CN110721726A - CdS-g-C3N4Loaded nano TiO2Photocatalytic hydrogen production composite catalyst and preparation method thereof - Google Patents
CdS-g-C3N4Loaded nano TiO2Photocatalytic hydrogen production composite catalyst and preparation method thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 55
- 239000001257 hydrogen Substances 0.000 title claims abstract description 54
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 54
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 50
- 239000003054 catalyst Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims description 33
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 78
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 75
- 230000001699 photocatalysis Effects 0.000 claims abstract description 43
- 229910017944 Ag—Cu Inorganic materials 0.000 claims abstract description 34
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims abstract description 12
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims abstract description 12
- YKYOUMDCQGMQQO-UHFFFAOYSA-L Cadmium chloride Inorganic materials Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 claims abstract description 7
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 89
- 238000006243 chemical reaction Methods 0.000 claims description 59
- 239000012153 distilled water Substances 0.000 claims description 52
- 238000010438 heat treatment Methods 0.000 claims description 39
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 32
- 239000012046 mixed solvent Substances 0.000 claims description 30
- 239000002904 solvent Substances 0.000 claims description 28
- 235000019441 ethanol Nutrition 0.000 claims description 25
- 238000001354 calcination Methods 0.000 claims description 24
- 239000000047 product Substances 0.000 claims description 24
- 239000012265 solid product Substances 0.000 claims description 24
- 238000001291 vacuum drying Methods 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 21
- 239000012298 atmosphere Substances 0.000 claims description 18
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 13
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 10
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 8
- 239000003638 chemical reducing agent Substances 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 8
- 239000012279 sodium borohydride Substances 0.000 claims description 8
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 239000008247 solid mixture Substances 0.000 claims description 8
- 239000000463 material Substances 0.000 abstract description 20
- 238000010521 absorption reaction Methods 0.000 abstract description 10
- 238000005215 recombination Methods 0.000 abstract description 5
- 230000006798 recombination Effects 0.000 abstract description 5
- 230000031700 light absorption Effects 0.000 abstract description 4
- 238000005054 agglomeration Methods 0.000 abstract description 3
- 230000005012 migration Effects 0.000 abstract description 3
- 238000013508 migration Methods 0.000 abstract description 3
- 229910017108 Fe—Fe Inorganic materials 0.000 abstract 1
- 239000000956 alloy Substances 0.000 abstract 1
- 229910045601 alloy Inorganic materials 0.000 abstract 1
- 230000007423 decrease Effects 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 24
- 239000004065 semiconductor Substances 0.000 description 13
- 229920000877 Melamine resin Polymers 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 6
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 4
- 238000006303 photolysis reaction Methods 0.000 description 4
- 230000015843 photosynthesis, light reaction Effects 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 229910012463 LiTaO3 Inorganic materials 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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- 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
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
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- 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
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The invention relates to the technical field of photocatalytic hydrogen production catalysts, and discloses CdS-g-C3N4Loaded nano TiO2The photocatalytic hydrogen production composite catalyst comprises the following raw materials in formula: thioacetamide, CdCl2Fe doped g-C3N4Ag-Cu modified nano TiO2. The CdS-g-C3N4Loaded nano TiO2The photocatalytic hydrogen production composite catalyst is prepared by doping Fe in g-C3N4The surface of the material forms crack-shaped and mesoporous structures, and g-C is increased3N4Specific surface area of Fe decreases g-C3N4The resistivity of the Fe-Fe alloy promotes the migration of photo-generated electrons, and Fe can capture photo-generated carriersThe flow reduces the recombination rate of photo-generated electrons and holes, enhances the hydrogen production efficiency of the photocatalytic material, and has CdS and g-C3N4Form heterojunction, and reduce g-C3N4Band gap energy of (CdS) g-C3N4The characteristic absorption edge is red-shifted, the light absorption wave band is increased, and Ag-Cu is in TiO2The surface of the nano TiO is formed into clusters, so that the nano TiO is enlarged2Porosity between molecules, such that CdS-g-C3N4The heterojunction can be uniformly loaded to the nano-TiO2Surface of CdS-g-C3N4Agglomeration and caking in water.
Description
Technical Field
The invention relates to the technical field of photocatalytic hydrogen production catalysts, in particular to CdS-g-C3N4Loaded nano TiO2The photocatalytic hydrogen production composite catalyst and the preparation method thereof.
Background
With the continuous increase of global energy demand and the increasing severity of environmental pollution, the research and development of new green energy are more and more concerned by people, and hydrogen energy is a secondary energy, has the advantages of cleanness, high efficiency, safety and the like, is the most ideal pollution-free green energy, and is currently used for H2The preparation method mainly comprises the methods of raw material hydrogen production, natural gas hydrogen production, heavy oil oxidation hydrogen production, hydrolysis hydrogen production and the like, wherein the hydrolysis hydrogen production method comprises electrocatalytic hydrogen production and photocatalytic hydrogen production.
