CN115318308A - Simple and convenient solvent thermal method for preparing In (OH) 3 /CdIn 2 S 4 Composite catalyst - Google Patents
Simple and convenient solvent thermal method for preparing In (OH) 3 /CdIn 2 S 4 Composite catalyst Download PDFInfo
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- CN115318308A CN115318308A CN202211066888.XA CN202211066888A CN115318308A CN 115318308 A CN115318308 A CN 115318308A CN 202211066888 A CN202211066888 A CN 202211066888A CN 115318308 A CN115318308 A CN 115318308A
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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
-
- B01J35/39—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- 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
Abstract
The invention relates to the technical field of photocatalytic hydrogen production, and discloses a simple and convenient solvent-thermal method for preparing In (OH) 3 /CdIn 2 S 4 A composite catalyst comprising the following materials: cdIn 2 S 4 Ethylene diamine and an aqueous solution. By CdIn 2 S 4 Respectively as substrate material and indium source, using ethylenediamine and water as solvent and-OH source, and adding CdIn 2 S 4 Second solvothermal at 180 ℃ to form In (OH) 3 /CdIn 2 S 4 The heterojunction, the preparation method is simple and feasible, and the experimental result of the photocatalytic hydrogen production shows that In (OH) 3 /CdIn 2 S 4 Active action of the heterojunction, in (OH) 3 /CdIn 2 S 4 Composite catalysisThe catalyst shows high catalytic hydrogen production activity under visible light (lambda is more than 420 nm), and the highest hydrogen production rate under visible light can reach 1.28mmol/g/h.
Description
Technical Field
The invention relates to the technical field of photocatalytic hydrogen production, in particular to In (OH) prepared by a solvothermal method 3 /CdIn 2 S 4 And (3) compounding a catalyst.
Background
Under the background of shortage of fossil energy and serious environmental pollution, development of green, efficient and renewable energy is crucial, hydrogen energy is considered as one of the best alternative energy sources due to the renewability and no pollution, a photocatalytic hydrogen production technology is considered as an important approach for solving the increasingly serious environmental problems and energy shortage due to the capability of converting solar energy into hydrogen energy, the main principle of the green and environment-friendly technology is that a photocatalyst generates photoproduction electrons and holes under the irradiation of sunlight, the photoproduction electrons and the holes migrate to the surface of the catalyst and participate in a series of photocatalytic oxidation reduction reactions, a semiconductor photocatalytic reaction is the core of the photocatalytic technology, titanium dioxide is proved to be capable of decomposing water and producing hydrogen by photocatalysis in 1972, various semiconductors are used for the photocatalytic fields of decomposing water and degrading organic pollutants, oxides, sulfides and the like, the titanium dioxide is widely researched due to the excellent photocatalytic activity, the band gap of the titanium dioxide is 3.2eV, only ultraviolet light can be absorbed, the vast majority of light in sunlight cannot be utilized, compared with metal sulfides, the metal sulfides have proper band gap and non-toxic light conductivity, the effective light absorption range can be generally increased from the following aspects: (1) The light absorption range is expanded, and the utilization rate of solar energy is improved; (2) The recombination rate of photo-generated electrons and holes is reduced, and (3) the hydrogen evolution overpotential is reduced.
CdIn 2 S 4 One of the important ternary chalcogenide semiconductors is considered a better photocatalyst due to its low toxicity, appropriate bandgap (-2.4 eV) and relatively high chemical stability, however, like most semiconductor-based photocatalysts, pure CdIn 2 S 4 The photocatalytic hydrogen production activity is lower, because the photoproduction electron and the hole are seriously compounded, and the hydrogen evolution overpotential is larger, which seriously influences the practical application of the photocatalytic hydrogen production, thereby providing a simple solvothermal method for preparing In (OH) 3 /CdIn 2 S 4 And (3) compounding a catalyst.
Disclosure of Invention
The invention provides In (OH) prepared by a solvothermal method 3 /CdIn 2 S 4 The composite catalyst has the advantages of improving the separation efficiency of carriers and reducing hydrogen evolution overpotential, and solves the problem of CdIn 2 S 4 The photocatalytic hydrogen production activity is low, the recombination of photogenerated electrons and holes is serious, and the overpotential of hydrogen evolutionLarge, seriously affecting the practical application in photocatalysis.
The invention provides the following technical scheme: simple and convenient solvent-thermal method for preparing In (OH) 3 /CdIn 2 S 4 A composite catalyst comprising the following materials: cdIn 2 S 4 Ethylene diamine and an aqueous solution.
Preferably, the CdIn is 2 S 4 As a substrate material and indium source.
