CN110054212B - Compound NH4GaS2And preparation method and application thereof - Google Patents
Compound NH4GaS2And preparation method and application thereof Download PDFInfo
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 229910005541 GaS2 Inorganic materials 0.000 claims abstract description 46
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 24
- 230000001699 photocatalysis Effects 0.000 claims abstract description 18
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 claims abstract description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 11
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910001195 gallium oxide Inorganic materials 0.000 claims abstract description 11
- 239000001257 hydrogen Substances 0.000 claims abstract description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 11
- 239000013078 crystal Substances 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 8
- 238000007789 sealing Methods 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- -1 polytetrafluoroethylene Polymers 0.000 claims description 15
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 14
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 7
- 239000012298 atmosphere Substances 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 abstract description 19
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 abstract description 17
- 230000000694 effects Effects 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 230000002194 synthesizing effect Effects 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- FGMHLDAQUBQLDU-UHFFFAOYSA-N oxalic acid;thiourea Chemical compound NC(N)=S.OC(=O)C(O)=O FGMHLDAQUBQLDU-UHFFFAOYSA-N 0.000 abstract description 2
- 150000004763 sulfides Chemical class 0.000 abstract description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 18
- 238000005303 weighing Methods 0.000 description 9
- 239000000843 powder Substances 0.000 description 7
- 230000004580 weight loss Effects 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 229910052593 corundum Inorganic materials 0.000 description 4
- 239000010431 corundum Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 229910005228 Ga2S3 Inorganic materials 0.000 description 3
- 239000005083 Zinc sulfide Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 229910003437 indium oxide Inorganic materials 0.000 description 3
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 229910052984 zinc sulfide Inorganic materials 0.000 description 3
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical group [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 3
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 2
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 150000002259 gallium compounds Chemical class 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000004729 solvothermal method Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000012795 verification Methods 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 102100021202 Desmocollin-1 Human genes 0.000 description 1
- 229910002601 GaN Inorganic materials 0.000 description 1
- 229910005540 GaP Inorganic materials 0.000 description 1
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 description 1
- 101000968043 Homo sapiens Desmocollin-1 Proteins 0.000 description 1
- 101000880960 Homo sapiens Desmocollin-3 Proteins 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000004455 differential thermal analysis Methods 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- HZXMRANICFIONG-UHFFFAOYSA-N gallium phosphide Chemical compound [Ga]#P HZXMRANICFIONG-UHFFFAOYSA-N 0.000 description 1
- BVSHTEBQPBBCFT-UHFFFAOYSA-N gallium(iii) sulfide Chemical compound [S-2].[S-2].[S-2].[Ga+3].[Ga+3] BVSHTEBQPBBCFT-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- GKCNVZWZCYIBPR-UHFFFAOYSA-N sulfanylideneindium Chemical compound [In]=S GKCNVZWZCYIBPR-UHFFFAOYSA-N 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 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
- B01J27/24—Nitrogen compounds
-
- 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G15/00—Compounds of gallium, indium or thallium
- C01G15/006—Compounds containing, besides gallium, indium, or thallium, two or more other elements, with the exception of oxygen or hydrogen
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a compound NH4GaS2The preparation method and the application thereof comprise the following steps: uniformly mixing gallium oxide and thiourea, adding the mixture into a reaction kettle, adding oxalic acid, sealing the reaction kettle, heating the reaction kettle for reaction, and obtaining white granular crystals, namely the compound NH4GaS2. The invention adopts a simple thiourea oxalate method to synthesize a compound NH4GaS2The method is simple and easy to implement, does not need to be carried out under harsh vacuum reaction conditions, has cheap and easily-obtained raw materials, low cost and low energy consumption, and is easy for industrial production. The compound has good photocatalytic hydrogen production activity under simulated sunlight, can be used as a raw material for synthesizing other gallium-containing sulfides, and has good application prospect.
Description
Technical Field
The invention relates to the technical field of sulfide preparation, in particular to a compound NH4GaS2And a preparation method and application thereof.