The photolytic water reaction can convert light energy into chemical energy, the photocatalytic reaction is divided into 'energy barrier reduction' and 'energy barrier increase' reactions, and water is decomposed to generate H2And O2Belongs to high energy barrier reaction, the Gibbs free energy of the reaction is more than zero, and in order to decompose water and release hydrogen, the conduction band potential of a semiconductor photocatalytic material is required to be more than the hydrogen electrode potential EH +/H thermodynamically2Negative, and the valence band potential should be higher than the oxygen electrode potential EO2/H2The principle of photolysis of water is as follows: light is radiated onto a semiconductor material, and when the energy of the radiation is greater than the forbidden bandwidth of the semiconductor, electrons in the semiconductor are excited to transition from the valence band to the conduction band, while holes remain in the valence band, causing the electrons and holes to separate, and then reducing water to hydrogen and oxidizing to oxygen at different locations of the semiconductor, respectively.
The existing photolytic water splitting material mainly comprises tantalate LiTaO3、KTaO3Niobate K4Nb6O17Titanate K2La2Ti3O10ZnSeS and Znln multicomponent sulfide2S4，g-C3N4Heterojunction semiconductor materials, etc., present g-C3N4The heterojunction semiconductor material has high crystallinity, low specific surface area, insufficient contact with water molecules, and g-C3N4The heterojunction has narrow ultraviolet and visible light absorption wave band, cannot completely absorb light energy of different wave bands, and simultaneously g-C3N4In a heterojunctionThe photo-generated electrons and the holes are easy to combine, the number of effective photo-generated electrons and holes is reduced, and the efficiency of hydrogen production by photocatalytic material photolysis water is greatly reduced.
Disclosure of Invention
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides CdS-g-C3N4Loaded nano TiO2The photocatalytic hydrogen production composite catalyst and the preparation method solve the problem of g-C3N4The semiconductor material has low specific surface area and can not be fully contacted with water molecules, and simultaneously solves the problem that g-C is not fully contacted with water molecules3N4The ultraviolet and visible absorption band of the semiconductor material is narrow, and the photo-generated electrons and holes are easy to recombine.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: CdS-g-C3N4Loaded nano TiO2The photocatalytic hydrogen production composite catalyst comprises the following formula raw materials in parts by weight: 12-16 parts of thioacetamide and 30-40 parts of CdCl224-43 parts of Fe-doped g-C3N415-20 parts of Ag-Cu modified nano TiO2。
Preferably, the Fe is doped with g-C3N4The preparation method comprises the following steps:
(1) adding FeCl into a mixed solvent of distilled water and ethanol with the volume ratio of 1.5-2:1 in sequence3Thiourea and melamine, heating the solution to 100-120 ℃, reacting for 12-15 h, placing the solution in a vacuum drying oven, and removing the mixed solvent.
(2) The solid product was placed in an atmospheric resistance furnace and N was passed through2The heating rate of the resistance furnace is 3-5 ℃/min, and the calcination is carried out for 4-6 h at the temperature of 580-600 ℃, and the calcination product is Fe-doped g-C3N4。
Preferably, the FeCl3The mass molar ratio of the three substances is 1:24-30: 4-5.5.
Preferably, the Ag-Cu modified nano TiO2The preparation method comprises the steps ofThe following steps:
(1) adding tetrabutyl titanate, Cu (NO) into absolute ethyl alcohol solvent3)3And AgNO3Reacting the solution at-5-0 deg.c for 40-45 hr, adding NaBH as reductant4Reacting for 2-3 h at-10-0 ℃.
(2) Distilling the solution under reduced pressure to remove the solvent, washing the solid product, drying, placing the solid mixture in an atmosphere resistance furnace and introducing N2The heating rate of the resistance furnace is 3-5 ℃/min, the calcination is carried out for 3-6 h at the temperature of 620-640 ℃, and the calcination product is the Ag-Cu modified nano TiO2。
Preferably, the tetrabutyl titanate, Cu (NO)3)3、AgNO3And NaBH4The molar ratio of the four substances is 120-150:1-1.5:1: 2.5-3.
Preferably, the CdS-g-C3N4Loaded nano TiO2The preparation method of the photocatalytic hydrogen production composite catalyst comprises the following steps:
(1) adding 12-16 parts of thioacetamide and 30-40 parts of CdCl into a mixed solvent of distilled water and ethanol with the volume ratio of 1.5-2:1 in sequence2And 24-43 parts of Fe-doped g-C3N4Performing ultrasonic dispersion treatment on the solution at 40-50 ℃ for 2-3 h with the ultrasonic frequency of 20-25KHz, heating the solution to 70-80 ℃, performing reflux reaction for 2-4 h, putting the solution in a vacuum drying oven to evaporate the solvent, washing and drying the solid product to prepare the CdS-Fe modified g-C3N4A composite material.
