CN116984003A - CdIn without sacrificial agent hydrogen evolution 2 S 4 /MoO 3-x Composite photocatalyst and preparation method thereof - Google Patents
CdIn without sacrificial agent hydrogen evolution 2 S 4 /MoO 3-x Composite photocatalyst and preparation method thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 41
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 40
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000003795 chemical substances by application Substances 0.000 title abstract description 15
- 230000001699 photocatalysis Effects 0.000 claims abstract description 32
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- 238000000034 method Methods 0.000 claims abstract description 8
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- 239000002135 nanosheet Substances 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 25
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 239000006185 dispersion Substances 0.000 claims description 11
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 229910052717 sulfur Inorganic materials 0.000 claims description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- 239000011593 sulfur Substances 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 150000001661 cadmium Chemical class 0.000 claims description 5
- 150000002471 indium Chemical class 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 229910052724 xenon Inorganic materials 0.000 claims description 5
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 2
- 230000001678 irradiating effect Effects 0.000 claims description 2
- 239000002057 nanoflower Substances 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 4
- 238000012546 transfer Methods 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 2
- 230000027756 respiratory electron transport chain Effects 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 239000000969 carrier Substances 0.000 abstract 1
- 238000007146 photocatalysis Methods 0.000 description 9
- 238000002156 mixing Methods 0.000 description 8
- 229910021617 Indium monochloride Inorganic materials 0.000 description 6
- APHGZSBLRQFRCA-UHFFFAOYSA-M indium(1+);chloride Chemical group [In]Cl APHGZSBLRQFRCA-UHFFFAOYSA-M 0.000 description 6
- 230000031700 light absorption Effects 0.000 description 6
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical group CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 description 6
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 6
- 238000000926 separation method Methods 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000005215 recombination Methods 0.000 description 3
- 230000006798 recombination Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000002800 charge carrier Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
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- 230000002708 enhancing effect Effects 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
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- 238000001878 scanning electron micrograph Methods 0.000 description 2
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- 230000002195 synergetic effect Effects 0.000 description 2
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
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- 238000010168 coupling process Methods 0.000 description 1
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- 238000001362 electron spin resonance spectrum Methods 0.000 description 1
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- 239000003574 free electron Substances 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000001259 photo etching Methods 0.000 description 1
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- 231100000331 toxic Toxicity 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the technical field of photocatalytic hydrogen production, and in particular relates to a CdIn without a sacrificial agent for hydrogen evolution 2 S 4 /MoO 3‑x A composite photocatalyst and a preparation method thereof. In the invention, the flaky MoO is prepared by a hydrothermal method 3‑x Then the CdIn is treated by an oil bath method 2 S 4 MoO (MoO) loaded on surface of nanometer flower ball 3‑x Nano-sheet, preparing CdIn 2 S 4 /MoO 3‑x A composite photocatalyst. CdIn 2 S 4 And MoO 3‑x The formation of the Mo-S covalent bond can serve as an "electron bridge" to regulate electron transfer while MoO 3‑x And CdIn 2 S 4 The S-shaped heterojunction is formed, and the transfer of photo-generated carriers can be promoted. The invention innovatively discovers that CdIn 2 S 4 And MoO 3‑x The brand new material formed by the double-vacancy composite material has good stability and hydrogen production activity under the condition of no sacrificial agent.
Description
Technical Field
The invention belongs to the technical field of photocatalytic hydrogen production, and particularly relates to a method for preparing hydrogen by using a catalystAnd CdIn rich in double vacancies 2 S 4 /MoO 3-x The composite photocatalyst and the preparation method thereof can catalyze and produce hydrogen in a catalyst system without a sacrificial agent.
