CN111054434B - TS-1 molecular sieve catalyst with special structure and application thereof in photocatalytic water hydrogen production - Google Patents
TS-1 molecular sieve catalyst with special structure and application thereof in photocatalytic water hydrogen production Download PDFInfo
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 96
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 96
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 47
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 239000001257 hydrogen Substances 0.000 title claims abstract description 42
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 42
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 37
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 35
- 239000003054 catalyst Substances 0.000 title claims abstract description 31
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- 239000002149 hierarchical pore Substances 0.000 claims abstract description 18
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 239000003513 alkali Substances 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- 230000001678 irradiating effect Effects 0.000 claims description 10
- 229910052724 xenon Inorganic materials 0.000 claims description 10
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 6
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- 238000013032 photocatalytic reaction Methods 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 5
- 230000008021 deposition Effects 0.000 claims description 5
- 238000007146 photocatalysis Methods 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 239000004310 lactic acid Substances 0.000 claims description 3
- 235000014655 lactic acid Nutrition 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 2
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 16
- 230000000694 effects Effects 0.000 abstract description 5
- 239000002096 quantum dot Substances 0.000 abstract description 4
- 239000011148 porous material Substances 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 14
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- 238000012546 transfer Methods 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 230000006798 recombination Effects 0.000 description 4
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- 239000004065 semiconductor Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 229910003077 Ti−O Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
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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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
-
- B01J35/39—
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- B01J35/60—
-
- B01J35/61—
-
- B01J35/63—
-
- 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
-
- 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 discloses a TS-1 molecular sieve catalyst with a special structure and application thereof in photocatalytic water hydrogen production. TS-1 molecular sieve with a hierarchical pore structure is used as a carrier, noble metal is loaded, and photocatalytic hydrogen production reaction is enhanced in the presence of a sacrificial agent and quantum dot CdS. The TS-1 molecular sieve catalyst with the special structure has the characteristics of wide photoresponse range, capability of effectively separating photoproduction electrons and hole pairs, high photocatalytic activity and good photocatalytic hydrogen production effect in the field of photocatalytic water hydrogen production.
Description
Technical Field
The invention relates to the technical field of photocatalytic water hydrogen production, in particular to a TS-1 molecular sieve catalyst with a special structure and application thereof in photocatalytic water hydrogen production.
Background
High oil prices and increasing greenhouse gas emissions are an unsolved problem for global economy and climate. In order to solve the problems of the sustainable development of human beings, the comprehensive utilization of resources, the environmental protection, the harmony with nature, the shortage of fossil energy and the global environment need to be solved urgently. Hydrogen energy, a clean and pollution-free energy source, has been receiving increasing attention from many people. Hydrogen has the following characteristics: good heat conduction, easy recovery, good combustion performance, small loss, environmental protection, non-corrosiveness of product water and high energy per unit mass.
Although the traditional hydrogen production method is efficient in generating hydrogen by reforming hydrocarbon steam, electrolyzing water and oxidizing heavy oil, the development of friendly hydrogen energy resources is limited by large energy consumption and harmful substance generation in the conversion process. Therefore, the conversion of water into hydrogen by solar energy is considered to be a promising approach to solve these problems.
The general limitations of photocatalytic water hydrogen production process mainly derive from two factors: competition between recombination and transfer of photogenerated electrons and holes; the solar energy is not fully utilized. The ideal photocatalyst has a wide photoresponse range and can effectively inhibit the recombination of photogenerated charges and holes.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a TS-1 molecular sieve catalyst with a special structure and application thereof in photocatalytic water hydrogen production.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: a TS-1 molecular sieve catalyst with a special structure is prepared by the following steps:
(1) 0.1-0.3 g of TS-1 molecular sieve is taken, noble metal precursor is added, so that the content of the noble metal simple substance in the added noble metal precursor is 0.4-1.2 wt% of the mass of the TS-1 molecular sieve, 40-60 mL of water is added, and the mixture is stirred for 20-120 min. Then 10-25 mL of anhydrous methanol is added, and the mixture is loaded into a reactor and vacuumized. And finally, irradiating by using a 300W xenon lamp, and carrying out light deposition for 1-4 h to obtain the TS-1 molecular sieve deposited with the noble metal.
(2) And washing the TS-1 molecular sieve deposited with the noble metal with water to remove impurities, and drying to obtain the catalyst for photocatalysis.
