CN113413920A - Single metal In2S3Application of/In-MOF semiconductor material In photolysis of water to produce hydrogen - Google Patents
Single metal In2S3Application of/In-MOF semiconductor material In photolysis of water to produce hydrogen Download PDFInfo
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- 239000013346 indium-based metal-organic framework Substances 0.000 title claims abstract description 56
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 27
- 239000001257 hydrogen Substances 0.000 title claims abstract description 27
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 239000004065 semiconductor Substances 0.000 title claims abstract description 22
- 239000000463 material Substances 0.000 title claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 14
- 239000002184 metal Substances 0.000 title claims abstract description 14
- 238000006303 photolysis reaction Methods 0.000 title claims abstract description 5
- 230000015843 photosynthesis, light reaction Effects 0.000 title claims abstract description 5
- 239000011941 photocatalyst Substances 0.000 claims abstract description 14
- 238000002360 preparation method Methods 0.000 claims abstract description 13
- 239000002131 composite material Substances 0.000 claims abstract description 12
- 239000008367 deionised water Substances 0.000 claims abstract description 8
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims description 28
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- YZZFBYAKINKKFM-UHFFFAOYSA-N dinitrooxyindiganyl nitrate;hydrate Chemical compound O.[In+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YZZFBYAKINKKFM-UHFFFAOYSA-N 0.000 claims description 12
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 7
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 7
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 7
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 4
- 238000009210 therapy by ultrasound Methods 0.000 claims description 4
- 238000004817 gas chromatography Methods 0.000 claims description 3
- 238000005286 illumination Methods 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 238000010276 construction Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- GKCNVZWZCYIBPR-UHFFFAOYSA-N sulfanylideneindium Chemical compound [In]=S GKCNVZWZCYIBPR-UHFFFAOYSA-N 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims 1
- 238000005086 pumping Methods 0.000 claims 1
- 239000002994 raw material Substances 0.000 claims 1
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- 239000000779 smoke Substances 0.000 abstract 1
- 239000002699 waste material Substances 0.000 abstract 1
- 230000001699 photocatalysis Effects 0.000 description 11
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000003917 TEM image Methods 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000002905 metal composite material Substances 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000002803 fossil fuel Substances 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 2
- 239000012621 metal-organic framework Substances 0.000 description 2
- 238000013032 photocatalytic reaction Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000004577 artificial photosynthesis Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000004770 chalcogenides Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
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- 238000013329 compounding Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- LKRFCKCBYVZXTC-UHFFFAOYSA-N dinitrooxyindiganyl nitrate Chemical compound [In+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O LKRFCKCBYVZXTC-UHFFFAOYSA-N 0.000 description 1
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- 238000003837 high-temperature calcination Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
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- 150000004767 nitrides Chemical class 0.000 description 1
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- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
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- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/30—Complexes comprising metals of Group III (IIIA or IIIB) as the central metal
- B01J2531/33—Indium
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The invention discloses a single metal In2S3The application of the/In-MOF semiconductor material In the photolysis of water to produce hydrogen. Adopts a single metal semiconductor composite material In2S3the/In-MOF is a photocatalyst, and hydrogen is prepared under the irradiation of visible light. Compared with the prior art, the invention has the advantages that: (1) the preparation process only uses a hydrothermal method and an oil bath method, the operation process is simple, the preparation is convenient, and the requirement on equipment is low; (2) in of prepared single metal heterojunction2S3Compared with other catalytic materials which are reported In the prior publication, the In-MOF composite photocatalyst has obviously improved catalytic effect; (3) the reaction adopts deionized water and DMF as reaction media, the process is safe and stable, no open fire or smoke is generated, no three-waste discharge is generated, the environment is friendly, and the industrial amplification is easy.
Description
Technical Field
The invention relates to a single metal In2S3An application method of an In-MOF semiconductor photocatalytic material for preparing hydrogen by decomposing water under the irradiation of visible light belongs to the field of novel semiconductor materials and new energy.