(2) Adding 15-20 parts of Ag-Cu modified nano TiO into distilled water solvent in sequence2And g-C modified by CdS-Fe prepared in the step (1)3N4The composite material is prepared by subjecting the solution to ultrasonic dispersion treatment at 60-80 deg.C for 2-3 h with ultrasonic frequency of 20-25KHz, placing the solution in a vacuum drying oven to evaporate solvent, and fully drying the solid mixed product to obtain CdS-g-C3N4Loaded nano TiO2The photocatalytic hydrogen production composite catalyst.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
the CdS-g-C3N4Loaded nano TiO2The photocatalytic hydrogen production composite catalyst adopts an in-situ method to dope Fe with g-C3N4In g-C3N4Form rich pore structures inside, form crack-shaped and mesoporous structures on the surface, and increase the g-C3N4The specific surface area of the catalyst increases the contact area with water molecules, improves the efficiency of photolysis water hydrogen production, and improves g-C by doping Fe3N4The band structure promotes the absorption of light energy, and simultaneously Fe reduces g-C3N4The resistivity of the material improves the conductivity of the semiconductor material, promotes the diffusion and migration processes of photo-generated electrons, and Fe can capture photo-generated carriers, so that the recombination rate of the photo-generated electrons and holes is reduced, and the photocatalytic activity and the hydrogen production efficiency of the photocatalytic material are enhanced.
The CdS-g-C3N4Loaded nano TiO2The CdS and g-C are made by in-situ compounding3N4Forming crystal face recombination to prepare CdS-g-C3N4Heterojunction, reduced g-C3N4Band gap energy of (CdS) g-C3N4The characteristic absorption edge is red-shifted, so that the visible light region of the ultraviolet-visible absorption spectrum of the heterojunction semiconductor material is extended, the wave band of the ultraviolet-visible absorption light is increased, and the utilization rate of light energy is improved.
The CdS-g-C3N4Loaded nano TiO2The photocatalytic hydrogen production composite catalyst uses Ag-Cu to modify nano TiO2As CdS-g-C3N4Carrier of heterojunction, Ag-Cu modification on TiO2The surface of the steel is added with nano TiO2Specific surface area of (2), and Ag-Cu in TiO2Cluster is formed on the surface, and the nano TiO is enlarged2Porosity and pore volume between molecules, such that CdS-g-C3N4The heterojunction can be uniformly loaded to the nano-TiO2Surface of CdS-g-C3N4Has poor dispersibility in water and forms clustersThe aggregation and agglomeration reduce the utilization effect of light energy, and the modification of Ag expands TiO2The spectrum absorption range of the composite material increases the ultraviolet-visible absorption light wave band of the photocatalytic composite material, and enhances the utilization rate of the composite material to light energy and the hydrogen production efficiency.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: CdS-g-C3N4Loaded nano TiO2The photocatalytic hydrogen production composite catalyst comprises the following formula raw materials in parts by weight: 12-16 parts of thioacetamide and 30-40 parts of CdCl224-43 parts of Fe-doped g-C3N415-20 parts of Ag-Cu modified nano TiO2。
Fe doped g-C3N4The preparation method comprises the following steps:
(1) adding a proper amount of distilled water and ethanol mixed solvent into a reaction bottle, wherein the volume ratio of the distilled water to the ethanol is 1.5-2:1, and sequentially adding FeCl3The mass molar ratio of the three substances is 1:24-30:4-5.5, the reaction bottle is placed in an oil bath pot and heated to 120 ℃, the reaction is carried out for 12-15 h under uniform stirring, the solution is placed in a vacuum drying box and heated to 70-80 ℃, and the mixed solvent is removed.
(2) The solid product was placed in an atmospheric resistance furnace and N was passed through2The heating rate of the resistance furnace is 3-5 ℃/min, and the calcination is carried out for 4-6 h at the temperature of 580-600 ℃, and the calcination product is Fe-doped g-C3N4。
Ag-Cu modified nano TiO2The preparation method comprises the following steps:
(1) adding tetrabutyl titanate into absolute ethyl alcohol solvent, stirring uniformly, and adding Cu (NO)3)3And AgNO3Placing the solution in a low-temperature reactor, uniformly stirring and reacting for 40-45 h at-5-0 ℃, adding a reducing agent NaBH into the solution4Tetrabutyl titanate, Cu (NO)3)3、AgNO3And NaBH4The weight molar ratio of the four substances is 150:1-1.5:1:2.5-3, and the four substances are stirred at a constant speed at the temperature of-10-0 ℃ for reaction for 2-3 h.
(2) Distilling the solution under reduced pressure to remove the solvent, washing the solid product with appropriate amount of distilled water and anhydrous ethanol and drying thoroughly, placing the solid mixture in an atmosphere resistance furnace and introducing N2The heating rate of the resistance furnace is 3-5 ℃/min, the calcination is carried out for 3-6 h at the temperature of 620-640 ℃, and the calcination product is the Ag-Cu modified nano TiO2。
CdS-g-C3N4Loaded nano TiO2The preparation method of the photocatalytic hydrogen production composite catalyst comprises the following steps:
(1) adding a proper amount of a mixed solvent of distilled water and ethanol into a reaction bottle, wherein the volume ratio of the distilled water to the ethanol is 1.5-2:1, and sequentially adding 12-16 parts of thioacetamide and 30-40 parts of CdCl2And 24-43 parts of Fe-doped g-C3N4Placing the solution in an ultrasonic disperser with ultrasonic frequency of 20-25KHz, performing ultrasonic dispersion treatment at 40-50 deg.C for 2-3 h, placing the reaction flask in a constant temperature water bath, heating to 70-80 deg.C, stirring at constant speed, refluxing for 2-4 h, placing the solution in a vacuum drying oven, heating to 60-70 deg.C, completely evaporating solvent, washing solid product with appropriate amount of distilled water, and fully drying to obtain CdS-Fe modified g-C3N4A composite material.