Further, the noble metal precursor is at least one of simple substances Pd, pt and Au or at least one of compounds of Pd, pt and Au.
Further, the TS-1 molecular sieve is of a hierarchical pore structure, and the hierarchical pore structure is obtained by the following method:
(1) Taking 50-75 mL of 0.3-5.0 mol/L alkali solution, and carrying out alkali treatment on 1.5-3.0 g of TS-1 molecular sieve for 0.5-6.0 h by adopting a hydrothermal method at 60-100 ℃ to obtain the alkalified TS-1 molecular sieve.
(2) And (3) washing the alkalized TS-1 molecular sieve to be neutral by using water, drying at the temperature of 60 ℃, and roasting at the temperature of 520-580 ℃ for 3-6 hours to obtain the TS-1 molecular sieve with the hierarchical pore structure.
Further, the alkali solution is at least one of ammonia water, sodium carbonate, sodium hydroxide and potassium hydroxide solution.
An application of the catalyst in photocatalytic water hydrogen production.
Further, 75-90 mL of water is added into 0.0008-0.0030 mol of CdS and 40-60 mg of catalyst to obtain a mixed solution, and the mixed solution is subjected to ultrasonic treatment to uniformly disperse the mixed solution. The mixed solution is poured into a reactor, 10 to 25mL of sacrificial agent is added, and stirring is carried out. And vacuumizing the photocatalytic reaction device, and irradiating the photocatalytic reaction device by using a 300-watt xenon lamp to perform photocatalytic hydrogen production from water.
Further, the sacrificial agent is at least one of lactic acid, formic acid, methanol, isopropanol, triethanolamine and ethanol.
Compared with the prior art, the invention has the following beneficial effects:
1. with bulk TiO 2 Compared with the TS-1 molecular sieve, the high-dispersion Ti-O part in the framework greatly improves the photocatalytic activity.
2.TiO 2 The CdS coupling can reduce the energy required by exciting electrons, and the photoresponse is expanded to a visible light region, so that the invention provides that CdS is doped in the TS-1 molecular sieve and applied to the photocatalytic water hydrogen production reaction, and the CdS-doped molecular sieve has better activity in the visible light region.
3. The molecular sieve is used as a carrier, has larger specific surface area, is beneficial to high dispersion of CdS, and enhances the photocatalytic activity.
4. The noble metal has good conductivity, can form a Schottky barrier with the surface of the semiconductor, electrons generated on the semiconductor reach the metal through a Schottky interface to form drift current without accumulation, so the electrons are enriched on the metal, the holes are enriched on the semiconductor, and the recombination of the electrons and the holes is inhibited. The noble metal has larger work function and high activity, and the hydrogen production reaction of semiconductor photocatalytic water can be promoted by adding the noble metals such as palladium, platinum and gold.
5. The pore structure of the hierarchical pore TS-1 molecular sieve is adjusted by an alkali solution, and the average pore diameter of the TS-1 molecular sieve can be increased and the diffusion barrier of particles can be reduced by treating the TS-1 molecular sieve by the alkali; in addition, the higher mesoporous volume, total pore volume and mesoporous specific surface area of the hierarchical pore TS-1 molecular sieve can promote more active sites and excellent photocatalytic activity. Certain mesopores are formed in the molecular sieve, so that the mass transfer resistance can be effectively reduced, and the accessibility of active sites is improved.
The TS-1 molecular sieve loaded noble metal with the hierarchical pore structure can effectively inhibit the recombination of electrons and holes, and has better photocatalytic water hydrogen production activity in a visible light region in the presence of quantum dot CdS and a sacrificial agent. The carrier hierarchical pore TS-1 molecular sieve has larger average pore diameter, higher mesoporous pore volume, total pore volume and higher mesoporous specific surface area, can effectively reduce mass transfer resistance, and improves the accessibility of active sites.
Drawings
FIG. 1 is an XRD spectrum of the TS-1 molecular sieves obtained in examples 2-5 and comparative example 1.
Detailed Description
The invention is described in detail below with reference to the figures and the embodiments, but the invention is not limited to the scope of the invention. The invention aims to explore a visible light response photocatalyst, improve the separation efficiency of a photon-generated carrier and promote hydrogen production reaction, and provides a TS-1 molecular sieve catalyst with a special structure, which strengthens the hydrogen production reaction by photocatalytic water in the presence of a sacrificial agent and quantum dot CdS.