Background
At present, under the influence of the high-speed development of the industry in China and the consumption of fossil fuels, the problem of novel energy supply is urgently needed to be solved, meanwhile, the conversion of solar energy into electric energy is one of the main scientific challenges facing researchers, semiconductor materials can be used for the energy conversion, and on the basis, the preparation of a novel pollution-free energy source instead of fossil fuels becomes a primary target. Visible light can be converted to chemical energy by catalyzing the formation of chemical bonds. One of the research points of this method is photocatalytic decomposition of water to generate hydrogen and oxygen from water; photocatalytic reduction of carbon dioxide to carbon-based chemicals is also one of the focus of research and development. The semiconductor photocatalyst is utilized to carry out artificial photosynthesis to produce clean chemical fuels such as hydrogen and the like, and as a promising approach for meeting the global renewable energy supply requirement and reducing the harmful effects of fossil fuel combustion, the semiconductor photocatalyst is widely concerned, and researchers prepare a semiconductor photocatalytic material (In) on the basis of indium oxide through continuous research and exploration2O3/g-C3N4) The method is used for preparing the novel pollution-free energy (Cao S-W, Liu X-F, Yuan Y-P, Zhang Z-Y, Liao Y-S, Fan J, et al Solar-to-fuels conversion over In) of hydrogen under visible light2O3/g-C3N4hybrid photocatalysts. Applied catalysts B: environmental 2014; 147: 940-6.) and semiconductor photocatalytic material (In)2O3/In2S3) For the photoelectrochemical production of hydrogen (Li H, Chen C, Huang X, Leng Y, Hou M, Xiao X, et al, catalysis of In2O3/In2S3core-shell nanocubes for enhanced optoelectronic performance, Journal of Power sources 2014, 247: 915-9). The hydrogen production by photocatalytic decomposition of water by visible light energy has the advantages of reproducibility, environmental protection and the like, is considered to be a promising strategy for solving the increasingly serious energy crisis, and accords with the strategic direction of carbon peak reaching and carbon neutralization in the world.
Various semiconductor photocatalysts, including metal oxides, chalcogenides, nitrides and metal organic frameworks, have found wide application in various photocatalytic reactions. Finally, theThe formation of semiconductor heterojunctions has been found to be a common and efficient method. Due to the good matching energy band and good photoelectric property, the charge transfer efficiency and the photoelectric conversion efficiency can be improved. Therefore, we need to further explore a more cost-effective photocatalyst. The semiconductor composite material containing two or three different materials or phases can effectively promote charge separation and carrier transfer, and greatly improve the efficiency of photocatalysis and photoelectrochemistry, but the preparation, separation, post-treatment, recovery and the like of the double or multi-metal composite material have certain difficulties. Therefore, the invention adopts an oil bath-hydrothermal method with simple and convenient operation to prepare In2S3And In-MOF single metal composite semiconductor material, In is constructed2S3the/In-MOF heterojunction composite photocatalyst is applied to hydrogen production by natural photocatalysis.
Disclosure of Invention
The object of the present invention is to provide an In2S3And a new application method of the In-MOF single metal composite semiconductor material In the preparation of hydrogen. By using In2S3Adding the/In-MOF single metal composite semiconductor material serving as a photocatalyst into 10wt% triethanolamine aqueous solution, performing ultrasonic or stirring dispersion for 30 min, transferring the solution to a hydrogen production device, and preparing hydrogen under the illumination condition.