Background
Gallium is a low-melting point and high-boiling point rare dispersion metal and has the reputation of the ridge beam in the electronic industry. Gallium compounds are excellent semiconductor materials and widely used in the optoelectronics industry and the microwave communications industry, for example, gallium nitride, gallium arsenide, gallium phosphide, etc. are commonly used semiconductors. Gallium compounds are also used in the manufacture of solar cells, such as gallium arsenide iii-v solar cells, which have good thermal and radiation resistance and very high photoelectric conversion efficiency. Originally, the production and use costs are very high, and the method is often applied to the fields of aerospace and military industry. In recent years, gallium-containing compounds have also received attention for use in photocatalysts, such as CuIn1-xGaxSe2，CuIn1-xGaxS2，ZnGa2S4，CuGaS2And the like. Therefore, the research on the novel gallium-containing sulfide has important research significance.
At present, the preparation of gallium-containing sulfide also becomes a research hotspot, for example, Jang Bo Shim and the like successfully synthesize CuInSe by taking acetic acid as a solvent and adopting a solvothermal method2Film, study of crystallinity and particle size of reaction productThe degree increases with increasing reaction temperature and time (J.B.Shim, et al.Hydrothennal synthesis of CuInSe)2nanoparticles in acetic acid[J]Journal of Physics and Chemistry of Solids,2013,74(6): 867-; ben Rabeh et al successfully synthesized CuInS on heated glass substrate by thermal evaporation method under vacuum condition2Films and their structural characteristics were studied (Rabch M B, Khcdmi N, Fcxlha M A, et al. the Effect of the Thickness on Optical Band Gap and N-type G) and the conductivity of CuInS2 Thin Films Annealed in Air Atmosphere[J]Energy Procedia,2014,44: 52-60). However, the above methods often require complicated steps of solvothermal methods or high vacuum conditions during the synthesis.
The photocatalytic material can generate photo-generated electron hole pairs under the excitation of certain energy light, and carriers migrate to the surface of the material and can undergo redox reaction with surface adsorbed substances. By utilizing the characteristic, the photocatalytic material can be applied to the fields of organic pollutant degradation, water photolysis hydrogen production and the like. However, the application of the photocatalytic material still faces many problems, such as the optimal excitation light of the photocatalytic material is sunlight, but most of the photocatalytic material only responds to ultraviolet light with a small proportion in the solar spectrum, so that the sunlight utilization rate is low; many of the photocatalytic materials reported at present contain precious metal components, which results in higher preparation cost of the photocatalytic materials.
Disclosure of Invention
In view of the above-mentioned disadvantages of the prior art, the present invention provides a compound NH4GaS2And the variety of the sulfide containing gallium is enriched.
The invention also provides a compound NH4GaS2The preparation method solves the problems of complex operation, high energy consumption and the like of the existing preparation method of the sulfide containing gallium.
The invention also provides a compound NH4GaS2The photocatalytic material can be used for realizing hydrogen production by water decomposition by utilizing simulated sunlight.
The invention adopts the following technical scheme: compound NH4GaS2The preparation method comprises the following steps: uniformly mixing gallium oxide and thiourea, adding the mixture into a reaction kettle, adding oxalic acid, sealing the reaction kettle, heating the reaction kettle for reaction, and obtaining white granular crystals, namely the compound NH4GaS2。
Furthermore, the molar ratio of Ga to S in the gallium oxide and the thiourea is 1: 10-30.
Furthermore, the molar ratio of the oxalic acid to the gallium oxide is 5-30: 1.
Further, the reaction temperature is 230-250 ℃, and the reaction time is 3-7 d.
Further, the lining material of the reaction kettle is polytetrafluoroethylene.
Compound NH4GaS2Prepared according to the method.
Compound NH4GaS2The application in photocatalytic hydrogen production.
Compound NH4GaS2And the application of the thermal decomposition product thereof in the synthesis of the sulfide containing gallium; the thermal decomposition product is Ga2S3。
Further, the gallium-containing sulfide is ZnGa2S4Or CuGaS2。
Further, weighing NH4GaS2Or Ga2S3Then adding sulfide, then loading the sulfide into a corundum boat, and calcining the corundum boat for 2-4 hours at 600-800 ℃ in an inert gas atmosphere to obtain the gallium-containing sulfide; the sulfide is zinc sulfide or copper sulfide.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention synthesizes the compound NH by adopting a simple thiourea oxalate method for the first time4GaS2The method is simple and easy to implement, does not need to be carried out under harsh vacuum reaction conditions, has cheap and easily-obtained raw materials, low cost and low energy consumption, is easy for industrial production, provides a new idea for synthesizing the gallium-containing sulfide, and has good economic benefit.