(2) Adding a proper amount of distilled water into a reaction bottle, and sequentially adding 15-20 parts of Ag-Cu modified nano TiO2And g-C modified by CdS-Fe prepared in the step (1)3N4The composite material is prepared by placing the solution in an ultrasonic disperser with ultrasonic frequency of 20-25KHz, performing ultrasonic dispersion treatment at 60-80 deg.C for 2-3 h, placing the reaction flask in a vacuum drying oven, heating to 60-70 deg.C, removing distilled water, and fully drying the solid mixed product to obtain CdS-g-C3N4Loaded nano TiO2The photocatalytic hydrogen production composite catalyst.
Example 1:
(1) preparation of Ag-Cu modified nano TiO2Component 1: adding tetrabutyl titanate into absolute ethyl alcohol solvent, stirring uniformly, and adding Cu (NO)3)3And AgNO3Putting the solution into a low-temperature reactor, reacting for 40 h at 0 ℃ under uniform stirring, and adding a reducing agent NaBH into the solution4Tetrabutyl titanate, Cu (NO)3)3、AgNO3And NaBH4The molar ratio of the four substances is 120:1:1:2.5, the mixture is stirred at a constant speed at 0 ℃ for reaction for 2 hours, the solution is distilled under reduced pressure to remove the solvent, a proper amount of distilled water and absolute ethyl alcohol are used for washing a solid product and are fully dried, the solid mixture is placed in an atmosphere resistance furnace, and N is introduced into the atmosphere resistance furnace2The temperature rise rate of the resistance furnace is 3 ℃/min, the material is calcined for 3 hours at the temperature of 620 ℃, and the calcined product is Ag-Cu modified nano TiO2And (3) component 1.
(2) Preparation of Fe-doped g-C3N4Component 1: adding a proper amount of distilled water and ethanol mixed solvent into a reaction bottle, wherein the volume ratio of the distilled water to the ethanol mixed solvent is 1.5:1, and sequentially adding FeCl3Thiourea and melamine with the mass molar ratio of 1:24:4, placing a reaction bottle in an oil bath pot, heating to 100 ℃, stirring at a constant speed for reaction for 12 hours, placing the solution in a vacuum drying oven, heating to 70 ℃, removing the mixed solvent, placing the solid product in an atmosphere resistance furnace, and introducing N2The temperature rise rate of the resistance furnace is 3 ℃/min, and the calcination is carried out for 4 h at 580 ℃, and the calcination product is Fe-doped g-C3N4And (3) component 1.
(3) CdS-Fe modified g-C3N4Composite material 1: the preparation method comprises the steps of adding a proper amount of a mixed solvent of distilled water and ethanol into a reaction bottle, sequentially adding 12 parts of thioacetamide and 30 parts of CdCl, wherein the volume ratio of the distilled water to the ethanol is 1.5:12And 43 parts of Fe-doped g-C3N4Placing the solution into an ultrasonic disperser with ultrasonic frequency of 20 KHz for ultrasonic dispersion treatment at 40 ℃ for 2 h, placing a reaction bottle into a constant-temperature water bath kettle, heating to 70 ℃, stirring at constant speed for reflux reaction for 2 h, placing the solution into a vacuum drying oven, heating to 60 ℃, completely evaporating the solvent, washing the solid product with a proper amount of distilled water, fully drying, and preparing the CdS-Fe modified g-C3N4A composite material 1.
(4) Preparation of CdS-g-C3N4Loaded nano TiO2The photocatalytic hydrogen production composite catalyst 1: adding a proper amount of distilled water into a reaction bottle, and sequentially adding 15 parts of Ag-Cu modified nano TiO2Component 1 and step (3) aboveThe prepared CdS-Fe modified g-C3N4Placing the solution in an ultrasonic disperser with ultrasonic frequency of 20 KHz, performing ultrasonic dispersion treatment at 60 deg.C for 2 h, placing the reaction flask in a vacuum drying oven, heating to 60 deg.C, removing distilled water, and fully drying the solid mixed product to obtain CdS-g-C3N4Loaded nano TiO2The photocatalytic hydrogen production composite catalyst 1.
Example 2:
(1) preparation of Ag-Cu modified nano TiO2And (2) component: adding tetrabutyl titanate into absolute ethyl alcohol solvent, stirring uniformly, and adding Cu (NO)3)3And AgNO3Placing the solution in a low-temperature reactor, stirring at constant speed for 45 h at-5 ℃, adding a reducing agent NaBH into the solution4Tetrabutyl titanate, Cu (NO)3)3、AgNO3And NaBH4The molar ratio of the four substances is 120:1.5:1:2.5, the mixture is stirred at a constant speed at 0 ℃ for reaction for 2 hours, the solution is distilled under reduced pressure to remove the solvent, a proper amount of distilled water and absolute ethyl alcohol are used for washing a solid product and are fully dried, the solid mixture is placed in an atmosphere resistance furnace, and N is introduced into the atmosphere resistance furnace2The temperature rise rate of the resistance furnace is 5 ℃/min, the calcination is carried out for 3 h at 640 ℃, and the calcination product is Ag-Cu modified nano TiO2And (3) component 2.