The technical solution for realizing the aim of the invention is that the prepared In-MOF precursor and indium nitrate hydrate In (NO)3)3·4H2O and thioacetamide are completed by means of a hydrothermal method and the like, wherein the monometallic indium sulfide semiconductor material In2S3The specific steps of the construction of the/In-MOF are as follows:
step 1) preparation of In-MOF: adding terephthalic acid and indium nitrate hydrate In (NO) into N, N-dimethylformamide3)3·4H2And O, putting the mixture into an ultrasonic cleaner for ultrasonic treatment for 30 min to fully mix, and heating the mixture to 120 ℃ in an oil bath for 1 h after uniform stirring. Naturally cooling to room temperature along with the oil bath pan, standing for layering, absorbing most of clear liquid, centrifuging at 3000 rpm, washing with DMF for the first time and ethanol for the second time to obtain white precipitate, and vacuum drying at 60 deg.C for 2 hr to obtain target intermediateWherein In (NO) is a hydrate of terephthalic acid and indium nitrate3)3·4H2The mass ratio of O is 1: 1;
step 2) In2S3Preparing an In-MOF composite photocatalyst: the In-MOF obtained In the step 1, indium nitrate hydrate In (NO)3)3·4H2Dissolving O and thioacetamide In deionized water, ultrasonically treating the mixture for 30 min to fully mix the O and thioacetamide, putting the mixture into a stainless steel hydrothermal reaction kettle, heating the mixture at 180 ℃ for 10 h to 12 h, cooling the mixture to room temperature, centrifuging the obtained mixed solution at 3000 rpm, respectively washing the mixed solution twice with deionized water and ethanol, and drying the mixed solution In vacuum at 60 ℃ for 2 h to obtain khaki In2S3In-MOF. In the experiment by changing indium nitrate hydrate InCl3·4H2The molar ratio of In to S is changed by feeding O and TAA, so as to synthesize a series of In with different proportions2S3In-MOF, where In: S is 1:1, 1:1.5, 1:2, 1:4, 1:6 respectively denoted as In2S3/In-MOF-1，In2S3/In-MOF-1.5，In2S3/In-MOF-2，In2S3/In-MOF-4，In2S3/In-MOF-6。
In of the invention2S3The mass ratio of the/In-MOF semiconductor material to the 10wt% triethanolamine aqueous solution is 1:2500, after the hydrogen production device extracts vacuum, the light is irradiated for a certain time, and the hydrogen production rate is calculated according to the peak area and the time point obtained by the gas chromatography.
The key technology of the technical solution for realizing the aim of the invention is as follows: firstly, preparing an In-MOF precursor by oil bath heating, and then reacting the precursor with indium nitrate hydrate In (NO)3)3·4H2Obtaining In of single metal heterojunction by O and thioacetamide In a hydrothermal reaction kettle2S3In-MOF composite photocatalyst (shown In attached figures 1-4), electrons excited by illumination of semiconductor In are quickly conducted out through a carbon skeleton In a heterojunction MOF structure to perform photocatalytic reaction, so that recombination of electrons and holes is effectively prevented, and catalytic activity is lost, and the performance of preparing hydrogen by photocatalysis is greatly improved.
Compared with the prior art, the invention has the advantages that: (1) The preparation process only uses common heating modes of a hydrothermal method and an oil bath method, complex processes such as high-temperature calcination in a muffle furnace and a tubular furnace, inert gas protection and the like are not needed, the operation process is simple, the preparation is convenient, and the requirement on equipment is low; (2) in of prepared single metal heterojunction2S3Compared with other single metal catalytic materials reported In the prior art, the In-MOF composite photocatalyst has the advantages that the catalytic effect is remarkably improved, the structural stability and the catalytic activity are good, and the In-MOF composite photocatalyst is close to or even superior to composite catalysts such as bimetallic catalysts and polymetallic catalysts; (3) deionized water and DMF are adopted as reaction media in the reaction, the whole reaction and post-treatment processes are safe and stable, the solvent can be recovered, and the method is environment-friendly and easy for industrial amplification.
Drawings
The invention has the following 11 drawings:
FIG. 1 shows a single metal In2S3/In-MOF、In2S3、In-MOF、In2S3The XRD diffraction pattern of the standard spectrum,
FIG. 2 is In2S3 (a) In-MOF, (b), In2S3One of the SEM pictures of/In-MOF (c),
FIG. 3 is In2S3 (a) In-MOF, (b), In2S3Second SEM picture of/In-MOF (c),
FIG. 4 is In2S3 (a) In-MOF, (b), In2S3Third SEM picture of/In-MOF (c),
FIG. 5 is In2S3One of the TEM images of the/In-MOF,
FIG. 6 is In2S3The second TEM image of the/In-MOF,
FIG. 7 is In2S3Third TEM image of/In-MOF,
FIG. 8 is In2S3Four of the TEM images of/In-MOF,
FIG. 9 is In2S3XPS survey of/In-MOF,
figure 10 is one of the rate plots for photocatalytic hydrogen production,
FIG. 11 is a second graph of the rate of photocatalytic hydrogen production.