2. The invention is preparedTo the compound NH4GaS2The gallium sulfide is a new sulfide, has white granular crystals and better stability, enriches the types of gallium sulfides, can prepare the gallium trisulfide through simple thermal decomposition reaction, finally becomes the gallium oxide, can be used as a raw material for the research of synthesizing gallium-containing sulfides or oxides, and has good application value.
3. Compound NH prepared by the invention4GaS2Has good photocatalytic hydrogen production activity under sunlight, and provides a novel low-cost photocatalytic material.
Drawings
FIG. 1 shows NH prepared4GaS2A photograph of the sample under an optical microscope;
FIG. 2 shows NH prepared4GaS2X-ray powder diffractogram of the sample;
FIG. 3 shows NH prepared4GaS2Thermogravimetric differential thermal profile of the sample;
FIG. 4 shows NH prepared4GaS2A graph of photocatalytic hydrogen production performance of the sample;
FIG. 5 is NH prepared according to the invention4GaS2An X-ray powder diffraction pattern of gallium sulfide obtained by thermal decomposition of the sample;
FIG. 6 is NH prepared according to the invention4GaS2Powder diffraction pattern of the final product gallium oxide from oxidation of the sample in air.
Detailed Description
The present invention will be described in further detail with reference to the following specific embodiments and the accompanying drawings.
Mono, compound NH4GaS2Preparation method of (1)
Example 1
1) Weighing 1mmol of indium oxide and 20mmol of thiourea, uniformly mixing, adding into 20mL of polytetrafluoroethylene lining after uniformly mixing, weighing 1.5g of oxalic acid, pouring into the polytetrafluoroethylene lining, sealing the polytetrafluoroethylene lining, and putting the lining into a stainless steel outer sleeve.
2) Lining the polytetrafluoroethylene in the step 1) with stainless steelPutting the steel jacket into an oven, reacting for 72h at 230 ℃, washing the product with distilled water after the reaction is finished, removing the unreacted soluble impurities to obtain white granular crystals, namely compound NH4GaS2。
Example 2
1) Weighing 1mmol of indium oxide and 15mmol of thiourea, uniformly mixing, adding into 20mL of polytetrafluoroethylene lining after uniformly mixing, weighing 2.0g of oxalic acid, pouring into the polytetrafluoroethylene lining, sealing the polytetrafluoroethylene lining, and putting the lining into a stainless steel outer sleeve.
2) Putting the polytetrafluoroethylene lining and the stainless steel outer sleeve in the step 1) into an oven, reacting for 120h at 240 ℃, washing the product with distilled water after the reaction is finished, removing the unreacted soluble impurities completely to obtain white granular crystals, namely compound NH4GaS2。
Example 3
1) Weighing 1mmol of indium oxide and 30mmol of thiourea, uniformly mixing, adding into 20mL of polytetrafluoroethylene lining after uniformly mixing, weighing 1.0g of oxalic acid, pouring into the polytetrafluoroethylene lining, sealing the polytetrafluoroethylene lining, and putting the lining into a stainless steel outer sleeve.
2) Putting the polytetrafluoroethylene lining and the stainless steel outer sleeve in the step 1) into an oven, reacting for 168 hours at 230 ℃, washing the product with distilled water after the reaction is finished, removing the unreacted soluble impurities completely to obtain white granular crystals, namely compound NH4GaS2。
Bis, compound NH4GaS2Detection and verification of
1. NH prepared in the above example4GaS2The sample was observed under an optical microscope, and the results are shown in FIG. 1.
As can be seen from the figure, the samples were enlarged 80 times to appear white granular crystals, and the large granular samples were stacked from the smaller plate-like samples.
2. NH prepared in the above example4GaS2After grinding the sample in a mortar into powder, the sample was tested using a PANalytical X' pert powder diffractometer, copper target
The operating voltage was 40kV and the operating current was 40mA, and the results are shown in FIG. 2.
As can be seen from fig. 2, this sample crystallized well. And the powder diffraction pattern is refined by TOPAS software, and the result shows that the crystallography parameters are as follows: monoclinic system, space group C2/C,
β＝99.69°，
the spectra fit well and therefore the diffractogram can be used as a reference standard for the phase.
3. NH prepared in the above example4GaS2The sample was subjected to thermogravimetric differential thermal analysis using a Mettler-Toledo TGA/DSC1 thermogravimetric differential thermal instrument, and the sample was warmed from room temperature to 800 ℃ at 10 ℃ per minute under air atmosphere, the results are shown in FIG. 3.