(2) Preparation of Fe-doped g-C3N4And (2) component: adding a proper amount of distilled water and ethanol mixed solvent into a reaction bottle, wherein the volume ratio of the distilled water to the ethanol mixed solvent is 2:1, and sequentially adding FeCl3Thiourea and melamine with the mass molar ratio of 1:24:4, placing a reaction bottle in an oil bath pot, heating to 120 ℃, stirring at a constant speed for reaction for 12 hours, placing the solution in a vacuum drying oven, heating to 80 ℃, removing the mixed solvent, placing the solid product in an atmosphere resistance furnace, and introducing N2The temperature rise rate of the resistance furnace is 3 ℃/min, and the calcination is carried out for 4 h at 580 ℃, and the calcination product is Fe-doped g-C3N4And (3) component 2.
(3) CdS-Fe modified g-C3N4Composite material 2: the preparation method comprises adding appropriate amount of mixed solvent of distilled water and ethanol into a reaction flask at a volume ratio of 2:1, sequentially adding13 parts of thioacetamide, 33 parts of CdCl2And 38 parts of Fe-doped g-C3N4And (2) placing the solution into an ultrasonic disperser with ultrasonic frequency of 25KHz, performing ultrasonic dispersion treatment at 40 ℃ for 3 h, placing a reaction bottle into a constant-temperature water bath kettle, heating to 70 ℃, stirring at constant speed, performing reflux reaction for 2 h, placing the solution into a vacuum drying oven, heating to 60 ℃, completely evaporating the solvent, washing the solid product with a proper amount of distilled water, and fully drying to obtain the CdS-Fe modified g-C3N4A composite material 2.
(4) Preparation of CdS-g-C3N4Loaded nano TiO2The photocatalytic hydrogen production composite catalyst 2: adding a proper amount of distilled water into a reaction bottle, and sequentially adding 16 parts of Ag-Cu modified nano TiO2Component 2 and g-C modified by CdS-Fe prepared in step (3)3N4Placing the solution in an ultrasonic disperser with ultrasonic frequency of 20 KHz, performing ultrasonic dispersion treatment at 60 deg.C for 3 h, placing the reaction flask in a vacuum drying oven, heating to 70 deg.C, removing distilled water, and fully drying the solid mixed product to obtain CdS-g-C3N4Loaded nano TiO2The photocatalytic hydrogen production composite catalyst 2.
Example 3:
(1) preparation of Ag-Cu modified nano TiO2And (3) component: adding tetrabutyl titanate into absolute ethyl alcohol solvent, stirring uniformly, and adding Cu (NO)3)3And AgNO3Putting the solution into a low-temperature reactor, reacting for 42 h at-2 ℃ under uniform stirring, and adding a reducing agent NaBH into the solution4Tetrabutyl titanate, Cu (NO)3)3、AgNO3And NaBH4The molar ratio of the four substances is 135:1.2:1:2.8, the mixture is stirred at a constant speed at the temperature of minus 5 ℃ for reaction for 2.5 hours, the solution is decompressed and distilled to remove the solvent, a proper amount of distilled water and absolute ethyl alcohol are used for washing a solid product and fully drying, the solid mixture is placed in an atmosphere resistance furnace, and N is introduced into the atmosphere resistance furnace2The temperature rise rate of the resistance furnace is 4 ℃/min, the material is calcined for 5 hours at the temperature of 630 ℃, and the calcined product is Ag-Cu modified nano TiO2And (3) component.
(2) Preparation of Fe dopeHetero g-C3N4And (3) component: adding a proper amount of distilled water and ethanol mixed solvent into a reaction bottle, wherein the volume ratio of the distilled water to the ethanol mixed solvent is 1.8:1, and sequentially adding FeCl3Thiourea and melamine with the molar ratio of 1:28:4.8, placing a reaction bottle in an oil bath pot, heating to 110 ℃, stirring at a constant speed for reaction for 14 hours, placing the solution in a vacuum drying oven, heating to 75 ℃, removing the mixed solvent, placing the solid product in an atmosphere resistance furnace, and introducing N2The heating rate of the resistance furnace is 4 ℃/min, the calcination is carried out for 5 h at 590 ℃, and the calcination product is Fe-doped g-C3N4And (3) component.
(3) CdS-Fe modified g-C3N4Composite material 3: the preparation method comprises the steps of adding a proper amount of a mixed solvent of distilled water and ethanol into a reaction bottle, sequentially adding 14 parts of thioacetamide and 35 parts of CdCl, wherein the volume ratio of the distilled water to the ethanol is 1.8:12And 34 parts of Fe-doped g-C3N4And (3) placing the solution into an ultrasonic disperser with ultrasonic frequency of 25KHz, performing ultrasonic dispersion treatment at 45 ℃ for 2.5 h, placing a reaction bottle into a constant-temperature water bath kettle, heating to 75 ℃, stirring at constant speed, performing reflux reaction for 3 h, placing the solution into a vacuum drying oven, heating to 65 ℃, completely evaporating the solvent, washing the solid product with a proper amount of distilled water, and fully drying to prepare the CdS-Fe modified g-C3N4A composite material 3.
