiment 5
A kind of heterojunction composite photocatalyst is present embodiments provided, preparation method is as follows:
(1) presoma of heterojunction composite photocatalyst is prepared
Weigh 1.58g Ca (CH3COO)2(0.01mol) is added in 60mL polyglycol solution, and magnetic agitation is to complete overnight
Fully dissolved, then 5.68g titanium tetraisopropylate (0.02mol) is taken to be slowly added in solution, after magnetic agitation 30min, it is transferred to 100mL
240h is kept the temperature at 160 DEG C in ptfe autoclave.Room temperature is naturally cooled to after reaction, centrifugation obtains product, and
Three times with dehydrated alcohol centrifuge washing, dry 10h obtains white powder in 60 DEG C of vacuum ovens, and the as described hetero-junctions is multiple
The presoma of light combination catalyst.
(2) heterojunction composite photocatalyst is prepared
The presoma of above-mentioned photochemical catalyst is placed in mortar uniformly grind 30min be placed in corundum crucible with 5 DEG C/
Min heating rate heats the lower 700 DEG C of roastings 2h of certain temperature to get the heterojunction composite photocatalyst comprising
The rutile TiO of 89.7wt%2, 4.2wt% hexagonal crystal system CaTi4O9And the rhombic system CaTiO of 6.1wt%3。
Crystal phase test is carried out to above-mentioned heterojunction composite photocatalyst with X-ray diffractometer, according to test result it is found that originally
The heterojunction composite photocatalyst of embodiment contains three-phase, respectively rutile crystal type TiO2, hexagonal phase CaTi4O9And orthorhombic
It is CaTiO3。
Above-mentioned heterojunction composite photocatalyst is tested with specific surface area measuring instrument device, obtains the photochemical catalyst
Specific surface area is 20.02m2/ g, pore volume 0.11cm3/ g, aperture 12nm；
Above-mentioned heterojunction composite photocatalyst is tested with UV-vis DRS instrument, obtains the photochemical catalyst
Band-gap energy be 3.0eV.
Above-mentioned heterojunction composite photocatalyst is tested using transmission electron microscope (TEM), obtains the photochemical catalyst
Partial size is about 33nm.
Water hydrogen manufacturing test is catalytically decomposed in experimental example 1
300W xenon lamp (PLS-SXE300C) is selected to be used as simulated solar light source, the catalyst for taking 20mg different is separately added into
Into 50mL aqueous solution, and the formalin for being separately added into 1mL35wt% detects various photochemical catalyst effects as sacrifice agent
The generation rate of lower hydrogen, as a result see the table below shown in 1.
1 photocatalytic hydrogen production by water decomposition rate of table
| Test serial number | Catalyst type | Hydrogen generation rate (mmolh-1·g-1) |
| 1 | The catalyst of embodiment 1 | 27 |
| 2 | The catalyst of embodiment 2 | 47 |
| 3 | The catalyst of embodiment 3 | 35 |
| 4 | The catalyst of embodiment 4 | 30 |
| 5 | The catalyst of embodiment 5 | 33 |
| 6 | P25 photochemical catalyst | 9 |
| 7 | CaTiO3 | 5 |
By the data comparison in upper table 1 it is found that heterojunction composite photocatalyst of the invention is compared in the prior art
Photochemical catalyst, photocatalytic hydrogen production by water decomposition rate is significantly improved.
The reduction removal of experimental example 2 Cr (VI) test
Under simulated solar irradiation (300W xenon lamp), the catalyst for taking 20mg different is added separately to 50mL Cr (VI) concentration and is
Cr in aqueous solution (VI) concentration is measured in the aqueous solution of 50ppm, after illumination 150min respectively, and is respectively urged according to measurement result calculating
Agent see the table below shown in 1 the removal rate of Cr (VI), calculated result.
Removal rate of 2 different catalysts of table to Cr (VI)
By the data comparison in upper table 2 it is found that heterojunction composite photocatalyst of the invention is compared in the prior art
Photochemical catalyst, be significantly improved to the removal rate of Cr (VI).
Obviously, the above embodiments are merely examples for clarifying the description, and does not limit the embodiments.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or
It changes.There is no necessity and possibility to exhaust all the enbodiments.And it is extended from this it is obvious variation or
It changes still within the protection scope of the invention.
Claims (10)
1. a kind of heterojunction composite photocatalyst, which is characterized in that the rutile TiO including 31~90wt%2, 4~28wt%
Hexagonal crystal system CaTi4O9And the rhombic system CaTiO of 6~41wt%3。
2. heterojunction composite photocatalyst according to claim 1, which is characterized in that the partial size of the photochemical catalyst is 30
~40nm, specific surface area are 20~25m2/ g, pore volume are 0.07~0.16cm3/ g, aperture are 12~38nm, band-gap energy 3.0
~3.47eV.