Preferably, the CdIn is 2 S 4 The preparation method specifically comprises the following steps of ultrasonically dissolving 0.6665g of cadmium acetate dihydrate, 3.0085g of indium nitrate tetrahydrate and 6.0150g of glutathione until the solution is clear, pouring the solution into a hydrothermal reaction kettle, placing the hydrothermal reaction kettle into an oven, heating to 140 ℃ for reaction for 5 hours, naturally cooling to room temperature after the reaction is finished, pouring the reacted solution into a 100mL centrifuge tube, centrifugally washing the solution for three times by using water and ethanol, placing the centrifugally washed solution in a 60 ℃ drying environment, and placing the centrifugally washed solution for 12 hours, so that the preparation method is obtained.
Preferably, the volume ratio of the ethylenediamine to the aqueous solution is a, b, c, d and e, respectively, wherein a is 5:1 (water/ethylenediamine); b is 3:1 (water/ethylenediamine); c is 1:1 (water/ethylenediamine); d is 1:3 (water/ethylenediamine); and e is 1:5 (water/ethylenediamine).
Simple and convenient solvent-thermal method for preparing In (OH) 3 /CdIn 2 S 4 The preparation method of the composite catalyst comprises the following steps:
s1, dispersing 0.2g of CdIn in five ethylenediamine and aqueous solutions with different proportional volumes of a, b, c, d and e respectively 2 S 4 ;
S2, respectively obtaining a proportion sample In (OH) 3 /CdIn 2 S 4 (ii) a b proportional sample In (OH) 3 /CdIn 2 S 4 (ii) a c proportion sample In (OH) 3 /CdIn 2 S 4 (ii) a d proportion sample In (OH) 3 /CdIn 2 S 4 And e scale sample In (OH) 3 /CdIn 2 S 4 ;
S3, sampling five samples a, b, c, d and eRespectively performing ultrasonic treatment for 15min, pouring the solution into a hydrothermal reaction kettle, placing the hydrothermal reaction kettle In an oven, heating to 180 ℃, reacting for 12 hours, naturally cooling to room temperature, centrifugally washing the product with water and ethanol for three times, and drying at 60 ℃ for 12 hours to obtain a product In (OH) 3 /CdIn 2 S 4 。
The invention has the following beneficial effects:
1. in (OH) prepared by the solvothermal method 3 /CdIn 2 S 4 Composite catalyst of CdIn 2 S 4 Respectively as substrate material and indium source, using ethylenediamine and water as solvent and-OH source, and adding CdIn 2 S 4 Second solvothermal at 180 ℃ to form In (OH) 3 /CdIn 2 S 4 The heterojunction, the preparation method thereof is simple and easy to implement, so that the CdIn is formed 2 S 4 The catalytic hydrogen production activity and stability of the catalyst are optimized;
2. in (OH) prepared by the solvothermal method 3 /CdIn 2 S 4 A composite catalyst prepared by In (OH) 3 /CdIn 2 S 4 The heterojunction forms strong interface interaction, so that the obtained composite catalyst has higher photocatalytic activity, and provides a way for the separation and migration of photogenerated carriers, thereby improving the separation efficiency of photogenerated electrons and holes, and the experimental result of the photocatalytic hydrogen production shows that In (OH) 3 /CdIn 2 S 4 Active action of the heterojunction, in (OH) 3 /CdIn 2 S 4 The composite catalyst shows higher visible light (lambda)>420 nm), the highest hydrogen production rate under visible light can reach 1.28mmol/g/h, which is higher than that of pure CdIn 2 S 4 The hydrogen production rate is 0.28mmol/g/h, which is about 4.5 times higher.
Drawings
FIG. 1 shows In (OH) produced by the present invention 3 /CdIn 2 S 4 Scanning electron microscope images of the composite catalyst;
FIG. 2 shows In (OH) produced by the present invention 3 /CdIn 2 S 4 Transmission electron micrographs of the composite catalyst;
FIG. 3 is an X-ray diffraction pattern of a catalyst prepared according to the present invention;
FIG. 4 is a diagram of the visible light hydrogen production activity of several catalysts prepared by the present invention;
FIG. 5 shows In (OH) produced by the present invention 3 /CdIn 2 S 4 The stability of the photocatalytic reaction of the composite catalyst is shown.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Referring to FIGS. 1-5, a simple solvothermal method for preparing In (OH) 3 /CdIn 2 S 4 A composite catalyst comprising the following materials: cdIn 2 S 4 Ethylene diamine and aqueous solutions.
Wherein, cdIn 2 S 4 As a substrate material and indium source.