Wherein the compound NH4GaS2The weight loss chemical reaction during heating is as follows,
as can be seen from the figure, the sample lost weight in two stages. The weight loss in the first stage (200-400 ℃) is 21.5 percent, and the theoretical weight loss is 22.4 percent; the weight loss in the second stage (400-600 ℃) is 15.5%, the theoretical weight loss is 15.9%, and an endothermic peak is corresponded, which is caused by gallium sulfide oxidation. The total weight loss was 37.0%, based on NH4GaS2The principle of molecular formula (II) calculationThe theoretical weight loss is 38.3 percent, and is within a reasonable error range. Thus, the yellow granular crystal was determined to have a molecular formula of NH4GaS2Is correct.
4. Analysis of NH by powder diffraction4GaS2The products after thermal decomposition at 300 ℃ and 700 ℃ are respectively identified as gallium sulfide (shown in figure 5) and gallium oxide (shown in figure 6) by spectrogram verification; compared with an ICSD database, the powder diffraction patterns of gallium sulfide and gallium oxide are respectively consistent with the PDF card serial numbers 01-089-. Further confirms the compound NH obtained by the invention4GaS2The molecular formula (B) is correct.
III, compound NH4GaS2Application of
1. Using a CEL-SPH2N photocatalytic activity evaluation system with a 350W xenon lamp as a light source and methanol as a sacrificial agent, 0.1g of NH prepared in example 1 was added4GaS2The sample was added to a glass reactor containing 50mL of 20 vol% methanol solution. Before testing illumination, the reactor is vacuumized to ensure that the reaction test is carried out under anaerobic condition. For NH under simulated solar illumination4GaS2The photocatalytic hydrogen production performance of (2) was tested, and the results are shown in fig. 4.
The test result shows that the photocatalytic hydrogen production is prolonged along with the illumination time, and NH is generated under the simulated sunlight4GaS2The hydrogen production rate is about 10.0 mu mol/h/g. Description of NH prepared according to the invention4GaS2Has good photocatalytic hydrogen production activity under sunlight.
2. Weighing zinc sulfide and NH4GaS2Uniformly grinding Zn and Ga in a molar ratio of 1:2 in a mortar, loading into a corundum boat, and calcining at 650 ℃ for 2h in a tubular atmosphere furnace filled with nitrogen atmosphere to obtain ZnGa2S4And (3) sampling.
3. Weighing zinc sulfide and Ga2S3And indium sulfide, wherein the molar ratio of Zn to (Ga + In) is 1:2, the mixture is uniformly ground In a mortar, then the mixture is loaded into a corundum boat and calcined for 2 hours In a tubular atmosphere furnace with nitrogen atmosphere at the temperature of 700 ℃ to obtain ZnGa2-xInxS4(0<x<0.4) sample.
Finally, the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all of them should be covered in the claims of the present invention.
Claims (1)
1. Compound NH4GaS2The preparation method is characterized by comprising the following steps: uniformly mixing gallium oxide and thiourea, adding the mixture into a reaction kettle, adding oxalic acid, sealing the reaction kettle, heating the reaction kettle for reaction, and obtaining white granular crystals, namely the compound NH4GaS2；
Said compound NH4GaS2The method is used for photocatalytic hydrogen production by taking methanol as a sacrificial agent; under an air atmosphere, the compound NH4GaS2Ga is the product after thermal decomposition at 300 DEG C2S3Said compound NH4GaS2Ga is the product after thermal decomposition at 700 DEG C2O3；
The molar ratio of Ga to S in the gallium oxide and the thiourea is 1: 10-30;
the molar ratio of the oxalic acid to the gallium oxide is 5-30: 1;
the reaction temperature is 230-250 ℃, and the reaction time is 3-7 d;
the lining material of the reaction kettle is polytetrafluoroethylene.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910346089.XA CN110054212B (en) | 2019-04-26 | 2019-04-26 | Compound NH4GaS2And preparation method and application thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910346089.XA CN110054212B (en) | 2019-04-26 | 2019-04-26 | Compound NH4GaS2And preparation method and application thereof |
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| Publication Number | Publication Date |
|---|---|
| CN110054212A CN110054212A (en) | 2019-07-26 |
| CN110054212B true CN110054212B (en) | 2021-06-18 |
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