CN112958118B - Double sulfide composite material and preparation method and application thereof - Google Patents
Double sulfide composite material and preparation method and application thereof Download PDFInfo
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- CN112958118B CN112958118B CN202110276555.9A CN202110276555A CN112958118B CN 112958118 B CN112958118 B CN 112958118B CN 202110276555 A CN202110276555 A CN 202110276555A CN 112958118 B CN112958118 B CN 112958118B
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- 239000002131 composite material Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 title description 2
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 claims abstract description 40
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000001257 hydrogen Substances 0.000 claims abstract description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 24
- 230000001699 photocatalysis Effects 0.000 claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 52
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 42
- 238000001035 drying Methods 0.000 claims description 42
- 239000000243 solution Substances 0.000 claims description 42
- 238000006243 chemical reaction Methods 0.000 claims description 41
- 239000000463 material Substances 0.000 claims description 41
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 29
- 239000012266 salt solution Substances 0.000 claims description 28
- 238000005406 washing Methods 0.000 claims description 28
- OYFRNYNHAZOYNF-UHFFFAOYSA-N 2,5-dihydroxyterephthalic acid Chemical compound OC(=O)C1=CC(O)=C(C(O)=O)C=C1O OYFRNYNHAZOYNF-UHFFFAOYSA-N 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 21
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 20
- 238000001816 cooling Methods 0.000 claims description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 239000003446 ligand Substances 0.000 claims description 18
- 150000001661 cadmium Chemical class 0.000 claims description 16
- 150000002815 nickel Chemical class 0.000 claims description 16
- 229910052717 sulfur Inorganic materials 0.000 claims description 15
- 239000011593 sulfur Substances 0.000 claims description 15
- 238000001291 vacuum drying Methods 0.000 claims description 15
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 14
- 239000013384 organic framework Substances 0.000 claims description 14
- LHQLJMJLROMYRN-UHFFFAOYSA-L cadmium acetate Chemical compound [Cd+2].CC([O-])=O.CC([O-])=O LHQLJMJLROMYRN-UHFFFAOYSA-L 0.000 claims description 13
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 12
- 229940078494 nickel acetate Drugs 0.000 claims description 12
- -1 polytetrafluoroethylene Polymers 0.000 claims description 11
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 11
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- 238000010992 reflux Methods 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- 238000005119 centrifugation Methods 0.000 claims description 4
- 238000013508 migration Methods 0.000 abstract description 6
- 230000005012 migration Effects 0.000 abstract description 6
- 239000000969 carrier Substances 0.000 abstract description 5
- 238000000926 separation method Methods 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 2
- 150000003568 thioethers Chemical class 0.000 abstract 1
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 32
- 239000000203 mixture Substances 0.000 description 19
- 239000000725 suspension Substances 0.000 description 13
- 239000002244 precipitate Substances 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 7
- 229910052759 nickel Inorganic materials 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229910052793 cadmium Inorganic materials 0.000 description 4
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 230000006798 recombination Effects 0.000 description 4
- 238000005215 recombination Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 3
- 239000013110 organic ligand Substances 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000006862 quantum yield reaction Methods 0.000 description 3
- 238000004073 vulcanization Methods 0.000 description 3
- 229910052724 xenon Inorganic materials 0.000 description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 238000013507 mapping Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229910001453 nickel ion Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- 239000012922 MOF pore Substances 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
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000002003 electron diffraction Methods 0.000 description 1
- 238000002524 electron diffraction data Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000001453 impedance spectrum Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 238000000103 photoluminescence spectrum Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000000985 reflectance spectrum Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- B01J27/043—Sulfides with iron group metals or platinum group metals
-
- B01J35/33—
-
- 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
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
- B01J37/20—Sulfiding
-
- 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
- B01J37/30—Ion-exchange
-
- 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 provides a preparation method of a disulfide composite material, the disulfide composite material prepared by the preparation method and application of the disulfide composite material in photocatalytic hydrogen evolution. The invention obtains the disulfide composite material through coordination reaction-ion exchange-hydrothermal reaction, has simple preparation process and lower cost, and is easy for industrial application. In the disulfide composite material obtained by the preparation method, two sulfides have a tight combination interface to form a large number of p-n junctions, so that the separation and migration of photo-generated carriers are promoted, and the disulfide composite material has good catalytic hydrogen production performance under visible light. In addition, the obtained disulfide composite material has higher stability and reproducibility.