Background
Currently, energy crisis is one of the most urgent problems in the world, and thus, development of new clean energy is urgent. Hydrogen (H) 2 ) Are considered ideal energy sources due to their sustainability and high energy density. Photocatalytic hydrolysis is a valuable technique for producing hydrogen, which can convert inexhaustible solar energy into useful chemical energy. Therefore, developing a novel photocatalyst with advantages of high efficiency, low cost, environmental friendliness and the like is a current primary task. In order to increase the photocatalytic efficiency, sacrificial agents are generally added to existing photocatalytic systems. However, many sacrificial agents such as methanol, lactic acid, triethanolamine are environmentally hazardous. Therefore, the photocatalysis hydrogen evolution research without using the sacrificial agent has important significance for environmental protection. However, photocatalytic bulk water splitting presents a number of difficulties, and achieving efficient photocatalytic pure water splitting without sacrificing agents is very challenging.
CdIn as n-type semiconductor 2 S 4 Is considered as an ideal material in the field of photocatalysis. Its suitable conduction band site is H 2 Provides sufficient power. However, the rapid recombination of photo-generated holes and electrons and the photo-etching limit their development in photocatalysis. To realize CdIn 2 S 4 Higher photocatalytic performance, sulfur vacancies are induced to CdIn 2 S 4 To regulate photo-carrier transport.
Compared with plasma metal, the plasma semiconductor has the advantages of remarkably reduced noble metal consumption, saved cost, and stronger light absorption in the near infrared region. MoO (MoO) 3-x Has been widely used in the field of photocatalysis because of the abundance of oxygen vacancies in the surface, resulting in an increase in free charge density, wherein free electrons, when illuminated, can resonate with incident light, producing Localized Surface Plasmon Resonance (LSPR) effects, enhancing light absorption, accelerating charge separation and transfer, and promoting surface catalytic reactionsThe method has outstanding advantages in the field of photocatalysis.
Disclosure of Invention
The inventor finds that the construction of heterojunction by coupling different materials with different energy level structures is an effective means for improving the photocatalytic performance. Thus constructing S-type heterostructure CdIn 2 S 4 /MoO 3-x The photo-induced electron and hole charge separation is accelerated. However CdIn 2 S 4 And MoO 3-x There is no direct intimate interface connection, impeding charge flow. The sulfur vacancy and the Mo-S covalent bond can be used as an electron bridge to regulate electron transfer, so that the charge transfer process is accelerated, and the photocatalytic hydrogen evolution reaction is realized without using a sacrificial agent.
The invention aims to provide a CdIn rich in double vacancies 2 S 4 /MoO 3-x The composite photocatalyst and the preparation method thereof can catalyze and produce hydrogen in a catalyst system without a sacrificial agent.
The CdIn provided by the invention 2 S 4 /MoO 3-x The composite photocatalyst has a 2D/3D structure, namely a sheet-like structure MoO 3-x Cover on nanometer flower ball CdIn 2 S 4 The surface of the structure can obviously inhibit the recombination of electron-hole pairs and enhance the light absorption.
The invention also provides the CdIn 2 S 4 /MoO 3-x The preparation method of the composite photocatalyst comprises the following specific steps: moO is carried out 3-x Uniformly dispersing in water to obtain MoO 3-x A dispersion; dissolving soluble cadmium salt, soluble indium salt and sulfur source in glycerol solution, and adding MoO 3-x The dispersion liquid is uniformly mixed to obtain a mixed solution; oil-bath reacting the mixed solution, cooling, centrifuging, washing, and drying to obtain CdIn 2 S 4 /MoO 3-x A composite photocatalyst.
Wherein MoO 3-x The mass concentration of the dispersion liquid is 2.5-10 mg/mL; glycerol solution and MoO 3-x The volume ratio of the dispersion liquid is 3-5:1.
In some preferred embodiments, the amount ratio of the soluble cadmium salt, the soluble indium salt, and the sulfur source is 1:2:8.
In some preferred embodiments, the soluble cadmium salt is CdCl 2 ·2.5H 2 O, the soluble indium salt is InCl 3 ·4H 2 O, the sulfur source is thioacetamide; cdCl 2 ·2.5H 2 O、InCl 3 ·4H 2 The mass ratio of O to thioacetamide is 1:2:8.
in some preferred embodiments, the conditions of the oil bath reaction are: reacting (1-3) for h at 80 ℃.