(4) Preparation of CdS-g-C3N4Loaded nano TiO2The photocatalytic hydrogen production composite catalyst 3: adding a proper amount of distilled water into a reaction bottle, and sequentially adding 17 parts of Ag-Cu modified nano TiO2Component 3 and g-C modified by CdS-Fe prepared in step (3)3N4Placing the solution in an ultrasonic disperser with ultrasonic frequency of 22 KHz for ultrasonic dispersion treatment at 70 deg.C for 3 h, placing the reaction flask in a vacuum drying oven, heating to 65 deg.C, removing distilled water, and fully drying the solid mixed product to obtain CdS-g-C3N4Loaded nano TiO2The photocatalytic hydrogen production composite catalyst 3.
Example 4:
(1) preparation of Ag-Cu modified nano TiO2Components4: adding tetrabutyl titanate into absolute ethyl alcohol solvent, stirring uniformly, and adding Cu (NO)3)3And AgNO3Placing the solution in a low-temperature reactor, stirring at constant speed for 45 h at-5 ℃, adding a reducing agent NaBH into the solution4Tetrabutyl titanate, Cu (NO)3)3、AgNO3And NaBH4The molar ratio of the four substances is 125:1.4:1:2.3, the mixture is stirred at a constant speed for reaction for 3 hours at the temperature of minus 8 ℃, the solution is decompressed and distilled to remove the solvent, a proper amount of distilled water and absolute ethyl alcohol are used for washing a solid product and fully drying, the solid mixture is placed in an atmosphere resistance furnace, and N is introduced into the atmosphere resistance furnace2The temperature rise rate of the resistance furnace is 4 ℃/min, the material is calcined for 4 hours at the temperature of 630 ℃, and the calcined product is Ag-Cu modified nano TiO2And (4) component.
(2) Preparation of Fe-doped g-C3N4And (4) component: adding a proper amount of distilled water and ethanol mixed solvent into a reaction bottle, wherein the volume ratio of the distilled water to the ethanol mixed solvent is 2:1, and sequentially adding FeCl3Thiourea and melamine with the mass molar ratio of 1:26:5, placing a reaction bottle in an oil bath pot, heating to 100 ℃, stirring at a constant speed for reaction for 15 hours, placing the solution in a vacuum drying oven, heating to 80 ℃, removing the mixed solvent, placing the solid product in an atmosphere resistance furnace, and introducing N2The temperature rise rate of the resistance furnace is 5 ℃/min, and the calcination is carried out for 5 h at 580 ℃, and the calcination product is Fe-doped g-C3N4And (4) component.
(3) CdS-Fe modified g-C3N4The composite material 4: the preparation method comprises the steps of adding a proper amount of a mixed solvent of distilled water and ethanol into a reaction bottle, sequentially adding 15 parts of thioacetamide and 38 parts of CdCl according to the volume ratio of 2:12And 29 parts of Fe-doped g-C3N4And (4) placing the solution into an ultrasonic disperser with ultrasonic frequency of 25KHz, performing ultrasonic dispersion treatment at 50 ℃ for 3 h, placing a reaction bottle into a constant-temperature water bath, heating to 70 ℃, stirring at constant speed for reflux reaction for 4 h, placing the solution into a vacuum drying oven, heating to 60 ℃, completely evaporating the solvent, washing the solid product with a proper amount of distilled water, and fully drying to obtain the CdS-Fe modified g-C3N4A composite material 4.
(4) Preparation of CdS-g-C3N4Loaded nano TiO2The photocatalytic hydrogen production composite catalyst 4: adding a proper amount of distilled water into a reaction bottle, and sequentially adding 18 parts of Ag-Cu modified nano TiO2Component 4 and g-C modified by CdS-Fe prepared in step (3)3N4Placing the solution in an ultrasonic disperser with ultrasonic frequency of 25KHz, performing ultrasonic dispersion treatment at 60 deg.C for 3 h, placing the reaction flask in a vacuum drying oven, heating to 70 deg.C, removing distilled water, and fully drying the solid mixed product to obtain CdS-g-C3N4Loaded nano TiO2The photocatalytic hydrogen production composite catalyst 4.
Example 5:
(1) preparation of Ag-Cu modified nano TiO2And (5) component: adding tetrabutyl titanate into absolute ethyl alcohol solvent, stirring uniformly, and adding Cu (NO)3)3And AgNO3Placing the solution in a low-temperature reactor, stirring at constant speed for 45 h at-5 ℃, adding a reducing agent NaBH into the solution4Tetrabutyl titanate, Cu (NO)3)3、AgNO3And NaBH4The weight molar ratio of the four substances is 150:1.5:1:3, the mixture is stirred at a constant speed at the temperature of minus 10 ℃ for reaction for 3 hours, the solution is distilled under reduced pressure to remove the solvent, a proper amount of distilled water and absolute ethyl alcohol are used for washing a solid product and are fully dried, the solid mixture is placed in an atmosphere resistance furnace, and N is introduced into the atmosphere resistance furnace2The temperature rise rate of the resistance furnace is 5 ℃/min, the calcination is carried out for 6 h at 640 ℃, and the calcination product is Ag-Cu modified nano TiO2And (5) component.