3. a kind of preparation method of heterojunction composite photocatalyst of any of claims 1 or 2, which is characterized in that including as follows
Step:
Calcium acetate is well-dispersed in organic solvent, TiO is added2Presoma, after mixing by mixed liquor at 150~200 DEG C
Lower progress 18~30h of solvent thermal reaction, cool down, separate, wash and dry to products therefrom compound to get the hetero-junctions
The presoma of photochemical catalyst；
To the presoma with the heating rate constant-speed heating of 4~6 DEG C/min to 650~750 DEG C, at least 1.8h is then kept the temperature,
Up to the heterojunction composite photocatalyst.
4. preparation method according to claim 3, which is characterized in that the calcium acetate and the TiO2The substance of presoma
Amount ratio be 1:(1~20).
5. preparation method according to claim 3 or 4, which is characterized in that the TiO2Presoma is organic titanium salt；It is described
Organic solvent is at least one of ethylene glycol, glycerine, polyethylene glycol.
6. preparation method according to claim 5, which is characterized in that the organic titanium salt is butyl titanate and/or four
Isopropyl titanate.
7. according to the described in any item preparation methods of claim 3-6, which is characterized in that further include before being heated to the presoma
The step of mechanical lapping is carried out to it.
8. preparation method according to claim 7, which is characterized in that the time of the mechanical lapping is 25~35min.
9. heterojunction composite photocatalyst of any of claims 1 or 2 or according to the described in any item preparation sides claim 3-8
Application of the heterojunction composite photocatalyst made from method in photocatalytic hydrogen production by water decomposition.
10. heterojunction composite photocatalyst of any of claims 1 or 2 or according to the described in any item preparations of claim 3-8
The application of heterojunction composite photocatalyst made from method in the treatment of waste water.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112916014A (en) * | 2021-01-25 | 2021-06-08 | 吉林大学 | All-solid-state vector Z mechanism composite photocatalyst CaTiO3/Cu/TiO2Preparation method and application thereof |
| CN113274997A (en) * | 2021-05-27 | 2021-08-20 | 浙江大学 | Two-phase composite photocatalytic material and preparation method and application thereof |
| CN113274998A (en) * | 2021-05-27 | 2021-08-20 | 浙江大学 | Three-phase blended calcium titanate photocatalytic material and preparation method and application thereof |
| CN114984965A (en) * | 2022-05-30 | 2022-09-02 | 吉林大学 | P-n heterojunction composite photocatalyst Cu 2 O/MTiO 3 Preparation method and application thereof |
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| CN104475129A (en) * | 2014-11-25 | 2015-04-01 | 辽宁石油化工大学 | Low-temperature preparation method of copper sulfide/titanium oxide hetero-junction photocatalyst |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104475129A (en) * | 2014-11-25 | 2015-04-01 | 辽宁石油化工大学 | Low-temperature preparation method of copper sulfide/titanium oxide hetero-junction photocatalyst |
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|---|---|---|---|---|
| CN112916014A (en) * | 2021-01-25 | 2021-06-08 | 吉林大学 | All-solid-state vector Z mechanism composite photocatalyst CaTiO3/Cu/TiO2Preparation method and application thereof |
| CN112916014B (en) * | 2021-01-25 | 2022-02-18 | 吉林大学 | All-solid-state vector Z mechanism composite photocatalyst CaTiO3/Cu/TiO2Preparation method and application thereof |
| CN113274997A (en) * | 2021-05-27 | 2021-08-20 | 浙江大学 | Two-phase composite photocatalytic material and preparation method and application thereof |
| CN113274998A (en) * | 2021-05-27 | 2021-08-20 | 浙江大学 | Three-phase blended calcium titanate photocatalytic material and preparation method and application thereof |
| CN113274997B (en) * | 2021-05-27 | 2022-05-06 | 浙江大学 | Two-phase composite photocatalytic material and preparation method and application thereof |
| CN113274998B (en) * | 2021-05-27 | 2022-05-06 | 浙江大学 | Three-phase blended calcium titanate photocatalytic material and preparation method and application thereof |
| CN114984965A (en) * | 2022-05-30 | 2022-09-02 | 吉林大学 | P-n heterojunction composite photocatalyst Cu 2 O/MTiO 3 Preparation method and application thereof |
| CN114984965B (en) * | 2022-05-30 | 2023-07-21 | 吉林大学 | P-n heterojunction composite photocatalyst Cu 2 O/MTiO 3 Preparation method and application thereof |
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