Detailed Description
The following examples further illustrate the invention in order to provide a better understanding of the invention. The examples do not limit the scope of the invention in any way. Modifications and adaptations of the present invention within the scope of the claims may occur to those skilled in the art and are intended to be within the scope and spirit of the present invention.
Example 1
Preparation of In-MOF: to 150 ml of N, N-dimethylformamide were added 1.2 g of terephthalic acid and 1.2 g of indium nitrate hydrate In (NO)3)3·xH2And O, putting the mixture into an ultrasonic cleaner for ultrasonic treatment for 30 min to fully mix, and heating the mixture to 120 ℃ in an oil bath for 1 h after uniform stirring. After naturally cooling to room temperature with the oil bath and standing for layering, most of the supernatant was decanted, then centrifuged (3000 rpm) and washed once with DMF and twice with ethanol to give a white precipitate. Finally, drying under vacuum at 60 ℃ for 2 h gave a white powder with a yield of about 0.8 g.
Example 2
In2S3Preparation of In-MOF: 0.1190 g of In-MOF, a certain amount of indium nitrate hydrate InCl3·4H2O and 0.02910 g TAA were dissolved in 20 ml deionized water. The mixture is subjected to ultrasonic treatment for 30 min to be fully mixed, and after the mixture is magnetically stirred uniformly, the mixture is placed into a 50 ml stainless steel reaction kettle, heated for 10 h to 12 h at 180 ℃, and then cooled to room temperature. The above solution was centrifuged (3000 rpm) and washed twice each with deionized water and ethanol. Finally vacuum drying at 60 ℃ for 2 h to obtain khaki In2S3the/In-MOF amounted to about 0.12 g. Preparation of pure In by the same preparation method without adding In-MOF2S3Blank comparison for precursors.
By changing indium nitrate hydrate InCl3·4H2The feeding of O and TAA is carried out to change the atomic mole ratio of In and S, thereby synthesizing a series of In with different proportions2S3The optimized In to S atomic molar ratios of 1:1, 1:1.5, 1:2, 1:4 and 1:6 are selected and respectively marked as In-MOF2S3/In-MOF-1，In2S3/In-MOF-1.5，In2S3/In-MOF-2，In2S3/In-MOF-4，In2S3In-MOF-6, In different proportions2S3the/In-MOF products were all earthy yellow powders.
40 mg of In prepared In example 2 were taken2S3Adding the/In-MOF into 50 mL of 10wt% triethanolamine aqueous solution, performing ultrasonic dispersion for 30 min, adding 50 mL of 10wt% triethanolamine aqueous solution, uniformly mixing, transferring to a hydrogen production reaction generating device, keeping the device closed, starting a light source after vacuum extraction, automatically sampling and recording a peak area every 30 min, continuously illuminating for 3 h, calculating a hydrogen production rate according to the peak area and a time point obtained by gas chromatography, wherein the data is shown In figure 10, and In order to compare the effects before and after compounding, the composite material In2S3In-MOF with In2S3FIG. 11 shows the results of comparison of In-MOF.