(2) Preparation of Fe-doped g-C3N4And (5) component: adding a proper amount of distilled water and ethanol mixed solvent into a reaction bottle, wherein the volume ratio of the distilled water to the ethanol mixed solvent is 2:1, and sequentially adding FeCl3Thiourea and melamine with the molar ratio of 1:30:5.5, placing a reaction bottle in an oil bath pot, heating to 120 ℃, stirring at a constant speed for reaction for 15 hours, placing the solution in a vacuum drying oven, heating to 80 ℃, removing the mixed solvent, placing the solid product in an atmosphere resistance furnace, and introducing N2The temperature rise rate of the resistance furnace is 5 ℃/min, the material is calcined for 4 h at the temperature of 600 ℃, and the calcined product is Fe dopedHetero g-C3N4And (5) component.
(3) CdS-Fe modified g-C3N4And (3) composite material 5: adding a proper amount of a mixed solvent of distilled water and ethanol into a reaction bottle, wherein the volume ratio of the distilled water to the mixed solvent is 2:1, and sequentially adding 16 parts of thioacetamide and 40 parts of CdCl2And 24 parts of Fe-doped g-C3N4And (5) placing the solution into an ultrasonic disperser with ultrasonic frequency of 25KHz, performing ultrasonic dispersion treatment at 50 ℃ for 3 h, placing a reaction bottle into a constant-temperature water bath kettle, heating to 80 ℃, stirring at constant speed, performing reflux reaction for 4 h, placing the solution into a vacuum drying oven, heating to 70 ℃, completely evaporating the solvent, washing the solid product with a proper amount of distilled water, and fully drying to obtain the CdS-Fe modified g-C3N4A composite material 5.
(4) Preparation of CdS-g-C3N4Loaded nano TiO2The photocatalytic hydrogen production composite catalyst 5: adding a proper amount of distilled water into a reaction bottle, and sequentially adding 20 parts of Ag-Cu modified nano TiO2Component 5 and g-C modified by CdS-Fe prepared in step (3)3N4Placing the solution in an ultrasonic disperser with ultrasonic frequency of 25KHz, performing ultrasonic dispersion treatment at-80 deg.C for 3 h, placing the reaction flask in a vacuum drying oven, heating to 70 deg.C, removing distilled water, and fully drying the solid mixed product to obtain CdS-g-C3N4Loaded nano TiO2The photocatalytic hydrogen production composite catalyst 5.
In summary, the CdS-g-C3N4Loaded nano TiO2The photocatalytic hydrogen production composite catalyst adopts an in-situ method to dope Fe with g-C3N4In g-C3N4Form rich pore structures inside, form crack-shaped and mesoporous structures on the surface, and increase the g-C3N4The specific surface area of the catalyst increases the contact area with water molecules, improves the efficiency of photolysis water hydrogen production, and improves g-C by doping Fe3N4The band structure promotes the absorption of light energy, and simultaneously Fe reduces g-C3N4Has improved conductivity of the semiconductor materialThe electric property promotes the diffusion and migration process of photo-generated electrons, and Fe can capture photo-generated carriers, so that the recombination rate of the photo-generated electrons and holes is reduced, and the photocatalytic activity and the hydrogen production efficiency of the photocatalytic material are enhanced.
CdS and g-C by in-situ method3N4Forming crystal face recombination to prepare CdS-g-C3N4Heterojunction, reduced g-C3N4Band gap energy of (CdS) g-C3N4The characteristic absorption edge is red-shifted, so that the visible light region of the ultraviolet-visible absorption spectrum of the heterojunction semiconductor material is extended, the wave band of the ultraviolet-visible absorption light is increased, and the utilization rate of light energy is improved.
Modification of nano TiO by Ag-Cu2As CdS-g-C3N4Carrier of heterojunction, Ag-Cu modification on TiO2The surface of the steel is added with nano TiO2Specific surface area of (2), and Ag-Cu in TiO2Cluster is formed on the surface, and the nano TiO is enlarged2Porosity and pore volume between molecules, such that CdS-g-C3N4The heterojunction can be uniformly loaded to the nano-TiO2Surface of CdS-g-C3N4The dispersion in water is not good, agglomeration and caking are formed to reduce the utilization effect of light energy, and the modification of Ag expands TiO2The spectrum absorption range of the composite material increases the ultraviolet-visible absorption light wave band of the photocatalytic composite material, and enhances the utilization rate of the composite material to light energy and the hydrogen production efficiency.