Example 1: preparing a TS-1 molecular sieve to be regulated and controlled by holes
The TS-1 molecular sieve to be alkalized is provided by Nanjing Xiancheng nano material science and technology Co. Roasting the mixture in a tubular furnace at 540 ℃ for 3h to remove impurities and adsorbed water before alkalization.
Example 2: pore regulation of TS-1 molecular sieve
(1) And taking 75mL of 5.0mol/L ammonia water solution, and carrying out alkali treatment on 3g of the TS-1 molecular sieve for 6 hours at 100 ℃ by adopting a hydrothermal method to obtain the alkalified TS-1 molecular sieve.
(2) And (3) washing the alkalized TS-1 molecular sieve with water to be neutral, drying at 60 ℃, and roasting at 580 ℃ for 6 hours to obtain the TS-1 molecular sieve with the hierarchical pore structure, wherein XRD test of the TS-1 molecular sieve is shown in figure 1.
Example 3: pore regulation of TS-1 molecular sieve
(1) 65mL of Na with a concentration of 0.4mol/L was taken 2 CO 3 And (3) carrying out alkali treatment on 2.5g of the TS-1 molecular sieve by a hydrothermal method for 2 hours at 80 ℃ to obtain the alkalized TS-1 molecular sieve.
(2) And (3) washing the alkalized TS-1 molecular sieve with water to be neutral, drying at 60 ℃, and roasting at 560 ℃ for 4h to obtain the TS-1 molecular sieve with the hierarchical pore structure, wherein XRD test of the TS-1 molecular sieve is shown in figure 1.
Example 4: pore regulation of TS-1 molecular sieve
(1) And taking 60mL of 0.3mol/L NaOH solution, and carrying out alkali treatment on 2g of the TS-1 molecular sieve for 0.5h by adopting a hydrothermal method at 65 ℃ to obtain the alkalized TS-1 molecular sieve.
(2) And (3) washing the alkalized TS-1 molecular sieve with water to be neutral, drying at 60 ℃, and roasting at 540 ℃ for 3h to obtain the TS-1 molecular sieve with the hierarchical pore structure, wherein XRD test of the TS-1 molecular sieve is shown in figure 1.
Example 5: pore regulation of TS-1 molecular sieve
(1) Taking 50mL of KOH solution with the concentration of 0.5mol/L, and carrying out alkali treatment on 1.5g of the TS-1 molecular sieve for 0.5h by adopting a hydrothermal method at 60 ℃ to obtain the alkalized TS-1 molecular sieve.
(2) And (3) washing the alkalized TS-1 molecular sieve to be neutral by using water, drying at the temperature of 60 ℃, and roasting at the temperature of 520 ℃ for 3 hours to obtain the TS-1 molecular sieve with the hierarchical pore structure, wherein an XRD test of the TS-1 molecular sieve is shown in figure 1.
Comparative example 1:
the TS-1 molecular sieve provided by Nanjing Xiancheng nano material science and technology Limited company is roasted for 3h at 540 ℃ to obtain the TS-1 molecular sieve, and the XRD test of the TS-1 molecular sieve is shown in figure 1.
As shown in FIG. 1, which is XRD spectra of TS-1 molecular sieves obtained in examples 2-5 and comparative example 1, it can be seen that after alkali treatment with different concentrations, TS-1 molecular sieves with hierarchical pore structures are obtained, and compared with TS-1 molecular sieves without alkali treatment in comparative example 1, characteristic diffraction peaks of TS-1 molecular sieves appear at 7.8 °, 8.8 °, 23.2 °, 23.8 ° and 24.3 °, which indicates that the structure of TS-1 with the pore structure adjusted by alkali treatment is not collapsed, and the framework structure of TS-1 is not damaged.
TABLE 1 pore Structure characteristics of TS-1 molecular sieves obtained in examples 2-5 and comparative example 1
The data in Table 1 show that the average pore diameter of the alkalized TS-1 molecular sieve is increased by 18-69%, the mesoporous pore volume is increased by 19-102%, the total pore volume is increased by 2-40%, the mesoporous specific surface area is increased by 40-80%, the microporous specific surface area is reduced by 15-32%, and the microporous pore volume is reduced by 15-32% compared with the TS-1 molecular sieve before alkalization. After the alkali treatment, the average pore diameter, the mesoporous volume, the total pore volume and the mesoporous specific surface area of the TS-1 molecular sieve are larger than those of a comparison sample, and the micropore specific surface area and the micropore volume are reduced than those of the comparison sample, which shows that a certain mesopore is formed in the molecular sieve, so that the mass transfer resistance can be effectively reduced, and the accessibility of an active site is improved.