In some exemplary embodiments, moO 3-x And CdIn 2 S 4 The mass ratio is (0.3-1.25): 1, a step of; preferably, moO 3-x And CdIn 2 S 4 The mass ratio is (0.625-1.25): 1, a step of; further preferred, moO 3-x And CdIn 2 S 4 The mass ratio is (0.625-1): 1.
in a specific embodiment of the present invention, the above CdIn 2 S 4 /MoO 3-x The preparation method of the composite photocatalyst comprises the following steps: moO (MoO) 3-x Is prepared through the following steps: adding Mo powder into n-butanol, and adding H 2 O 2 The solution is fully stirred and then subjected to hydrothermal reaction, and after the reaction is finished, the solution is cooled, centrifuged, washed and dried to obtain the MoO with a sheet-shaped structure 3-x A photocatalyst;
in some preferred embodiments, the Mo powder is used in combination with n-butanol, H 2 O 2 The dosage ratio of (2) is 0.03-0.07 g: 7-10 mL:1mL.
In some preferred embodiments, the hydrothermal reaction conditions are: reacting (10-15) for h at 140 ℃.
The invention also provides the CdIn 2 S 4 /MoO 3-x H is produced by the composite photocatalyst in photocatalysis 2 Is used in the field of applications.
In some exemplary embodiments, the application includes: irradiating with xenon lamp, deionized water and CdIn 2 S 4 /MoO 3-x Adding the composite photocatalyst into a photoreactor, using a 300W xenon lamp as a light source, and adding the light source into N 2 And (3) reacting in a gas atmosphere. In some particular embodiments, deionized water and CdIn 2 S 4 /MoO 3-x The amount of the composite photocatalyst was 50mL:0.02g.
The invention realizes the preparation of CdIn 2 S 4 /MoO 3-x Photocatalytic production of H for composite photocatalyst 2 Is a target of (a). Under the irradiation of simulated sunlight, the photocatalysis hydrogen evolution reaction is carried out in pure water, which is an efficient and environment-friendly technology.
Under the strong synergistic effect among Mo-S bond, internal electric field and sulfur vacancy, cdIn 2 S 4 /MoO 3-x The S-type heterojunction enhances charge transfer between components and achieves excellent sacrificial-free photocatalytic performance. The invention utilizes the synergistic effect of Mo-S bond and S-type heterojunction, gets rid of the traditional sacrificial agent and carries out photocatalysis hydrogen evolution reaction in pure water. The combination of S vacancies and O vacancy double vacancies has outstanding advantages in the fields of photocatalysis, such as enhancing light absorption, accelerating charge separation and transfer, promoting surface catalytic reaction, and the like. The research provides a new direction for preparing the noble metal-free catalyst with excellent hydrogen production performance in a pure water system.
Description of the drawings:
FIG. 1 shows the CdIn prepared in examples 1-4 of the present invention 2 S 4 /MoO 3-x XRD pattern of (b);
FIG. 2 shows the CdIn produced in example 1 of the present invention 2 S 4 /MoO 3-x Is an infrared spectrum of (2);
FIG. 3 shows the CdIn prepared in example 2 of the present invention 2 S 4 /MoO 3-x SEM images of (a);
FIG. 4 shows the CdIn prepared in example 2 of the present invention 2 S 4 /MoO 3-x A TEM image of (a);
FIG. 5 shows the CdIn produced in example 2 of the present invention 2 S 4 /MoO 3-x Is a mapping graph of (1);
FIG. 6 shows the CdIn produced in example 3 of the present invention 2 S 4 ，MoO 3-x And CdIn 2 S 4 /MoO 3-x UV-vis profile of (a);
FIG. 7 shows the CdIn produced in example 3 of the present invention 2 S 4 ，MoO 3-x And CdIn 2 S 4 /MoO 3-x An EPR profile of (c);
FIG. 8 shows the CdIn produced in examples 1 to 4 of the present invention 2 S 4 /MoO 3-x A photo-catalytic hydrogen production rate graph;
FIG. 9 shows the CdIn produced in example 4 of the present invention 2 S 4 /MoO 3-x And a photocatalytic hydrogen production cycle experiment diagram.