Description
Technical Field
The invention relates to the field of photocatalytic hydrogen evolution, in particular to a disulfide composite material and a preparation method and application thereof.
Background
Hydrogen is one of the cleanest, non-toxic fuels and is also a very important chemical feedstock in the chemical industry. However, industrial hydrogen is derived from hydrocarbons such as fossil fuel or biomass, consumes a large amount of energy, and causes serious environmental pollution. Solar-driven water splitting is considered to be a promising future hydrogen production process. The key to this process is the preparation of a highly efficient photocatalyst.
CdS has a suitable band position, which is considered one of the most suitable water splitting materials for visible light driving. However, problems of rapid recombination of photo-induced carriers, limited photo-response, and severe photo-corrosion greatly affect the efficiency and stability of photocatalysis. NiS is a readily available promoter that is well suited to enhance the photocatalytic performance of CdS. However, in the current research, the NiS particles are only loaded on the surface of CdS, and the photocatalysis is greatly affected due to the defect that CdS is easy to fall off.
Therefore, how to synthesize a tighter heterojunction between CdS and NiS remains a great challenge, and no more sophisticated solution exists at present.
Disclosure of Invention
The invention aims to provide a disulfide composite material, and a preparation method and application thereof. The Ni and Cd in the bimetallic framework material obtained by adopting the preparation method provided by the invention are well mixed, so that a compact p-n junction can be formed in the composite material obtained after in-situ vulcanization, the migration of carriers and the photocatalytic hydrogen production process are greatly promoted, and the photocatalytic hydrogen evolution performance of the composite material is effectively improved.
In order to achieve the above object, the present invention provides a method for preparing a disulfide composite material, comprising the steps of: (1) Mixing a certain amount of nickel salt solution with a certain amount of ligand solution, carrying out oil bath reflux reaction at a certain temperature, cooling to room temperature after reacting for a certain time, and obtaining a nickel metal organic framework material through centrifugation, washing and drying; (2) Dispersing a certain amount of the nickel metal organic framework material into a certain amount of cadmium salt solution, uniformly stirring, reacting for a certain time at a certain temperature, cooling to room temperature, centrifuging, washing and drying to obtain a bimetal organic framework material; (3) Dispersing a certain amount of the bimetal organic framework material into a certain amount of sulfur-containing organic solution, uniformly stirring, reacting for a certain time at a certain temperature, cooling to room temperature, and centrifuging, washing and drying to obtain the disulfide composite material.
Preferably, in step (1), the nickel salt solution is prepared by dissolving a nickel salt in deionized water, and the ligand solution is prepared by dissolving a ligand material in deionized water.
Preferably, the nickel salt comprises one or more of nickel acetate, nickel nitrate, nickel chloride, and the ligand material comprises one or more of 2, 5-dihydroxyterephthalic acid, ethanol, N-dimethylformamide, and tetrahydrofuran.
More preferably, the nickel salt is nickel acetate; the ligand material is 2, 5-dihydroxyterephthalic acid (H) 4 DOBDC). Wherein nickel acetate facilitates better dissolution of the ligand material.
Preferably, the mass ratio of the nickel salt to the ligand material is (5-10): 2-4. The utilization rate of the metal salt of the material synthesized by the proportion is up to 91.6 percent.
Preferably, in the step (1), the reaction temperature of the oil bath reflux reaction is 80-100 ℃ and the reaction time is 1-2h; the washing is to adopt deionized water and methanol to wash at least twice respectively; the drying is vacuum drying, the drying temperature is 70-80 ℃, and the drying time is 8-10h. In the step (1), nickel acetate and 2, 5-dihydroxyterephthalic acid undergo a coordination reaction, in the reaction process, acetate ions in the aqueous solution deprotonate the 2, 5-dihydroxyterephthalic acid, so that the nickel acetate and the 2, 5-dihydroxyterephthalic acid are well dissolved in a reaction solution, carboxylic acid groups at two end chains of a ligand respectively form ionic bond coordination with nickel ions, each nickel ion respectively coordinates with five oxygen atoms, and finally a porous nano material with a one-dimensional channel is formed, so that the nickel metal organic framework material (MOF-Ni) is obtained.