Example 6:
(1) 0.1g of the TS-1 molecular sieve with the hierarchical pore structure obtained in the example 2 or 3 is taken, chloroplatinic acid is added, the platinum content in the added chloroplatinic acid is 0.4wt% of the mass of the TS-1 molecular sieve, 40mL of water is added, and the mixture is stirred for 20min. 10mL of anhydrous methanol was then added, and the reactor was charged and evacuated. And finally, irradiating by using a 300W xenon lamp, and carrying out light deposition for 1h to obtain the TS-1 molecular sieve deposited with the noble metal.
(2) And washing the TS-1 molecular sieve deposited with the noble metal with water to remove impurities, and drying to obtain the catalyst for photocatalysis.
Example 7:
(1) 0.3g of the TS-1 molecular sieve with the hierarchical pore structure obtained in example 4 or 5 is taken, chloropalladite is added, the palladium content in the chloropalladite is 1.2wt% of the mass of the TS-1 molecular sieve, 60mL of water is added, and the mixture is stirred for 120min. Then 25mL of anhydrous methanol was added, and the reactor was charged and evacuated. And finally, irradiating by using a 300W xenon lamp, and carrying out light deposition for 4h to obtain the TS-1 molecular sieve deposited with the noble metal.
(2) And washing the TS-1 molecular sieve deposited with the noble metal with water to remove impurities, and drying to obtain the catalyst for photocatalysis.
Comparative example 2:
(1) 0.1g of the TS-1 molecular sieve in the comparative example 1 is taken, chloroplatinic acid is added, the platinum content in the added chloroplatinic acid is 0.4wt% of the mass of the TS-1 molecular sieve, 40mL of water is added, and the mixture is stirred for 20min. Then 10mL of anhydrous methanol was added, and the reactor was charged and evacuated. And finally, irradiating by using a 300W xenon lamp, and carrying out light deposition for 1h to obtain the TS-1 molecular sieve deposited with the noble metal.
(2) And washing the TS-1 molecular sieve deposited with the noble metal with water to remove impurities, and drying to obtain the catalyst for photocatalysis.
Example 8: application of catalyst in photocatalytic water hydrogen production reaction
Preparing a reaction solution: 75mL of water was added to 0.0008mol of CdS and 40mg of the catalyst prepared in example 6 to obtain a mixed solution, and the mixed solution was subjected to ultrasonic treatment to disperse the mixed solution uniformly. The above solution was poured into a reactor, 25mL of ethanol was added, and stirred. Vacuumizing the photocatalytic reaction device, irradiating by using a 300-watt xenon lamp added with a 420nm filter, detecting and analyzing the hydrogen production rate by using a gas chromatograph for 2.5 hours, sampling every half an hour, and recording experimental data.
Example 9: application of catalyst in photocatalytic water hydrogen production reaction
Preparing a reaction solution: 90mL of water was added to 0.0030mol of CdS and 60mg of the catalyst prepared in example 7 to obtain a mixed solution, and the mixed solution was subjected to ultrasonic treatment to disperse the mixed solution uniformly. The above solution was poured into a reactor, 10mL of lactic acid was added, and stirred. Vacuumizing the photocatalytic reaction device, irradiating by using a 300-watt xenon lamp added with a 420nm filter, detecting and analyzing the hydrogen production rate by using a gas chromatograph for 2.5 hours, sampling every half an hour, and recording experimental data.
Comparative example 3: application of catalyst in photocatalytic water hydrogen production reaction
Preparing a reaction solution: 75mL of water was added to 0.0008mol of CdS and 40mg of the catalyst prepared in comparative example 2 to obtain a mixed solution, and the mixed solution was subjected to ultrasonic treatment to disperse the mixed solution uniformly. The above solution was poured into a reactor, 25mL of ethanol was added, and stirred. Vacuumizing the photocatalytic reaction device, irradiating by using a 300W xenon lamp added with a 420nm filter, detecting and analyzing the hydrogen production rate by using a gas chromatograph for 2.5 hours, sampling every half hour, and recording experimental data.
