CN115069270A - CuSAP/CdS photolysis water hydrogen production catalyst and preparation method thereof - Google Patents
CuSAP/CdS photolysis water hydrogen production catalyst and preparation method thereof Download PDFInfo
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 238000006303 photolysis reaction Methods 0.000 title claims abstract description 24
- 230000015843 photosynthesis, light reaction Effects 0.000 title claims abstract description 23
- 239000000243 solution Substances 0.000 claims abstract description 50
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- 238000001354 calcination Methods 0.000 claims description 8
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- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 claims description 4
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 claims description 2
- WYYQVWLEPYFFLP-UHFFFAOYSA-K chromium(3+);triacetate Chemical compound [Cr+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WYYQVWLEPYFFLP-UHFFFAOYSA-K 0.000 claims description 2
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 2
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- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
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- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 2
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- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 2
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- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
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- 239000002028 Biomass Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
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- 239000005431 greenhouse gas Substances 0.000 description 1
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- 238000011065 in-situ storage Methods 0.000 description 1
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- 229910052709 silver Inorganic materials 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
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- WCTAGTRAWPDFQO-UHFFFAOYSA-K trisodium;hydrogen carbonate;carbonate Chemical class [Na+].[Na+].[Na+].OC([O-])=O.[O-]C([O-])=O WCTAGTRAWPDFQO-UHFFFAOYSA-K 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
- B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
- B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
- B01J27/1817—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates with copper, silver or gold
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
-
- B01J35/39—
-
- 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
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
Abstract
The invention discloses a CuSAP/CdS photolysis water hydrogen production catalyst and a preparation method thereof, wherein the preparation method comprises the following steps: ultrasonically dispersing a CdS catalyst in deionized water to obtain a solution A, and preparing a copper salt solution as a solution B; dropwise adding the solution B into the solution A, continuously stirring, and then drying the mixed solution; fully grinding the solid obtained after drying, and mixing the obtained powder with NaH 2 PO 2 Respectively arranged at two ends of a quartz boat with a cover, wherein NaH 2 PO 2 Placing the catalyst at one end of an air inlet, then placing the catalyst in a tubular furnace to calcine the catalyst in an inert atmosphere, cooling the catalyst to room temperature, and collecting the obtained powder, namely the CuSAP/CdS photocatalyst. The CuSAP/CdS photocatalyst finally shows high photocatalysisHigh activity for decomposing hydrogen produced by water, high stability and low cost.
Description
Technical Field
The invention relates to the technical field of photocatalysts, in particular to a CuSAP/CdS catalyst for hydrogen production through water photolysis and a preparation method thereof.
Background
The problems of energy and environment are becoming more serious, the development of clean renewable new energy is imminent, and hydrogen is considered as a promising clean fuel due to the advantages of abundant sources, high combustion value, low density, multiple available forms, no pollution, storage and the like. The hydrogen can be generated by renewable energy sources such as water power, wind power, solar energy, biomass energy and the like, and coal, natural gas and secondary energy electric energy. The hydrogen energy can be applied to the traditional field, emerging traffic vehicles, hydrogen energy power generation and the like, and is listed as a novel strategic energy source of the country. At the present stage, the main industrial hydrogen production method is the hydrogen production by fossil fuel, but the method still consumes fossil energy and generates greenhouse gas, and the green development concept is not satisfied. In 1972, scientists found that solar photocatalytic hydrogen production by water decomposition can be realized by using a semiconductor material as a catalyst, and the method is a clean and sustainable hydrogen production method. Among them, semiconductor photocatalysts are important mediators for converting solar energy into chemical energy, and CdS is considered as a semiconductor with great application prospect due to the appropriate energy band structure and conduction band potential (Eg ═ 2.40V, CB ═ 0.52V, and VB ═ 1.88V).
However, due to coulomb acting force, electrons and holes generated by the light excitation of the CdS are easy to recombine, and the photoelectric conversion efficiency is low; and sulfide is ubiquitous in the problem of photo-corrosion, namely S 2- Oxidized by the photoproduction cavity to generate sulfur simple substance (S), so that CdS is inactivated; moreover, the hydrogen production overpotential of the semiconductor catalyst is high, resulting in slow hydrogen release kinetics.