Detailed Description
The invention will be further described with reference to the drawings and the specific embodiments, but the scope of the invention is not limited thereto.
Because of the current field of photocatalytic hydrogen production, some of the sacrificial agents used are toxic. Therefore, the photocatalytic hydrogen evolution research without using a sacrificial agent has important significance for environmental protection. The inventors of the present invention, upon conducting studies in the art, found that surface defects in nanomaterials that produce highly localized electronic structural changes are considered to be H 2 Can act as a trapping site for photogenerated electrons to facilitate the separation of charge carriers in their localized electronic state. MoO with oxygen vacancy 3-x And CdIn with sulfur vacancy 2 S 4 The combination achieves a separation of efficient charge carriers and holes. Meanwhile, by utilizing the construction of the S-shaped heterojunction, the recombination of electron-hole pairs is obviously inhibited, and the photocatalytic hydrogen evolution capability is further enhanced.
Example 1
(1) Preparation of MoO 3-x : 0.192g of Mo powder was dissolved in 24mL of n-butanol. 3mL of a solution containing 30% H was further added dropwise 2 O 2 To the above solution and stirred until the solution turned bright yellow. Maintaining the solution at 140deg.C under hydrothermal condition for 12 hr, cooling to room temperature, centrifuging, washing with deionized water and ethanol respectively, and drying in oven at 60deg.C overnight to obtain MoO 3-x 。
(2) 0.4mmol CdCl 2 ·2.5H 2 O，0.8mmol InCl 3 ·4H 2 O and 3.2mmol thioacetamide are completely dissolved in 60ml of a solution containing 20% glycerol; 0.05g MoO 3-x Mixing the powder with 20mL distilled water to obtain MoO 3-x And (3) a dispersion liquid, and mixing the two solutions. Placing the solution into a constant temperature oil bath potIn the method, the reaction is carried out for two hours at 80 ℃, after the reaction is finished, the mixed solution is centrifuged, washed and dried, and then the CdIn is obtained 2 S 4 /MoO 3-x Composite photocatalyst (CISMO-1).
Example 2
(1) Preparation of MoO 3-x : as in example 1;
(2) 0.4mmol CdCl 2 ·2.5H 2 O，0.8mmol InCl 3 ·4H 2 O and 3.2mmol thioacetamide are completely dissolved in 60ml of a solution containing 20% glycerol; 0.1g MoO 3-x Mixing the powder with 20mL distilled water to obtain MoO 3-x And (3) a dispersion liquid, and mixing the two solutions. Placing the solution into a constant temperature oil bath pot, reacting for two hours at 80 ℃, centrifuging, washing and drying the mixed solution after the reaction is finished to obtain CdIn 2 S 4 /MoO 3-x Composite photocatalyst (CISMO-2).
Example 3
(1) Preparation of MoO 3-x : as in example 1;
(2) 0.4mmol CdCl 2 ·2.5H 2 O，0.8mmol InCl 3 ·4H 2 O and 3.2mmol thioacetamide are completely dissolved in 60ml of a solution containing 20% glycerol; 0.15g MoO 3-x Mixing the powder with 20mL distilled water to obtain MoO 3-x And (3) a dispersion liquid, and mixing the two solutions. Placing the solution into a constant temperature oil bath pot, reacting for two hours at 80 ℃, centrifuging, washing and drying the mixed solution after the reaction is finished to obtain CdIn 2 S 4 /MoO 3-x Composite photocatalyst (CISMO-3).
Example 4
(1) Preparation of MoO 3-x : as in example 1;
(2) 0.4mmol CdCl 2 ·2.5H 2 O，0.8mmol InCl 3 ·4H 2 O and 3.2mmol thioacetamide are completely dissolved in 60ml of a solution containing 20% glycerol; 0.2g MoO 3-x Mixing the powder with 20mL distilled water to obtain MoO 3-x And (3) a dispersion liquid, and mixing the two solutions. Placing the solution into a constant temperature oil bath pot, reacting at 80deg.C for two hours, centrifuging the mixed solution after the reaction is completed, and washingWashing and drying to obtain CdIn 2 S 4 /MoO 3-x Composite photocatalyst (CISMO-4).