Preferably, in step (2), the cadmium salt solution is prepared from cadmium acetate dissolved in water, ethanol, or DMF.
More preferably, in step (2), the cadmium salt solution is prepared from cadmium acetate dissolved in DMF. According to the invention, in the step (2), cadmium acetate and DMF are adopted to prepare a cadmium salt solution, the solubility of cadmium acetate in DMF is high, and the cadmium salt solution with higher concentration is suitable for preparation, so that cadmium ions can enter the nickel metal organic framework material to replace part of nickel metal, and the bimetallic organic framework material is obtained.
Preferably, the mass ratio of the cadmium acetate to the nickel metal organic framework material is (10-20) (1.5-2), and cadmium ions with a higher proportion are favorable for entering the nickel metal organic framework material to replace part of nickel metal, so that the bimetal organic framework material is obtained.
Preferably, in the step (2), the reaction temperature is 130-150 ℃ and the reaction time is 6-8 hours, and the reaction is carried out in a polytetrafluoroethylene reactor; the washing is to adopt DMF and ethanol to wash at least twice respectively; the drying is vacuum drying, the drying temperature is 70-80 ℃, and the drying time is 8-10h. According to the invention, in the step (2), the nickel metal organic framework material is dispersed in a high-concentration cadmium salt solution, cadmium ions continuously enter MOF pore channels, nickel oxygen breaks bonds, cadmium replaces part of nickel, namely, the cadmium ions are inserted into MOF-Ni obtained in the step (1) through ion exchange, so that a bimetal organic framework material (MOF-Ni/Cd) is obtained, and Ni and Cd in the MOF-Ni/Cd are well mixed.
Preferably, in step (3), the sulfur-containing organic solution is prepared from thioacetamide or thiourea in ethanol.
Preferably, the sulfur-containing organic solution is prepared by dissolving thioacetamide in ethanol, wherein the mass ratio of the thioacetamide to the bimetallic organic framework material is (4-5): 1. The thioacetamide has higher quality and is favorable for complete vulcanization in the reaction process.
Preferably, in the step (3), the reaction temperature is 130-150 ℃ and the reaction time is 6-8h; the washing is carried out for 3-5 times by adopting ethanol solution; the drying is vacuum drying, the drying temperature is 70-80 ℃, and the drying time is 8-10h.
Preferably, in step (3), the reaction is carried out under solvothermal conditions in a polytetrafluoroethylene reactor. According to the invention, step (3) is used for synthesizing the CdS@NiS composite material through simple solvothermal treatment, wherein the boiling point of ethanol is low, a high-pressure activated reactant is generated in a reaction kettle, and the vulcanization reaction is easier to carry out; thioacetamide is decomposed at high temperature to produce S 2- Ion, S of high concentration 2- Continuously enter the bimetallic organic framework material to form S 2- Compared with oxygen, the catalyst has stronger bonding capability, so that a metal-oxygen bond is broken, a metal-sulfur bond is established, a CdS@NiS composite material is formed, a compact p-n junction is formed in the composite material, the migration of carriers and the photocatalytic hydrogen production process are greatly promoted, and the photocatalytic hydrogen evolution performance of the composite material is effectively improved.
The invention also provides the disulfide composite material prepared by the preparation method. The disulfide composite material prepared by the preparation method disclosed by the invention has the advantages that CdS and NiS are uniformly distributed in the composite material to form a large number of compact p-n heterojunction interfaces, so that separation and migration of holes and electrons are greatly promoted, and the photocatalytic hydrogen evolution performance of the composite material is effectively improved.
The invention also provides application of the disulfide composite material in photocatalytic hydrogen evolution. The disulfide composite material has higher photocatalytic hydrogen evolution rate; at 450nm, the apparent quantum efficiency is as high as 13.23%; shows good photocatalytic recovery under visible light.