In recent years, researches show that the problems can be effectively alleviated by loading hydrogen production promoters, and the commonly used hydrogen production promoters are noble metals such as Pt, Au, Ag and the like, but the cost is too high to be suitable for industrial mass production. Therefore, the development of novel non-noble metal promoters with high efficiency and low cost is the focus of research. In recent years, it has been found that a Metal single-atom (MSA) catalyst can maximally expose active sites, and the atom utilization rate reaches 100%. The catalyst can be used as a cocatalyst in photocatalysis to improve the electrical conductivity and regulate the light absorption performance of a semiconductor, and can be used as an active site to promote the reduction reaction of protons on the surface. However, SACs tend to agglomerate during the catalytic reaction due to their high surface energy or unstable anchoring. Therefore, the preparation of highly dispersed monoatomic cocatalysts and the establishment of a stable coordination environment remain bottlenecks at this stage. Furthermore, there have been few and no intensive studies on non-noble metal monoatomic atoms. Therefore, to summarize, the key problems still faced by monatomic catalysis are: (1) preparing a stable and efficient monatomic catalyst; (2) because the influence of the local electronic structure on the material is large, the single atom-loaded site is accurately designed and regulated; (3) usually, the linking atom is composed of O, N and S with high electronegativity, but it easily causes high oxidation state or high coordination number of MSA, and reduces the catalytic activity. (4) Constructing a stable and efficient coordination environment and a charge transfer path; (5) deeply researching the design principle and the reaction mechanism of a non-noble metal monatomic catalyst in the field of photocatalytic hydrogen production; (6) how stably a monoatomic atom is supported on a metal sulfide semiconductor.
Patent CN202111300704.7 discloses a copper monatomic material, a preparation method thereof and photocatalytic CO 2 Application in reduction, capable of producing C with high selectivity 2+ And (3) obtaining the product. Patent CN202111085945.4 discloses a catalyst for photocatalytic reduction of carbon dioxide to produce ethylene and a preparation method thereof, wherein the catalyst is prepared by loading atomic-level dispersed Cu on CeO 2 -TiO 2 The heterogeneous structure is composed on the surface and can selectively remove CO under simulated sunlight 2 Reduced to ethylene. Patent CN201910706168.7 discloses a novel monatomic hydrogen production photocatalyst, which has an ultrathin porous sheet structure, Pt monatomic is reduced in situ through rich groups on the surface of Carbon Dots (CDs), the obtained catalyst expression is CdS @ CDs/Pt-SAs, and the hydrogen production efficiency by utilizing sunlight can be greatly improved. Patent CN202110752625.3 discloses a novel Pd monatomic supported graphite phase carbon nitride photocatalytic total hydrolysis catalyst, which has better photocatalytic total hydrolysis performance and stability than pure graphite phase carbon nitride and Pd nanoparticle supported graphite phase carbon nitride.
From the above examples, it can be seen that most of the noble metal monatomic and Cu monatomic systems used in the field of hydrogen production by photocatalytic water splitting are less studied, and usually, a metal monatomic is supported on an organic carrier or a carbide to stabilize the structure, and is more difficult to be supported on a metal sulfide and is less studied. And the Mott-Schottky junction is constructed by fixing a Cu monoatomic atom with a P atom to construct a unique coordination environment and loading the Cu monoatomic atom on the CdS surface.
Disclosure of Invention
In order to solve the technical problems, the invention provides a CuSAP/CdS water-photolysis hydrogen production catalyst and a preparation method thereof. The Mott-Schottky junction photocatalyst consists of non-noble metal monoatomic CuSAP fixed by phosphorus atoms and snowflake CdS, improves the atom utilization rate of a cocatalyst, fully exposes active sites, reduces the hydrogen production overpotential of a semiconductor, improves the conductivity of a semiconductor system, and shortens the migration distance of photo-generated electrons and holes. The CuSAP/CdS photocatalyst finally has the advantages of high photocatalytic water decomposition hydrogen production activity, high stability, low cost and the like.
In order to achieve the technical effects, the invention provides the following technical scheme:
a preparation method of a CuSAP/CdS photolysis water hydrogen production catalyst comprises the following steps: (1) ultrasonically dispersing a CdS catalyst in deionized water to obtain a solution A, and preparing a copper salt solution as a solution B; (2) dropwise adding the solution B into the solution A, continuously stirring, and then drying the mixed solution; (3) fully grinding the solid obtained after drying, and mixing the obtained powder with NaH 2 PO 2 Respectively arranged at two ends of a quartz boat with a cover, wherein NaH 2 PO 2 Placing the catalyst at one end of an air inlet, then placing the catalyst in a tubular furnace to calcine the catalyst in an inert atmosphere, cooling the catalyst to room temperature, and collecting the obtained powder, namely the CuSAP/CdS photocatalyst.