Example 5
CdIn 2 S 4 /MoO 3-x Photocatalytic H production of composite photocatalyst in sacrificial agent-free system 2 : in a photoreactor, 0.02g of the composite photocatalytic material prepared in examples 1 to 4 or pure MoO was irradiated with a xenon lamp 3-x Or CdIn 2 S 4 Adding the photocatalyst and 50mL deionized water into a reactor after ultrasonic dispersion, and continuously introducing N 2 And vacuumizing after gas, closing the gas outlet to enable the inside of the reactor to reach a certain pressure (0.1 MPa), sealing the reactor, and opening a light source, wherein the light source is a xenon lamp with the wavelength of 420nm, and reacting for 5 hours. Sampling analysis was performed at intervals of 0.5 h.
Experimental results:
referring to FIG. 1, the CdIn of the embodiment of the invention 2 S 4 /MoO 3-x (abbreviated as CISMO in the figure), and known samples CIS PDF#27-0060, moO 3-x As can be seen from XRD spectra of PDF #70-0615 and comparison of characteristic peaks, cdIn is successfully prepared according to the specific embodiment of the present invention 2 S 4 /MoO 3-x 。
Referring to FIG. 2, the embodiment of the present invention provides a CdIn prepared in example 1 2 S 4 /MoO 3-x An infrared spectrum of the photocatalyst; clearly shown in FIG. 2 is CdIn 2 S 4 /MoO 3-x Comprises MoO 3-x And CdIn 2 S 4 /MoO 3-x Is a characteristic peak of (1) and CdIn 2 S 4 /MoO 3-x Contains Mo-S characteristic peaks. This illustrates the embodiment of the present invention CdIn 2 S 4 And MoO 3-x Mo-S bonds are formed in the middle.
Referring to FIG. 3, the embodiment of the present invention is shown as example 2 of CdIn 2 S 4 /MoO 3-x FIG. 4 is an SEM image of a composite photocatalyst, showing the CdIn of example 2 in an embodiment of the invention 2 S 4 /MoO 3-x TEM image of composite photocatalyst; the MoO is clearly seen in FIGS. 3 and 4 3-x The nano-sheet uniformly wraps CdIn 2 S 4 A nanometer flower ball.
FIG. 5 shows the CdIn of example 2 in the embodiment of the invention 2 S 4 /MoO 3-x The mapping graph of the composite photocatalyst shows that In, cd, S, mo and O elements are uniformly distributed, and further shows MoO 3-x /Cu 0.5 Cd 0.5 S composite photocatalyst is successfully prepared.
Referring to FIG. 6, a CdIn is prepared according to an exemplary embodiment of the present invention 2 S 4 、MoO 3-x With CdIn prepared in example 3 2 S 4 /MoO 3-x From the figure, it can be seen that the UV-vis spectrum of (C) is comparable to CdIn alone 2 S 4 And MoO 3-x In contrast, the composite CdIn 2 S 4 /MoO 3-x The light absorption capacity is significantly enhanced.
Referring to FIG. 7, it can be seen that CdIn is prepared for the exemplary embodiment of the present invention 2 S 4 、MoO 3-x With CdIn prepared in example 3 2 S 4 /MoO 3-x From the EPR spectrum of (C), it can be seen that CdIn 2 S 4 S vacancy, moO 3-x With O vacancy, cdIn 2 S 4 /MoO 3-x There are double vacancies.
Referring to FIG. 8, it can be seen that, compared to MoO 3-x And CdIn 2 S 4 CdIn examples 1 to 4 in the embodiment of the present invention 2 S 4 /MoO 3-x Has better photocatalytic hydrogen production performance.
Please refer to fig. 9, which shows CdIn in example 4 2 S 4 /MoO 3-x Through continuous test for 25h, cdIn 2 S 4 /MoO 3-x There was no significant decrease in the photocatalytic rate, indicating CdIn 2 S 4 /MoO 3-x- The composite material has high hydrogen production stability.