Claims (6)
1. CdS-g-C3N4Loaded nano TiO2The photocatalytic hydrogen production composite catalyst comprises the following formula raw materials in parts by weight, and is characterized in that: 12-16 parts of thioacetamide and 30-40 parts of CdCl224-43 parts of Fe-doped g-C3N415-20 parts of Ag-Cu modified nano TiO2。
2. CdS-g-C according to claim 13N4Loaded nano TiO2The photocatalytic hydrogen production composite catalyst is characterized in that: the Fe is doped with g-C3N4The preparation method comprises the following steps:
(1) adding FeCl into a mixed solvent of distilled water and ethanol with the volume ratio of 1.5-2:1 in sequence3Heating the solution to 100-120 ℃, reacting for 12-15 h, placing the solution in a vacuum drying box, and removing the mixed solvent;
(2) the solid product was placed in an atmospheric resistance furnace and N was passed through2The heating rate of the resistance furnace is 3-5 ℃/min, and the calcination is carried out for 4-6 h at the temperature of 580-600 ℃, and the calcination product is Fe-doped g-C3N4。
3. CdS-g-C according to claim 23N4Loaded nano TiO2The photocatalytic hydrogen production composite catalyst is characterized in that: the FeCl3The mass molar ratio of the three substances is 1:24-30: 4-5.5.
4. CdS-g-C according to claim 13N4Loaded nano TiO2The photocatalytic hydrogen production composite catalyst is characterized in that: the Ag-Cu modified nano TiO2The preparation method comprises the following steps:
(1) adding tetrabutyl titanate, Cu (NO) into absolute ethyl alcohol solvent3)3And AgNO3Reacting the solution at-5-0 deg.c for 40-45 hr, adding NaBH as reductant4Reacting for 2-3 h at-10-0 ℃;
(2) distilling the solution under reduced pressure to remove the solvent, washing the solid product, drying, placing the solid mixture in an atmosphere resistance furnace and introducing N2The heating rate of the resistance furnace is 3-5 ℃/min, the calcination is carried out for 3-6 h at the temperature of 620-640 ℃, and the calcination product is the Ag-Cu modified nano TiO2。
5. CdS-g-C according to claim 43N4Loaded nano TiO2The photocatalytic hydrogen production composite catalyst is characterized in that: tetrabutyl titanate, Cu (NO)3)3、AgNO3And NaBH4The molar ratio of the four substances is 120-150:1-1.5:1: 2.5-3.
6. CdS-g-C according to claim 43N4Loaded nano TiO2The photocatalytic hydrogen production composite catalyst is characterized in that: the CdS-g-C3N4Loaded nano TiO2The preparation method of the photocatalytic hydrogen production composite catalyst comprises the following steps:
(1) adding 12-16 parts of thioacetamide and 30-40 parts of CdCl into a mixed solvent of distilled water and ethanol with the volume ratio of 1.5-2:1 in sequence2And 24-43 parts of Fe-doped g-C3N4Performing ultrasonic dispersion treatment on the solution at 40-50 ℃ for 2-3 h with the ultrasonic frequency of 20-25KHz, heating the solution to 70-80 ℃, performing reflux reaction for 2-4 h, putting the solution in a vacuum drying oven to evaporate the solvent, washing and drying the solid product to prepare the CdS-Fe modified g-C3N4A composite material;
(2) adding 15-20 parts of Ag-Cu modified nano TiO into distilled water solvent in sequence2And g-C modified by CdS-Fe prepared in the step (1)3N4The composite material is prepared by subjecting the solution to ultrasonic dispersion treatment at 60-80 deg.C for 2-3 h with ultrasonic frequency of 20-25KHz, placing the solution in a vacuum drying oven to evaporate solvent, and fully drying the solid mixed product to obtain CdS-g-C3N4Loaded nano TiO2The photocatalytic hydrogen production composite catalyst.
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| CN111437864A (en) * | 2020-04-17 | 2020-07-24 | 大连理工大学 | High-dispersion Cu/NC nano-cluster catalyst and preparation method thereof |
| CN113117718A (en) * | 2021-03-29 | 2021-07-16 | 安徽建筑大学 | NiCoP-g-C3N4/CdS composite photocatalyst, preparation method and application thereof |
| CN113209998A (en) * | 2021-04-09 | 2021-08-06 | 华南理工大学 | Graphite-phase carbon nitride composite photocatalyst and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111437864A (en) * | 2020-04-17 | 2020-07-24 | 大连理工大学 | High-dispersion Cu/NC nano-cluster catalyst and preparation method thereof |
| CN111437864B (en) * | 2020-04-17 | 2022-12-02 | 大连理工大学 | High-dispersion Cu/NC nano-cluster catalyst and preparation method thereof |
| CN113117718A (en) * | 2021-03-29 | 2021-07-16 | 安徽建筑大学 | NiCoP-g-C3N4/CdS composite photocatalyst, preparation method and application thereof |
| CN113209998A (en) * | 2021-04-09 | 2021-08-06 | 华南理工大学 | Graphite-phase carbon nitride composite photocatalyst and preparation method thereof |
| CN113209998B (en) * | 2021-04-09 | 2022-09-20 | 华南理工大学 | Graphite-phase carbon nitride composite photocatalyst and preparation method thereof |
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