The further technical scheme is that the preparation method of the CdS catalyst comprises the following steps: adding cadmium salt, a sulfur source and strong acid into deionized water, mixing and stirring uniformly to obtain a suspension, heating the suspension for reaction, cooling after reaction, centrifuging and washing a product to obtain a precipitate, drying the precipitate and grinding to obtain the CdS catalyst.
The further technical scheme is that the cadmium salt is selected from any one of chromium acetate, cadmium chloride or cadmium nitrate, the sulfur source is selected from any one of thiourea, sodium sulfide or sodium thiosulfate, and the strong acid is selected from any one of hydrofluoric acid, hydrochloric acid or sulfuric acid.
Preferably, the cadmium salt is Cd (CH3COO) 2 ·3H 2 O, the sulfur source is thiourea, and the strong acid is hydrofluoric acid.
The further technical scheme is that the heating reaction is specifically that the suspension is transferred to a polytetrafluoroethylene reaction kettle, the suspension is heated from room temperature to 190-.
The further technical scheme is that the washing is specifically washing for 2-4 times by using deionized water and ethanol until a supernatant is transparent, and collecting the obtained precipitate.
The further technical proposal is that the mol ratio of the cadmium salt to the sulfur source is (4-6) mmol: (5-7) mmol, wherein the molar volume ratio of the cadmium salt to the strong acid is (4-6) mmol: (804-806) μ L.
The further technical scheme is that the mass volume ratio of the CdS to the deionized water in the step (1) is (0.1-0.3) g: (45-55) ml, and the concentration of the solution B is 0.05-0.15 mmol/L.
The further technical scheme is that the copper salt in the step (1) is copper chloride or copper sulfate.
Preferably, the copper salt is CuCl 2 ·2H 2 O。
The further technical proposal is that the drying condition in the step (2) is drying for 20-30h at 50-70 ℃.
The further technical proposal is that the calcining condition in the step (3) is that the temperature is increased from room temperature to 350-450 ℃, the temperature increasing rate is 2-8 ℃, and the calcining time is 5-15 min.
The invention also provides a catalyst for hydrogen production by water photolysis of CuSAP/CdS, which is prepared by the preparation method.
The Cu monoatomic cocatalyst is prepared by a simple physical adsorption method, and P atoms are introduced by utilizing PH3 gas generated by high-temperature decomposition of sodium dihydrogen phosphate to form a Cu-P coordination environment and fix the Cu monoatomic catalysts; unlike the more studied high electronegativity O, N and S atoms which are used as connecting atoms, the P atom is used for constructing a stable coordination environment, so that the problem that the MSA is easily in a high oxidation state or a high coordination number is solved; cu shows a Local Surface Plasmon Resonance (LSPR) effect in a visible light region and can form a unique Mott-Schottky junction with CdS; the dynamics performance of the nucleation growth of the CdS crystal is regulated and controlled by adding hydrofluoric acid, hydrochloric acid or sulfuric acid, so that a pinnate leaf with an included angle of 60 degrees between the leaf and the branch is prepared, and six single pinnate leaves can further form symmetrically distributed snowflake crystals; the Cu monoatomic atom fixed by the phosphorus atom is used as a hydrogen production promoter of a CdS system to construct a Mott-Schottky junction photocatalyst CuPAS/CdS, so that photo-generated electrons can be extracted, and the energy barrier of proton reduction can be remarkably reduced.
Compared with the prior art, the invention has the following beneficial effects: the invention uses a simple physical adsorption method to prepare the Cu single-atom cocatalyst and utilizes the PH generated by the pyrolysis of the sodium dihydrogen phosphate 3 Introducing P atoms into gas to form a Cu-P coordination environment and fixing Cu single atoms; unlike the more studied high electronegativity O, N and S atoms which are used as connecting atoms, the P atom is used for constructing a stable coordination environment, so that the problem that the MSA is easily in a high oxidation state or a high coordination number is solved; the Cu monoatomic atom fixed by the phosphorus atom is used as a hydrogen production promoter of a CdS system to construct a Mott-Schottky junction photocatalyst CuPAS/CdS, so that photo-generated electrons can be extracted, and the energy barrier of proton reduction can be remarkably reduced. Strong acid such as hydrofluoric acid, hydrochloric acid or sulfuric acid is added to intervene the dynamic performance of crystal nucleation growth, so that the morphological structure of CdS is regulated and controlled, feather-shaped CdS is prepared, the included angle between leaves and branches is regular 60 degrees, and part of the included angle forms regular snowflake shapes; the transition metal Cu shows Local Surface Plasmon Resonance (LSPR), hot electrons generated by light excitation have higher energy, and the surface plasmon resonance effect can improve the light absorption performance of the catalyst, enhance the light absorption intensity and widen the light absorption range. HealdThe composite photocatalyst obtained by the method is greatly improved in hydrogen production activity and stability, and the production cost is greatly reduced, so that the development of a technology for decomposing water into hydrogen by photocatalysis is promoted.