The invention obtains the disulfide composite material through coordination reaction-ion exchange-hydrothermal reaction, has simple preparation process and lower cost, and is easy for industrial application. In the disulfide composite material obtained by the preparation method, two sulfides have a tight combination interface to form a large number of p-n junctions, so that the separation and migration of photo-generated carriers are promoted, and the disulfide composite material has good catalytic hydrogen production performance under visible light. In addition, the obtained disulfide composite material has higher stability and reproducibility.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope of the present invention.
FIG. 1 is a Fourier transform infrared spectrum of the product obtained in each step of example 1 of the present invention and its organic ligand;
FIG. 2 is an X-ray photoelectron spectrum of CdS@NiS prepared in example 1 of the present invention, wherein (a) is a total spectrum; (b) Cd 3d; (c) Ni 2p; (d) S2 p;
FIG. 3 is a high resolution transmission electron microscope, a field emission scanning electron microscope, an element mapping image and a zoned electron diffraction pattern of CdS@NiS prepared in example 1 of the present invention;
FIG. 4 is a powder X-ray diffraction spectrum of the disulfide composite material prepared in example 1, comparative example 1-2 of the present invention;
FIG. 5 (a) shows the hydrogen evolution rate of the disulfide composite materials prepared in example 1, comparative examples 1-2 of the present invention; (b) The quantum yield and ultraviolet visible diffuse reflection spectrum of CdS@NiS prepared in the embodiment 1 of the invention;
FIG. 6 is a graph showing the UV-visible diffuse reflectance spectrum of (a) the disulfide composite material prepared in example 1, comparative examples 1-2 of the present invention; (b) photoluminescence spectra; (c) fluorescence lifetime; (d) electrochemical impedance spectroscopy.
Detailed Description
The term as used herein:
the terms "comprising," "including," "having," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, step, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, step, method, article, or apparatus.
When an equivalent, concentration, or other value or parameter is expressed as a range, preferred range, or a range bounded by a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when ranges of "1 to 5" are disclosed, the described ranges should be construed to include ranges of "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a numerical range is described herein, unless otherwise indicated, the range is intended to include its endpoints and all integers and fractions within the range.
One embodiment of the present invention provides a method for preparing a disulfide composite material, comprising the steps of:
(1) Mixing a certain amount of nickel salt solution with a certain amount of ligand solution, carrying out oil bath reflux reaction at a certain temperature, cooling to room temperature after reacting for a certain time, and obtaining a nickel metal organic framework material through centrifugation, washing and drying;
in the step, the nickel salt solution is prepared by dissolving nickel acetate in deionized water, and the ligand solution is prepared by dissolving 2, 5-dihydroxyterephthalic acid in deionized water; wherein the mass ratio of nickel acetate to 2, 5-dihydroxyterephthalic acid is (5-10) (2-4);
the reaction temperature of the oil bath reflux reaction is 80-100 ℃ and the reaction time is 1-2h; the washing is to adopt deionized water and methanol to wash at least twice respectively; the drying is vacuum drying, the drying temperature is 70-80 ℃, and the drying time is 8-10h;
(2) Dispersing a certain amount of the nickel metal organic framework material into a certain amount of cadmium salt solution, uniformly stirring, reacting for a certain time at a certain temperature, cooling to room temperature, centrifuging, washing and drying to obtain a bimetal organic framework material;
in the step, the cadmium salt solution is prepared by dissolving cadmium acetate in DMF; wherein the mass ratio of the cadmium acetate to the nickel metal organic framework material is (10-20) (1.5-2);
the reaction temperature is 130-150 ℃ and the reaction time is 6-8h, and the reaction is carried out in a polytetrafluoroethylene reactor; the washing is to adopt DMF and ethanol to wash at least twice respectively; the drying is vacuum drying, the drying temperature is 70-80 ℃, and the drying time is 8-10h;
(3) Dispersing a certain amount of the bimetal organic framework material into a certain amount of sulfur-containing organic solution, uniformly stirring, reacting for a certain time at a certain temperature, cooling to room temperature, and centrifuging, washing and drying to obtain the disulfide composite material;
in the step, the sulfur-containing organic solution is prepared by dissolving thioacetamide in ethanol, wherein the mass ratio of the thioacetamide to the bimetallic organic framework material is (4-5): 1;
the reaction temperature is 130-150 ℃ and the reaction time is 6-8h, and the reaction is carried out in a polytetrafluoroethylene reactor under the hydrothermal condition; the washing is carried out for 3-5 times by adopting ethanol solution; the drying is vacuum drying, the drying temperature is 70-80 ℃, and the drying time is 8-10h.