Among them, cdIn 2 S 4 The preparation method specifically comprises the following steps of ultrasonically dissolving 0.6665g of cadmium acetate dihydrate, 3.0085g of indium nitrate tetrahydrate and 6.0150g of glutathione until the solution is clear, pouring the solution into a hydrothermal reaction kettle, placing the hydrothermal reaction kettle into an oven, heating to 140 ℃ for reaction for 5 hours, naturally cooling to room temperature after the reaction is finished, pouring the reacted solution into a 100mL centrifuge tube, centrifugally washing the solution for three times by using water and ethanol, placing the centrifugally washed solution in a 60 ℃ drying environment, and placing the centrifugally washed solution for 12 hours, so that the preparation method is obtained.
Wherein the volume ratio of the ethylenediamine to the aqueous solution is a, b, c, d and e respectively, a is 5:1 (water/ethylenediamine); b is 3:1 (water/ethylenediamine); c is 1:1 (water/ethylenediamine); d is 1:3 (water/ethylene diamine); e is 1:5 (water/ethylenediamine).
Simple and convenient solvent-thermal method for preparing In (OH) 3 /CdIn 2 S 4 Preparation of composite catalystThe preparation method comprises the following steps:
s1, dispersing 0.2g of CdIn in ethylene diamine and water solution with different proportional volumes of a, b, c, d and e respectively 2 S 4 ;
S2, respectively obtaining a proportion sample In (OH) 3 /CdIn 2 S 4 (ii) a b proportion sample In (OH) 3 /CdIn 2 S 4 (ii) a c proportional sample In (OH) 3 /CdIn 2 S 4 (ii) a d proportion sample In (OH) 3 /CdIn 2 S 4 And e scale sample In (OH) 3 /CdIn 2 S 4 );
S3, respectively carrying out ultrasonic treatment on the samples a, b, c, d and e for 15min, pouring the solution into a hydrothermal reaction kettle, placing the hydrothermal reaction kettle In an oven, heating to 180 ℃, reacting for 12 hours, naturally cooling to room temperature, centrifugally washing the product with water and ethanol for three times respectively, and drying at 60 ℃ for 12 hours to obtain a product In (OH) 3 /CdIn 2 S 4 。
Experimental example 1:
adding 0.6665g of cadmium acetate dihydrate, 3.0085g of indium nitrate tetrahydrate and 6.0150g of glutathione into a beaker filled with 60mL of deionized water, performing ultrasonic treatment until the solution is clear, pouring the solution into a hydrothermal reaction kettle, heating to 140 ℃ under the self pressure for reaction for 5 hours, naturally cooling to room temperature after the reaction is finished, respectively centrifuging the product three times by using distilled water and absolute ethyl alcohol, placing the product into an oven, and drying at 60 ℃ for 12 hours to obtain the CdIn 2 S 4 And (4) sampling.
Experimental example 2:
the CdIn of example 1 was reacted with a suitable solvent 2 S 4 Weighing 0.2g, dispersing in a mixed solution of 50mL of water and 10mL of ethylenediamine, sonicating for 15min, transferring the resulting solution to a 100mL stainless steel autoclave lined with polytetrafluoroethylene, heating at 180 ℃ for 12 hours, naturally cooling to room temperature, centrifuging the product three times with distilled water and absolute ethanol, respectively, placing in an oven, drying at 60 ℃ for 12 hours, the total volume of the hydrothermal solvent for all samples being kept constant (60 mL).
Examples 3 to 6 the same procedure as in example 2 was followed, except that:
the reaction solution in Experimental example 3 was 45mL of water and 15mL of ethylenediamine;
the reaction solution in Experimental example 4 was 30mL of water and 30mL of ethylenediamine;
the reaction solution in Experimental example 5 was 15mL of water and 45mL of ethylenediamine;
the reaction solution in Experimental example 6 was 10mL of water and 50mL of ethylenediamine.
The particle size and morphology of the composite catalyst were characterized by scanning electron microscope (zeissGeminSEM 500), and it can be observed from FIG. 1 that the surface of the flower-ball-shaped structure with a size of about 0.5-1 μm is loaded with about 50-400nm of In (OH) 3 And (3) nanoparticles.
The composite catalyst was characterized by a transmission electron microscope (JEOLJEM-1400), and the In (OH) at about 50nm was observed from FIG. 2 as a transmission electron micrograph shown In FIG. 2 3 The nanoparticles were loaded on the surface of the flower spheres, which is consistent with the results of scanning electron microscopy.