Drawings
FIG. 1 is a schematic diagram of a preparation process of the composite catalyst of the present invention;
FIG. 2 is an XRD pattern of CdS and CuSAP/CdS;
FIG. 3 is a UV-VIS absorption spectrum of CdS and CuSAP/CdS;
FIG. 4 is a UV-VIS absorption spectrum and LSPR absorption of CuSAP;
FIG. 5 is an SEM image of CdS and CuSAP/CdS;
FIG. 6 shows the activity (a) and stability (b) of photocatalytic decomposition water of a sample.
Detailed Description
The invention will be further explained and explained with reference to the drawings and the embodiments.
Example 1
Example one
A preparation method of a catalyst for hydrogen production by photolysis of water by phosphorus atom fixed Cu monoatomic load with snowflake-shaped CdS heterojunction comprises the following steps:
1. 4.0mmol of Cd (CH) 3 COO) 2 ·3H 2 O, 5.0mmol thiourea and 804.0 mu L hydrofluoric acid are added into 79.0ml deionized water and stirred for 1 h;
2. transferring the suspension into a polytetrafluoroethylene reaction kettle, heating the suspension from room temperature to 190 ℃ by using a drying oven, preserving heat, reacting for 19 hours, and naturally cooling to room temperature after the reaction is finished;
3. centrifuging the product obtained in the step 2, washing the product for 2 times by using deionized water and ethanol until the supernatant is transparent, collecting the obtained precipitate, finally drying the precipitate in a drying oven at 90 ℃ for several hours, and fully grinding the precipitate to obtain the CdS catalyst;
4. ultrasonically dispersing 0.1g of the dried CdS obtained in the step 3 in 45ml of deionized water to mark as a solution A, and preparing 0.05mmol/L CuCl by using a volumetric flask 2 ·2H 2 The O solution is marked as solution B;
5. dropwise adding 50ml of the solution B prepared in the step into the solution A, continuously stirring, and then drying the mixed solution for 20 hours at 50 ℃;
6. the solid fraction obtained by drying in step 5 was ground and the powder obtained was then admixed with 0.1g of NaH 2 PO 2 Respectively arranged at two ends of a quartz boat with a cover, wherein NaH 2 PO 2 Placing the catalyst at one end of an air inlet, then placing the catalyst in a tubular furnace to calcine the catalyst in Ar atmosphere, heating the catalyst from room temperature to 350 ℃, heating the catalyst at the rate of 2 ℃ for 5min, cooling the catalyst to room temperature, and collecting the obtained powder, namely the CuSAP/CdS photocatalyst.
Example two
A preparation method of a phosphorus atom fixed Cu monoatomic load snowflake-shaped CdS heterojunction water photolysis hydrogen production catalyst comprises the following steps:
1. 5.0mmol of Cd (CH) 3 COO) 2 ·3H 2 O, 5.0mmol of thiourea and 804.0 mu L of hydrofluoric acid are added into 79.4ml of deionized water and stirred for 1-3 h;
2. transferring the suspension into a polytetrafluoroethylene reaction kettle, heating the suspension from room temperature to 190 ℃ by using a drying oven, preserving heat, reacting for 19 hours, and naturally cooling to room temperature after the reaction is finished;
3. centrifuging the product obtained in the step 2, washing the product for 4 times by using deionized water and ethanol until the supernatant is transparent, collecting the obtained precipitate, finally drying the precipitate in a drying oven at 90 ℃ for several hours, and fully grinding the precipitate to obtain the CdS catalyst;
4. ultrasonically dispersing 0.2g of the dried CdS obtained in the step 3 in 50ml of deionized water to mark as a solution A, and preparing 0.05mmol/L CuCl by using a volumetric flask 2 ·2H 2 The O solution is marked as solution B;
5. dropwise adding 50ml of the solution B prepared in the step into the solution A, continuously stirring, and then drying the mixed solution for 30 hours at 70 ℃;
6. the solid obtained by drying in step 5 was thoroughly ground and the powder obtained was then mixed with 0.2g of NaH 2 PO 2 Respectively arranged at two ends of a quartz boat with a cover, wherein NaH 2 PO 2 Placing at one end of the gas inlet, then placing in a tube furnace, calcining in Ar atmosphere, and raising from room temperatureAnd (3) heating to 450 ℃, heating at the rate of 8 ℃, calcining for 5min, cooling to room temperature, and collecting the obtained powder, namely the CuSAP/CdS photocatalyst.