Another embodiment of the invention provides a disulfide composite material prepared by the preparation method. The disulfide composite material prepared by the preparation method disclosed by the invention has the advantages that CdS and NiS are uniformly distributed in the composite material to form a large number of compact p-n heterojunction interfaces, so that separation and migration of holes and electrons are greatly promoted, and the photocatalytic hydrogen evolution performance of the composite material is effectively improved.
Another embodiment of the invention provides an application of the disulfide composite material in photocatalytic hydrogen evolution. The disulfide composite material has higher photocatalytic hydrogen evolution rate; at 450nm, the apparent quantum efficiency is as high as 13.23%; shows good photocatalytic recovery under visible light.
Embodiments of the present invention will be described in detail below with reference to specific examples, but it will be understood by those skilled in the art that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1
The embodiment provides a preparation method of a disulfide composite material, which comprises the following steps:
(1) Dissolving 10g of nickel acetate in 50mL of deionized water, and carrying out ultrasonic stirring to obtain a uniform nickel salt solution; dissolving 4g of 2, 5-dihydroxyterephthalic acid in 150mL of deionized water, and stirring by ultrasonic to obtain a uniform ligand solution; mixing the prepared nickel salt solution with the ligand solution, pouring the mixture into a glass flask, carrying out oil bath reflux reaction at 100 ℃, stirring the mixture for 2 hours, cooling the mixture to room temperature, centrifuging the mixture to obtain solid precipitate, respectively washing the solid precipitate with deionized water and methanol for 3 times, and carrying out vacuum drying at 80 ℃ for 8 hours to obtain a nickel metal organic framework material (MOF-Ni);
(2) 2g of cadmium acetate is dissolved in 15mL of DMF, and the mixture is stirred by ultrasonic until the mixture is completely dissolved, so as to obtain clear cadmium salt solution; dispersing 200mg of MOF-Ni obtained in the step (1) in the prepared cadmium salt solution, and stirring for 0.5h to obtain a uniformly mixed suspension; placing the suspension in a polytetrafluoroethylene reactor, heating to 150 ℃ for reaction for 8 hours, cooling to room temperature after the reaction is completed, centrifuging to obtain solid precipitate, respectively washing 3 times by adopting DMF and ethanol, and drying in vacuum at 80 ℃ for 8 hours to obtain a bimetal organic framework material (MOF-Ni/Cd);
(3) 1g of Thioacetamide (TAA) is dissolved in 15mL of ethanol solution, and stirred by ultrasonic until the thioacetamide is completely dissolved, thus obtaining uniform sulfur-containing organic solution; dispersing 220mg of MOF-Ni/Cd obtained in the step (2) in the prepared sulfur-containing organic solution, and magnetically stirring for 30min to obtain a uniform suspension; heating the suspension in a polytetrafluoroethylene reactor to 150 ℃ under hydrothermal condition for reaction for 8 hours, cooling to room temperature, centrifuging to obtain solid precipitate, washing 3 times by adopting ethanol, and drying in vacuum at 80 ℃ for 8 hours to obtain the disulfide composite material (CdS@NiS).
The product obtained in each step in this example and the organic ligand H 4 DOBDC was subjected to Fourier transform infrared spectrogram test (see FIG. 1), from which it can be seen that CdS@NiS no longer has an organic ligand H 4 The characteristic peak of DOBDC has been substantially converted to a cadmium sulfide material. The X-ray photoelectron spectrum (figure 2) proves that CdS@NiS has valence state characteristic peaks of cadmium, nickel and sulfur elements. By testing a transmission electron microscope, a scanning electron microscope, an element mapping diagram and an electron diffraction diagram (figure 3) of CdS@NiS, the internal structure of the CdS@NiS can be seen, the particle size of the CdS@NiS is obviously reduced, and a larger specific surface area is provided for catalytic reaction; and obvious crystal lines exist around the amorphous nickel sulfide, the p-type semiconductor nickel sulfide and the n-type semiconductor cadmium sulfide are in close contact, valence band electrons and conduction band electrons are gradually complemented and tend to balance, and a new energy band is formed, namely a p-n heterojunction is formed inside the material.