In conclusion, the CdIn is prepared by a hydrothermal oiling bath method 2 S 4 /MoO 3-x- The composite material has improved light absorption and photocatalysisThe enhancement and the better cyclic hydrogen production performance are realized. Compared with other samples, the optimized CdIn 2 S 4 /MoO 3-x An S-type (S-Scheme) heterojunction is formed. The maximum hydrogen production efficiency is 108.75 mu mol.h without adding a sacrificial agent -1 ·g -1 The invention provides an effective method for obtaining a stable photocatalytic hydrogen production system.
The foregoing is only a preferred or exemplary embodiment of the invention, it being noted that: it will be apparent to those skilled in the art that various modifications or adaptations can be made without departing from the principles of the present invention, and such modifications or adaptations are intended to be within the scope of the invention.
Claims (10)
1. CdIn 2 S 4 /MoO 3-x The composite photocatalyst is characterized in that the CdIn 2 S 4 /MoO 3-x The composite photocatalyst has a 2D/3D structure and MoO 3-x The nano-sheets are covered on the nano-flower ball CdIn 2 S 4 Forming an S-shaped heterojunction on the surface; the CdIn 2 S 4 /MoO 3-x The composite photocatalyst catalyzes the production of hydrogen in a sacrificial agent-free catalytic system.
2. A CdIn as claimed in claim 1 2 S 4 /MoO 3-x The preparation method of the composite photocatalyst is characterized by comprising the following steps: dissolving soluble cadmium salt, soluble indium salt and sulfur source in glycerol solution, and adding MoO 3-x The dispersion liquid is uniformly mixed to obtain a mixed solution; carrying out oil bath reaction on the mixed solution, centrifuging, washing and drying after the reaction is finished to obtain CdIn 2 S 4 /MoO 3-x A composite photocatalyst.
3. CdIn according to claim 2 2 S 4 /MoO 3-x The preparation method of the composite photocatalyst is characterized in that the mass ratio of the soluble cadmium salt to the soluble indium salt to the sulfur source is 1:2:8.
4. CdIn according to claim 2 2 S 4 /MoO 3-x The preparation method of the composite photocatalyst is characterized by comprising the steps of 3-x The mass concentration of the dispersion liquid is 2.5-10 mg/mL; glycerol solution and MoO 3-x The volume ratio of the dispersion liquid is 3-5:1.
5. CdIn according to claim 2 2 S 4 /MoO 3-x The preparation method of the composite photocatalyst is characterized in that the temperature of the oil bath reaction is 80 ℃ and the reaction time is 1-3 h.
6. CdIn according to claim 2 2 S 4 /MoO 3-x The preparation method of the composite photocatalyst is characterized by comprising the steps of 3-x And CdIn 2 S 4 The mass ratio is 0.3-1.25: 1.
7. CdIn according to claim 2 2 S 4 /MoO 3-x The preparation method of the composite photocatalyst is characterized by comprising the steps of 3-x The preparation method of (2) is as follows: adding Mo powder into n-butanol, and adding H 2 O 2 The solution is fully stirred and then is subjected to hydrothermal reaction for 10 to 15 hours at 140 ℃, and after the reaction is finished, the solution is cooled, centrifuged, washed and dried to obtain the MoO with a sheet-shaped structure 3-x The method comprises the steps of carrying out a first treatment on the surface of the Wherein Mo powder, n-butanol and H 2 O 2 The dosage ratio of (2) is 0.03-0.07 g: 7-10 mL:1mL.
8. A CdIn as claimed in claim 1 2 S 4 /MoO 3-x The application of the composite photocatalyst in the photocatalytic hydrogen production.
9. The use according to claim 8, characterized by the steps of: irradiating with light source to obtain CdIn 2 S 4 /MoO 3-x Uniformly dispersing the composite photocatalyst in deionized water, adding into a photoreactor, and adding the solution into N 2 And (3) reacting under the irradiation of a xenon lamp in a gas atmosphere.
10. The use according to claim 9, characterized in that CdIn 2 S 4 /MoO 3-x The mass volume ratio of the composite photocatalyst to deionized water is 20mg:50mL.
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