EXAMPLE III
A preparation method of a catalyst for hydrogen production by photolysis of water by phosphorus atom fixed Cu monoatomic load with snowflake-shaped CdS heterojunction comprises the following steps:
1. adding 6.0mmol of Cd (CH) 3 COO) 2 ·3H 2 O, 5.0mmol thiourea and 804.0-806.0 mu L hydrofluoric acid are added into 79.0ml deionized water and stirred for 3 hours;
2. transferring the suspension into a polytetrafluoroethylene reaction kettle, heating the suspension from room temperature to 210 ℃ by using a drying oven, preserving heat, reacting for 20 hours, and naturally cooling to room temperature after the reaction is finished;
3. centrifuging the product obtained in the step 2, washing the product for 2 times by using deionized water and ethanol until the supernatant is transparent, collecting the obtained precipitate, finally drying the precipitate in a drying oven at 100 ℃ for several hours, and fully grinding the precipitate to obtain the CdS catalyst;
4. ultrasonically dispersing 0.1g of the dried CdS obtained in the step 3 in 45ml of deionized water to mark as a solution A, and preparing 0.15mmol/L CuCl by using a volumetric flask 2 ·2H 2 The O solution is marked as solution B;
5. dropwise adding 150ml of the solution B prepared in the step into the solution A, continuously stirring, and then drying the mixed solution for 24 hours at 50-70 ℃;
6. the solid obtained by drying in step 5 was thoroughly ground and the powder obtained was then mixed with 0.3g of NaH 2 PO 2 Respectively arranged at two ends of a quartz boat with a cover, wherein NaH 2 PO 2 Placing the catalyst at one end of an air inlet, then placing the catalyst in a tubular furnace to calcine the catalyst in Ar atmosphere, heating the catalyst from room temperature to 350 ℃, heating the catalyst at the rate of 2 ℃ for 10min, cooling the catalyst to room temperature, and collecting the obtained powder, namely the CuSAP/CdS photocatalyst.
Example four
A preparation method of a catalyst for hydrogen production by photolysis of water by phosphorus atom fixed Cu monoatomic load with snowflake-shaped CdS heterojunction comprises the following steps:
the method comprises the following specific steps:
1. adding 5.0mmol of Cd (CH) 3 COO) 2 ·3H 2 O, 6.0mmol of thiourea and 806.0 mu L of hydrofluoric acid are added into 79.2ml of deionized water and stirred for 2 hours;
2. transferring the suspension into a polytetrafluoroethylene reaction kettle, heating the suspension to 200 ℃ from room temperature by using a drying box, preserving heat and reacting for 20 hours, and naturally cooling the suspension to room temperature after the reaction is finished;
3. centrifuging the product obtained in the step 2, washing the product for 4 times by using deionized water and ethanol until the supernatant is transparent, collecting the obtained precipitate, finally drying the precipitate in a drying oven for several hours at 110 ℃, and fully grinding the precipitate to obtain the CdS catalyst;
4. ultrasonically dispersing 0.3g of the dried CdS obtained in the step 3 in 55ml of deionized water to mark as a solution A, and preparing 0.10mmol/L CuCl by using a volumetric flask 2 ·2H 2 The O solution is marked as solution B;
5. dropwise adding 100ml of the solution B prepared in the step into the solution A, continuously stirring, and then drying the mixed solution for 30 hours at 60 ℃;
6. the solid obtained by drying in step 5 was thoroughly ground and the powder obtained was then mixed with 0.1g of NaH 2 PO 2 Respectively arranged at two ends of a quartz boat with a cover, wherein NaH 2 PO 2 Placing the catalyst at one end of an air inlet, then placing the catalyst in a tubular furnace to calcine the catalyst in Ar atmosphere, heating the catalyst from room temperature to 450 ℃, wherein the heating rate is 8 ℃, the calcining time is 15min, cooling the catalyst to room temperature, and collecting the obtained powder, namely the CuSAP/CdS photocatalyst.