Example 2
The embodiment provides a preparation method of a disulfide composite material, which comprises the following steps:
(1) Dissolving 5g of nickel acetate in 60mL of deionized water, and carrying out ultrasonic stirring to obtain a uniform nickel salt solution; 2g of 2, 5-dihydroxyterephthalic acid is dissolved in 120mL of deionized water, and the solution is stirred by ultrasonic waves to obtain uniform ligand solution; mixing the prepared nickel salt solution with the ligand solution, pouring the mixture into a glass flask, carrying out oil bath reflux reaction at 80 ℃, stirring the mixture for 1h, cooling the mixture to room temperature, centrifuging the mixture to obtain solid precipitate, respectively washing the solid precipitate with deionized water and methanol for 3 times, and carrying out vacuum drying at 70 ℃ for 10h to obtain MOF-Ni;
(2) 1g of cadmium acetate is dissolved in 25mL of DMF, and the mixture is stirred by ultrasonic until the cadmium acetate is completely dissolved, so as to obtain clear cadmium salt solution; dispersing 200mg of MOF-Ni obtained in the step (1) in the prepared cadmium salt solution, and stirring for 0.5h to obtain a uniformly mixed suspension; heating the suspension in a polytetrafluoroethylene reactor to 130 ℃ for reaction for 7 hours, cooling to room temperature after the reaction is completed, centrifuging to obtain solid precipitate, washing 3 times by adopting DMF and ethanol respectively, and drying in vacuum at 70 ℃ for 10 hours to obtain MOF-Ni/Cd;
(3) 0.8g of Thioacetamide (TAA) is dissolved in 25mL of ethanol solution, and stirred by ultrasonic until the thioacetamide is completely dissolved, thus obtaining uniform sulfur-containing organic solution; dispersing 200mg of MOF-Ni/Cd obtained in the step (2) in the prepared sulfur-containing organic solution, and magnetically stirring for 60min to obtain a uniform suspension; heating the suspension to 130 ℃ in a polytetrafluoroethylene reactor under hydrothermal condition for reaction for 7 hours, cooling to room temperature, centrifuging to obtain solid precipitate, washing with ethanol for 5 times, and vacuum drying at 70 ℃ for 10 hours to obtain CdS@NiS.
Example 3
The embodiment provides a preparation method of a disulfide composite material, which comprises the following steps:
(1) 8g of nickel acetate is dissolved in 50mL of deionized water, and the solution is stirred by ultrasonic waves to obtain a uniform nickel salt solution; 3g of 2, 5-dihydroxyterephthalic acid is dissolved in 130mL of deionized water, and the solution is stirred by ultrasonic waves to obtain uniform ligand solution; mixing the prepared nickel salt solution with the ligand solution, pouring the mixture into a glass flask, carrying out oil bath reflux reaction at 90 ℃, stirring the mixture for 1.5 hours, cooling the mixture to room temperature, centrifuging the mixture to obtain solid precipitate, respectively washing the solid precipitate with deionized water and methanol for 3 times, and carrying out vacuum drying at 70 ℃ for 9 hours to obtain MOF-Ni;
(2) 2g of cadmium acetate is dissolved in 20mL of DMF, and the mixture is stirred by ultrasonic until the mixture is completely dissolved, so as to obtain clear cadmium salt solution; dispersing 150mg of MOF-Ni obtained in the step (1) in the prepared cadmium salt solution, and stirring for 0.5h to obtain a uniformly mixed suspension; heating the suspension in a polytetrafluoroethylene reactor to 140 ℃ for reaction for 6 hours, cooling to room temperature after the reaction is completed, centrifuging to obtain solid precipitate, respectively washing 3 times by adopting DMF and ethanol, and drying in vacuum for 9 hours at 70 ℃ to obtain MOF-Ni/Cd;
(3) 0.9g of Thioacetamide (TAA) is dissolved in 20mL of ethanol solution, and stirred by ultrasonic until the thioacetamide is completely dissolved, thus obtaining uniform sulfur-containing organic solution; dispersing 180mg of MOF-Ni/Cd obtained in the step (2) in the prepared sulfur-containing organic solution, and magnetically stirring for 50min to obtain a uniform suspension; heating the suspension to 130 ℃ in a polytetrafluoroethylene reactor under hydrothermal condition for reaction for 6 hours, cooling to room temperature, centrifuging to obtain solid precipitate, washing with ethanol for 5 times, and vacuum drying at 70 ℃ for 10 hours to obtain CdS@NiS.