And (4) analyzing results: table 2 shows the hydrogen production rates of the catalysts prepared by the TS-1 molecular sieves before and after the pore regulation of the examples 2-5 and the comparative example 1, the hydrogen production rate of the catalyst prepared by the molecular sieve of the comparative example 1 is only 775.09 mu mol/h, while the hydrogen production rates of the catalysts prepared by the molecular sieves of the examples 2-5 are 1178.94, 1260.98, 2190.34 and 1605.10 mu mol/h respectively, which are better than the hydrogen production effect of the catalysts of the comparative examples. The molecular sieve regulated and controlled by the pores can effectively reduce mass transfer resistance and improve the accessibility of active sites, and after the noble metal is loaded, the photocatalytic hydrogen production reaction can be enhanced in the presence of a sacrificial agent and quantum dot CdS. The TS-1 molecular sieve catalyst with a special structure has the characteristics of wide photoresponse range, capability of effectively separating photoproduction electron and hole pairs, promotion of more active sites and better photocatalytic activity in the field of photocatalytic water hydrogen production. The catalyst prepared by the invention can better improve the hydrogen production rate of the photocatalytic water hydrogen production reaction and effectively improve the photocatalytic water hydrogen production reaction.
TABLE 2 hydrogen production rates of catalysts prepared from TS-1 molecular sieves of examples 2-5 and comparative example 1
| Example numbering | Hydrogen production rate (mu mol/h) |
| Comparative example 1 | 775.09 |
| Example 2 | 1178.94 |
| Example 3 | 1260.98 |
| Example 4 | 2190.34 |
| Example 5 | 1605.10 |
It should be noted that the above-mentioned embodiments do not limit the present invention in any way, and all technical solutions obtained by using equivalent alternatives or equivalent variations fall within the protection scope of the present invention.
Claims (5)
1. The application of the TS-1 molecular sieve catalyst with a special structure in photocatalytic water hydrogen production is characterized in that: the catalyst is prepared by the following method:
(1) Taking 0.1-0.3 g of TS-1 molecular sieve, adding a noble metal precursor to ensure that the content of the noble metal simple substance in the added noble metal precursor is 0.4-1.2wt% of the mass of the TS-1 molecular sieve, adding 40-60mL of water, and stirring for 20-120min; then adding 10 to 25mL of anhydrous methanol, filling the mixture into a reactor, and vacuumizing the reactor; finally, irradiating by using a 300W xenon lamp, and carrying out light deposition for 1-4h to obtain the TS-1 molecular sieve deposited with the noble metal;
(2) Washing the TS-1 molecular sieve deposited with the noble metal with water to remove impurities, and then drying to obtain a catalyst for photocatalysis;
the TS-1 molecular sieve is of a hierarchical pore structure, and the hierarchical pore structure is obtained by the following method:
taking 50-75mL of 0.3-5.0 mol/L alkali solution, and carrying out alkali treatment on 1.5-3.0 g of TS-1 molecular sieve for 0.5-6.0 h at 60-100 ℃ by adopting a hydrothermal method to obtain an alkalified TS-1 molecular sieve;
and (3) washing the alkalized TS-1 molecular sieve with water to be neutral, drying at 60 ℃, and roasting at 520-580 ℃ for 3-6 h to obtain the TS-1 molecular sieve with the hierarchical pore structure.
2. Use according to claim 1, characterized in that the noble metal precursor is at least one of the elements Pd, pt, au or at least one of the compounds of Pd, pt, au.
3. The use according to claim 1, wherein the alkali solution is at least one of ammonia, sodium carbonate, sodium hydroxide, potassium hydroxide solution.
4. The application of claim 1, wherein 75 to 90mL of water is added into 0.0008 to 0.0030mol of CdS and 40 to 60mg of catalyst to obtain a mixed solution, and the mixed solution is subjected to ultrasonic treatment to be uniformly dispersed; pouring the mixed solution into a reactor, adding 10 to 25mL of a sacrificial agent, and stirring; and vacuumizing the photocatalytic reaction device, irradiating by using a 300 watt xenon lamp, and carrying out photocatalytic hydrogen production from water.
5. The use according to claim 4, wherein the sacrificial agent is at least one of lactic acid, formic acid, methanol, isopropanol, triethanolamine, ethanol.
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