EXAMPLE five (optimal)
A preparation method of a catalyst for hydrogen production by photolysis of water by phosphorus atom fixed Cu monoatomic load with snowflake-shaped CdS heterojunction comprises the following steps:
1. adding 5.0mmol of Cd (CH) 3 COO) 2 ·3H 2 O, 6.0mmol of thiourea and 805.0 mu L of hydrofluoric acid are added into 79.2ml of deionized water and stirred for 2 hours;
2. transferring the suspension into a polytetrafluoroethylene reaction kettle, heating the suspension from room temperature to 200 ℃ by using a drying oven, preserving heat, reacting for 20 hours, and naturally cooling to room temperature after the reaction is finished;
3. centrifuging the product obtained in the step 2, washing the product for 3 times by using deionized water and ethanol until the supernatant is transparent, collecting the obtained precipitate, finally drying the precipitate in a drying oven at 100 ℃ for several hours, and fully grinding the precipitate to obtain the CdS catalyst;
4. ultrasonically dispersing 0.2g of the dried CdS obtained in the step 3 in 50ml of deionized water to mark as a solution A, and preparing 0.10mmol/L CuCl by using a volumetric flask 2 ·2H 2 The O solution is marked as solution B;
5. dropwise adding 100ml of the solution B prepared in the step into the solution A, continuously stirring, and then drying the mixed solution for 24 hours at 60 ℃;
6. the solid obtained by drying in step 5 was thoroughly ground and the powder obtained was then mixed with 0.2g of NaH 2 PO 2 Respectively arranged at two ends of a quartz boat with a cover, wherein NaH 2 PO 2 Placing the catalyst at one end of an air inlet, then placing the catalyst in a tubular furnace to calcine the catalyst in Ar atmosphere, heating the catalyst from room temperature to 400 ℃, heating the catalyst at the rate of 5 ℃ for 10min, cooling the catalyst to room temperature, and collecting the obtained powder, namely the CuSAP/CdS photocatalyst.
EXAMPLE six
A preparation method of a catalyst for hydrogen production by photolysis of water by phosphorus atom fixed Cu monoatomic load with snowflake-shaped CdS heterojunction comprises the following steps:
1. adding 6.0mmol of Cd (CH) 3 COO) 2 ·3H 2 O, 7.0mmol of thiourea and 806.0 mu L of hydrofluoric acid are added into 79.4ml of deionized water and stirred for 3 hours;
2. transferring the suspension into a polytetrafluoroethylene reaction kettle, heating the suspension from room temperature to 210 ℃ by using a drying oven, preserving heat, reacting for 21 hours, and naturally cooling to room temperature after the reaction is finished;
3. centrifuging the product obtained in the step 2, washing the product for 4 times by using deionized water and ethanol until the supernatant is transparent, collecting the obtained precipitate, finally drying the precipitate in a drying oven for several hours at 110 ℃, and fully grinding the precipitate to obtain the CdS catalyst;
4. ultrasonically dispersing 0.3g of the dried CdS obtained in the step 3 in 55ml of deionized water to mark as a solution A, and preparing 0.15mmol/L CuCl by using a volumetric flask 2 ·2H 2 The O solution is marked as solution B;
5. dropwise adding 50ml of the solution B prepared in the step into the solution A, continuously stirring, and then drying the mixed solution for 20 hours at 70 ℃;
6. the solid obtained by drying in step 5 was thoroughly ground and the powder obtained was then mixed with 0.2g of NaH 2 PO 2 Respectively arranged at two ends of a quartz boat with a cover, wherein NaH 2 PO 2 Placing the catalyst at one end of an air inlet, then placing the catalyst in a tubular furnace to calcine the catalyst in Ar atmosphere, heating the catalyst from room temperature to 400 ℃, heating the catalyst at the rate of 8 ℃ for 10min, cooling the catalyst to room temperature, and collecting the obtained powder, namely the CuSAP/CdS photocatalyst.