Comparative example 1
The comparative example provides a preparation method of a CdS-NiS composite material, which comprises the following steps:
(1) 1-2g Cd (NO) 3 ) 2 ·4H 2 Dissolving O and 2.5-3g of thioacetamide in 50-70mL of deionized water, and ultrasonically stirring for 0.5-1h to obtain a uniform solution; transferring the uniform solution into a 100 ml stainless steel autoclave lined with Teflon, heating at 130-150 ℃ for 20-22h, cooling to room temperature, collecting the final product through centrifugation, respectively washing 3-5 times by adopting deionized water and ethanol, and then drying in a vacuum drying oven at 70-80 ℃ for 8-10h to obtain CdS nano particles;
(2) 200mg of the CdS nano particles obtained in the step (1) together with 45mg of nickel nitrate and 12mg of TAA are dissolved in 15-25mL of water, stirred for 0.5-1h, transferred into a reaction kettle for reaction for 20-22h at 130-150 ℃, washed for 3 times by water, and dried in vacuum to obtain CdS-NiS.
Comparative example 2
The comparative example provides a preparation method of a CdS/NiS composite material, which comprises the following steps:
0.277g of cadmium nitrate, 0.174g of nickel nitrate and 0.113g of TAA are dissolved in 15-25mL of ethanol together, stirred for 0.5-1h, transferred into a reaction kettle for reaction for 20-22h at 130-150 ℃, washed for 3 times by ethanol, and dried in vacuum to obtain CdS/NiS.
Performance tests were performed on cds@nis prepared in example 1, cdS-NiS prepared in comparative example 1, and CdS/NiS prepared in comparative example 2, the test results being shown in fig. 4-6, wherein,
hydrogen production test: the photocatalytic hydrogen evolution test was performed in a 60mL closed quartz vessel. 5mg of the test material was dispersed in 16mL of water, and 4mL of lactic acid was added to the above solution, respectively. After 15min of ultrasonic treatment, the air in the bottle was removed by bubbling nitrogen. The reaction suspension was illuminated under stirring under a 300w xenon lamp. The hydrogen produced was detected by gas chromatography. The Apparent Quantum Yield (AQY) was obtained by irradiation of a 450nm filter with a 300 watt xenon lamp under 450nm monochromatic light. Apparent quantum yields were calculated as follows:
AQY = ((number of hydrogen molecules×2)/number of incident photons) ×100%
Photocurrent measurement: the process was carried out on a CHI-660 electrochemical workstation (Cinhua instruments Co., shanghai, china) in a conventional three-electrode configuration with a Pt foil as counter electrode and Ag/AgCl (saturated KCl) as reference electrode. A300W xenon lamp was used as a light source using 0.5M Na 2 SO 4 The aqueous solution serves as an electrolyte. The working electrode was prepared as follows: dispersing 2mg of material to be measured in 5mL of ethanol solution, carrying out ultrasonic treatment for 15min to obtain a uniform mixed solution, uniformly coating the mixed solution on a conductive glass (FTO) thin plate by using a plastic dropper, and drying the mixed solution in an oven; and clamping the obtained thin plate with the material to be measured in a platinum sheet electrode clamp to obtain the working electrode.