The microscopic crystal structure of the sample was characterized by X-ray powder diffraction (XRD) on the obtained catalyst, and CdIn can be seen from FIG. 3 2 S 4 Is in an amorphous state, and the obtained CdIn 2 S 4 A new diffraction peak appears after the secondary solvothermal reaction, and In (OH) appears along with the increase of the proportion of the ethylenediamine In the mixed solution 3 The diffraction peak of (2) is gradually reduced, and the comparison shows that the new diffraction peak is In (OH) 3 (JCPDS85-1338)。
Experimental example 7
CdIn is mixed with 2 S 4 And In (OH) 3 /CdIn 2 S 4 Respectively performing visible light (lambda)>420 nm), the obtained hydrogen production activity data is shown in figure 4, and the activity test experiment steps are as follows:
s1, performing photocatalytic hydrogen production in a quartz glass reactor, and detecting the photocatalytic hydrogen production on a gas chromatograph;
s2, dispersing 30mg of catalyst in a quartz glass reactor containing 100mL of 10v/v% triethanolamine aqueous solution, opening a condensed water and a stirrer switch after ultrasonic dispersion, and introducing argon for 15min before illumination to drive off the catalyst in the reaction systemAir, 300W xenon lamp equipped with filter for reactor: (>420nm, PerfectLightPLS-SXE300 + Beijing) vertical illumination;
s3, H released in the reaction process 2 The quantity is detected by a gas chromatograph and the thermal conductivity detector is measured by N 2 As a carrier gas, samples were taken every hour after the start of the reaction, and the reaction was stopped after five measurements.
Experimental example 8
The catalyst stability experiment is the same as that in experimental example 7, after 5 hours of photocatalytic reaction, 3mL of triethanolamine is added, after argon is introduced into the system for 15 minutes, a new activity test experiment is restarted, and four rounds of cycle tests are performed in total.
According to the activity data of photocatalytic hydrogen production, the formed In (OH) 3 /CdIn 2 S 4 The heterojunction structure can improve the activity of photocatalytic hydrogen production, the visible light catalytic activity of the composite catalyst can reach 1.28mmol/g/h to the maximum, and is about pure CdIn 2 S 4 4.5 times of the total weight of the product.
It should be noted that, in this document, relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (5)
1. Simple and convenient solvent thermal method for preparing In (OH) 3 /CdIn 2 S 4 A composite catalyst characterized by: comprises the following materials: cdIn 2 S 4 Ethylene diamine and aqueous solutions.
2. The simple solvothermal method for producing In (OH) according to claim 1 3 /CdIn 2 S 4 A composite catalyst characterized by: the CdIn is 2 S 4 As a base material and an indium source.
3. The simple solvothermal method for producing In (OH) according to claim 2 3 /CdIn 2 S 4 A composite catalyst characterized by: the CdIn is 2 S 4 The preparation method specifically comprises the following steps of ultrasonically dissolving 0.6665g of cadmium acetate dihydrate, 3.0085g of indium nitrate tetrahydrate and 6.0150g of glutathione until the solution is clear, pouring the solution into a hydrothermal reaction kettle, placing the hydrothermal reaction kettle into an oven, heating to 140 ℃ for reaction for 5 hours, naturally cooling to room temperature after the reaction is finished, pouring the reacted solution into a 100mL centrifuge tube, centrifugally washing the solution for three times by using water and ethanol, placing the centrifugally washed solution in a 60 ℃ drying environment, and placing the centrifugally washed solution for 12 hours, so that the preparation method is obtained.
4. The simple solvothermal method for producing In (OH) according to claim 1 3 /CdIn 2 S 4 A composite catalyst characterized by: the volume ratio of the ethylenediamine to the aqueous solution is a, b, c, d and e respectively, wherein a is 5:1 (water/ethylenediamine); b is 3:1 (water/ethylenediamine); c is 1:1 (water/ethylenediamine); d is 1:3 (water/ethylene diamine); and e is 1:5 (water/ethylenediamine).
5. Simple and convenient solvent-thermal method for preparing In (OH) 3 /CdIn 2 S 4 The preparation method of the composite catalyst is characterized by comprising the following steps:
s1, dispersing 0.2g of CdIn in ethylene diamine and water solution with different volume ratios of a, b, c, d and e respectively 2 S 4 ;
S2, respectively obtaining a proportion sample In (OH) 3 /CdIn 2 S 4 (ii) a b proportional sample In (OH) 3 /CdIn 2 S 4 (ii) a c proportional sample In (OH) 3 /CdIn 2 S 4 (ii) a d proportion sample In (OH) 3 /CdIn 2 S 4 And e proportion of sample In (OH) 3 /CdIn 2 S 4 ;
S3, respectively carrying out ultrasonic treatment on the five samples a, b, c, d and e for 15min, pouring the solution into a hydrothermal reaction kettle, placing the hydrothermal reaction kettle In an oven, heating to 180 ℃, reacting for 12 hours, naturally cooling to room temperature, washing the product with water and ethanol In a centrifugal manner for three times, and drying at 60 ℃ for 12 hours to obtain a product In (OH) 3 /CdIn 2 S 4 。
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CN109833885A (en) * | 2017-11-29 | 2019-06-04 | 张东军 | A kind of CdIn2S4The preparation method of catalyst |
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