EXAMPLE seven
A preparation method of a catalyst for hydrogen production by photolysis of water by phosphorus atom fixed Cu monoatomic load with snowflake-shaped CdS heterojunction comprises the following steps:
1. adding 6.0mmol of Cd (CH) 3 COO) 2 ·3H 2 O, 7.0mmol of thiourea and 806.0 mu L of hydrofluoric acid are added into 79.4ml of deionized water and stirred for 3 hours;
2. transferring the suspension into a polytetrafluoroethylene reaction kettle, heating the suspension to 210 ℃ from room temperature by using a drying box, preserving heat, reacting for 21 hours, and naturally cooling the suspension to room temperature after the reaction is finished;
3. centrifuging the product obtained in the step 2, washing the product for 4 times by using deionized water and ethanol until the supernatant is transparent, collecting the obtained precipitate, finally drying the precipitate in a drying oven for several hours at 110 ℃, and fully grinding the precipitate to obtain the CdS catalyst;
4. ultrasonically dispersing 0.3g of the dried CdS obtained in the step 3 in 55ml of deionized water to mark as a solution A, and preparing 0.15mmol/L CuCl by using a volumetric flask 2 ·2H 2 The O solution is marked as solution B;
5. dropwise adding 150ml of the solution B prepared in the step into the solution A, continuously stirring, and then drying the mixed solution for 30 hours at 70 ℃;
6. the solid obtained by drying in step 5 was thoroughly ground and the powder obtained was then mixed with 0.3g of NaH 2 PO 2 Respectively arranged at two ends of a quartz boat with a cover, wherein NaH 2 PO 2 Placing at one end of the air inlet, calcining in a tubular furnace under Ar atmosphere, heating from room temperature to 450 deg.C at a heating rate of 8 deg.C for 15min, cooling to room temperatureAnd collecting the obtained powder after warming, namely the CuSAP/CdS photocatalyst.
Test examples
The composite photocatalyst of the embodiment 1-7 is used for carrying out a photocatalytic water decomposition hydrogen production experiment, and the reaction conditions are as follows: the comprehensive test equipment for Pofely LaBSOLAR-6A photocatalyst consists of light source, reaction equipment, magnetically controlled gas circulating unit, vacuum unit, collecting unit, chromatographic test unit, etc. The hydrogen production system by photolysis of water is connected with a gas chromatograph, and the generated gas is injected into the gas chromatograph for analysis. The gas chromatograph is provided with a thermal conductivity testing device (TCD), a 5A molecular sieve is used as a chromatographic column, and high-purity N is used 2 Used as carrier gas, experimental parameters were set as: the TCD unit was set at 150 deg.C, the vaporizer at 110 deg.C, and the column at 50 deg.C. The specific operation of the photocatalytic hydrogen evolution experiment is as follows: 50mg of photocatalyst was well dispersed in a quartz reaction apparatus containing 10mL of lactic acid +90mL of deionized water, which served to consume holes. The simulated light source used was a 300W xenon lamp, and an optical filter (lambda) was used>420nm, AM ═ 1.5) filters light in the ultraviolet band. And detecting the hydrogen production rate by using a gas chromatograph. High-purity N needs to be introduced before illumination 2 Degassing the whole system (including the solution) to discharge O in the device 2 . The temperature of the reaction system is kept at 10 +/-0.5 ℃ by using a constant-temperature water bath method. The hydrogen production test results are shown in Table 1, and the highest hydrogen production rate of the photocatalyst of the system can reach 136.8mmol h -1 g -1 。
TABLE 1 rate of hydrogen production by photocatalytic decomposition of the examples
| Hydrogen production rate (mmol h) -1 g -1 ) | Stability to Hydrogen (h) | |
| Example one | 122.5 | ≥24 |
| Example two | 124.1 | ≥24 |
| EXAMPLE III | 126.0 | ≥24 |
| Example four | 117.6 | ≥24 |
| EXAMPLE five | 136.8 | ≥24 |
| EXAMPLE six | 125.1 | ≥24 |
| EXAMPLE seven | 120.2 | ≥24 |
Comparative example
In order to compare the level of the performance of the photocatalyst of the system for decomposing hydrogen by water, the hydrogen production rate of the composite photocatalyst of the CdS system is listed. Patent CN112808280A discloses an S-doped TiO 2 The optimal hydrogen production rate of the composite photocatalytic hydrogen production material of CdS is about 1.31mmol h under the illumination condition of a 300W xenon lamp -1 g -1 . Patent CN112121834A discloses an MXene/CdS composite photocatalyst with an optimal hydrogen production rate of about 3.71mmol h -1 g -1 . The patent CN113398998A discloses a Zr-MOF @ CdS photocatalyst, and the optimal hydrogen production rate is about 1.86mmol h on average -1 g -1 . Patent CN103381367A discloses CdS/Ba 0.9 Zn 0.1 TiO 3 The optimal hydrogen production rate of the composite photocatalyst is about 1.47mmol h -1 g -1 . Therefore, the photocatalyst synthesized by the method has obviously higher performance of photocatalytic water decomposition to produce hydrogen.