As can be seen from FIG. 4, both example 1 and comparative examples 1-2 synthesized well cadmium sulfide, which was matched to CdS standard X-ray diffraction spectrum (JCPDS # 65-3414); according to FIG. 5, the hydrogen evolution rate of CdS@NiS is highest, and the apparent quantum efficiency at 450nm is as high as 13.23%; in FIG. 6 (a), cdS@NiS has the best light absorbing capacity in the visible-infrared region; the photoluminescence intensity is the degree of electron-hole recombination, the greater the intensity, the more serious the recombination, and as can be seen from fig. 6 (b), the weakest the cds@nis intensity and the lowest the recombination rate; in FIG. 6 (c), the average fluorescence lifetimes of CdS@NiS, cdS/NiS and CdS-NiS are 5.72ns, 3.70ns and 2.59ns respectively, so that the fluorescence lifetime of CdS@NiS is the longest and the performance is the best; in fig. 6 (d), the radius of the electrochemical impedance spectrum of cds@nis is the smallest, which indicates that the impedance is the smallest and the conducting effect is the best.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Furthermore, those skilled in the art will appreciate that while some embodiments herein include some features but not others included in other embodiments, combinations of features of different embodiments are meant to be within the scope of the invention and form different embodiments. For example, in the claims below, any of the claimed embodiments may be used in any combination. The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Claims (7)
1. A method for preparing a disulfide composite material, comprising the steps of:
(1) Mixing a certain amount of nickel salt solution with a certain amount of ligand solution, carrying out oil bath reflux reaction at a certain temperature, cooling to room temperature after reacting for a certain time, and obtaining a nickel metal organic framework material through centrifugation, washing and drying; wherein the nickel salt solution is prepared by dissolving nickel acetate in deionized water, and the ligand solution is prepared by dissolving 2, 5-dihydroxyterephthalic acid in deionized water; the mass ratio of nickel acetate to 2, 5-dihydroxyterephthalic acid is (5-10): 2-4;
(2) Dispersing a certain amount of the nickel metal organic framework material into a certain amount of cadmium salt solution, uniformly stirring, reacting for 6-8 hours at 130-150 ℃, cooling to room temperature, centrifuging, washing and drying to obtain the bimetal organic framework material; wherein the cadmium salt solution is prepared by dissolving cadmium acetate in DMF, and the mass ratio of the cadmium acetate to the nickel metal organic framework material is (10-20) (1.5-2);
(3) Dispersing a certain amount of the bimetallic organic framework material into a certain amount of sulfur-containing organic solution, uniformly stirring, reacting for 6-8 hours at the temperature of 130-150 ℃, cooling to room temperature, centrifuging, washing and drying to obtain the disulfide composite material, wherein the sulfur-containing organic solution is prepared by dissolving thioacetamide in ethanol, and the mass ratio of the thioacetamide to the bimetallic organic framework material is (4-5): 1.
2. The method for producing a disulfide composite material according to claim 1, wherein in the step (1), the reaction temperature of the oil bath reflux reaction is 80 to 100 ℃ and the reaction time is 1 to 2 hours; the washing is to adopt deionized water and methanol to wash at least twice respectively; the drying is vacuum drying, the drying temperature is 70-80 ℃, and the drying time is 8-10h.
3. The method of preparing a disulfide composite material according to claim 1, wherein in the step (2), the washing is at least twice with DMF and ethanol, respectively; the drying is vacuum drying, the drying temperature is 70-80 ℃, and the drying time is 8-10h.
4. The method of preparing a disulfide composite material according to claim 1, wherein in the step (3), the washing is performed 3 to 5 times with an ethanol solution; the drying is vacuum drying, the drying temperature is 70-80 ℃, and the drying time is 8-10h.
5. The method of preparing a disulfide composite material as claimed in claim 4, wherein in step (3), the reaction is performed in a polytetrafluoroethylene reactor under solvothermal conditions.
6. A disulfide composite material obtained by the preparation method according to any one of claims 1 to 5.
7. The use of the disulfide composite material of claim 6 in photocatalytic hydrogen evolution.
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| CN108927178A (en) * | 2018-06-21 | 2018-12-04 | 三峡大学 | A kind of In-situ sulphiding method of metal-organic framework material prepares the method and application of NiS/CdS composite catalyst |
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