Claims (2)
1. Single metal In2S3The application of the/In-MOF material In photolysis water to produce hydrogen is characterized In that: adopts a single metal semiconductor composite material In2S3the/In-MOF is a photocatalyst, is added into 10wt% triethanolamine aqueous solution, is dispersed for 30 min by ultrasonic wave or stirring, is transferred into a hydrogen production device, and is used for preparing hydrogen under the condition of simulating natural illumination, wherein, the single metal indium sulfide semiconductor material In2S3The specific steps of the construction of the/In-MOF are as follows:
step 1) preparation of In-MOF: adding terephthalic acid and indium nitrate hydrate In (NO) into N, N-dimethylformamide3)3·4H2O, then putting the mixture into an ultrasonic cleaner for ultrasonic treatment for 30 min to fully mix the mixture, heating the mixture In an oil bath to 120 ℃ after stirring uniformly, maintaining the temperature for 1 h, naturally cooling the mixture to room temperature along with an oil bath pan, standing the mixture for layering, absorbing most of clear liquid, centrifuging the mixture at the rotating speed of 3000 rpm, washing the mixture with DMF (dimethyl formamide) and washing the mixture with ethanol twice to obtain white precipitate, and drying the white precipitate In vacuum at the temperature of 60 ℃ for 2 h to obtain a target intermediate, wherein terephthalic acid and indium nitrate hydrate In (NO) are used as raw materials3)3·4H2The mass ratio of O is 1: 1;
step 2) In2S3In-MOF composite photocatalystPreparation of the reagent: the In-MOF obtained In the step 1, indium nitrate hydrate In (NO)3)3·4H2Dissolving O and thioacetamide In deionized water, ultrasonically treating the mixture for 30 min to fully mix the O and thioacetamide, putting the mixture into a stainless steel hydrothermal reaction kettle, heating the mixture at 180 ℃ for 10 h to 12 h, cooling the mixture to room temperature, centrifuging the obtained mixed solution at 3000 rpm, washing the mixed solution twice with deionized water and ethanol respectively, and drying the mixed solution In vacuum at 60 ℃ for 2 h to obtain In2S3In-MOF by changing indium nitrate hydrate In (NO)3)3·xH2Material ratio of O to thioacetamide to regulate In2S3In-MOF Material surface In2S3So that a series of In with different proportions can be obtained2S3/In-MOF。
2. Monometallic In according to claim 12S3The application of the/In-MOF material In photolysis water to produce hydrogen is characterized In that: single metal In2S3The mass ratio of the In-MOF to the 10wt% triethanolamine aqueous solution is 1:2500, the hydrogen production device is used for illuminating for a certain time after vacuum pumping, and the hydrogen production rate is calculated according to the peak area and the time point obtained by gas chromatography.
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| CN114345418A (en) * | 2021-12-27 | 2022-04-15 | 东北大学 | Preparation method and application of hollow tubular MIL-68(In)/In2S3/ZnIn2S4 photocatalyst |
| CN116393145A (en) * | 2023-02-27 | 2023-07-07 | 广东石油化工学院 | Ga doped In 2 S 3 Preparation method and application of catalyst |
| CN116510765A (en) * | 2023-04-20 | 2023-08-01 | 广东工业大学 | A kind of photothermal catalyst and its preparation method and application |
| CN119406429A (en) * | 2024-10-09 | 2025-02-11 | 华北水利水电大学 | Preparation method and application of MOF-derived In2S3/ZnIn2S4 composite material for photocatalytic hydrogen evolution |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114345418A (en) * | 2021-12-27 | 2022-04-15 | 东北大学 | Preparation method and application of hollow tubular MIL-68(In)/In2S3/ZnIn2S4 photocatalyst |
| CN116393145A (en) * | 2023-02-27 | 2023-07-07 | 广东石油化工学院 | Ga doped In 2 S 3 Preparation method and application of catalyst |
| CN116393145B (en) * | 2023-02-27 | 2024-04-26 | 广东石油化工学院 | Ga doped In2S3Preparation method and application of catalyst |
| CN116510765A (en) * | 2023-04-20 | 2023-08-01 | 广东工业大学 | A kind of photothermal catalyst and its preparation method and application |
| CN119406429A (en) * | 2024-10-09 | 2025-02-11 | 华北水利水电大学 | Preparation method and application of MOF-derived In2S3/ZnIn2S4 composite material for photocatalytic hydrogen evolution |
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