Although the present invention has been described herein with reference to the illustrated embodiments thereof, which are intended to be preferred embodiments of the present invention, it is to be understood that the invention is not limited thereto, and that numerous other modifications and embodiments can be devised by those skilled in the art that will fall within the spirit and scope of the principles of this disclosure.
Claims (10)
1. A preparation method of a CuSAP/CdS photolysis water hydrogen production catalyst is characterized by comprising the following steps: (1) ultrasonically dispersing a CdS catalyst in deionized water to obtain a solution A, and preparing a copper salt solution as a solution B; (2) dropwise adding the solution B into the solution A, continuously stirring, and then drying the mixed solution; (3) fully grinding the solid obtained after drying, and mixing the obtained powder with NaH 2 PO 2 Respectively arranged at two ends of a quartz boat with a cover, wherein NaH 2 PO 2 Placing the catalyst at one end of an air inlet, then placing the catalyst in a tubular furnace to calcine the catalyst in an inert atmosphere, cooling the catalyst to room temperature, and collecting the obtained powder, namely the CuSAP/CdS photocatalyst.
2. The preparation method of the CuSAP/CdS photolysis water-splitting hydrogen production catalyst according to claim 1, wherein the preparation method of the CdS catalyst comprises the following steps: adding cadmium salt, a sulfur source and strong acid into deionized water, mixing and uniformly stirring to obtain a suspension, heating the suspension for reaction, cooling after reaction, centrifuging and washing a product to obtain a precipitate, drying and grinding the precipitate to obtain the CdS catalyst.
3. The preparation method of the CuSAP/CdS catalyst for hydrogen production from photolysis of water according to claim 2, wherein the cadmium salt is selected from any one of chromium acetate, cadmium chloride or cadmium nitrate, the sulfur source is selected from any one of thiourea, sodium sulfide or sodium thiosulfate, and the strong acid is selected from any one of hydrofluoric acid, hydrochloric acid or sulfuric acid.
4. The preparation method of the CuSAP/CdS photolysis water-hydrogen-production catalyst as claimed in claim 2, wherein the heating reaction is specifically to transfer the suspension into a polytetrafluoroethylene reaction kettle, heat the suspension from room temperature to 190 ℃ with a drying oven, and carry out heat preservation reaction for 19-21h, and naturally cool the reaction product to room temperature after the reaction is finished.
5. The preparation method of the CuSAP/CdS photolysis water-hydrogen-production catalyst according to claim 2, wherein the washing is specifically washing with deionized water and ethanol for 2-4 times until the supernatant is transparent, and collecting the obtained precipitate.
6. The preparation method of the CuSAP/CdS photolytic hydrogen production catalyst according to claim 2, wherein the molar ratio of the cadmium salt to the sulfur source is (4-6) mmol: (5-7) mmol, wherein the molar volume ratio of the cadmium salt to the strong acid is (4-6) mmol: (804-806) μ L.
7. The preparation method of the CuSAP/CdS photolysis water-splitting hydrogen production catalyst according to claim 1, wherein the mass-to-volume ratio of CdS to deionized water in step (1) is (0.1-0.3) g: (45-55) ml, the concentration of the solution B is 0.05-0.15mmol/L, and the copper salt is copper chloride or copper sulfate.
8. The preparation method of the CuSAP/CdS photolysis water-hydrogen-production catalyst according to claim 1, wherein the drying condition in the step (2) is 50-70 ℃ for 20-30 h.
9. The preparation method of the CuSAP/CdS catalyst for hydrogen production from water photolysis as claimed in claim 1, wherein the calcination in step (3) is performed under the conditions of temperature rise from room temperature to 350-450 ℃, temperature rise rate of 2-8 ℃ and calcination time of 5-15 min.
10. A catalyst for hydrogen production by water photolysis of CuSAP/CdS, which is prepared by the preparation method of any one of claims 1 to 9.
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