CN112958118A - Double-sulfide composite material and preparation method and application thereof - Google Patents
Double-sulfide composite material and preparation method and application thereof Download PDFInfo
- Publication number
- CN112958118A CN112958118A CN202110276555.9A CN202110276555A CN112958118A CN 112958118 A CN112958118 A CN 112958118A CN 202110276555 A CN202110276555 A CN 202110276555A CN 112958118 A CN112958118 A CN 112958118A
- Authority
- CN
- China
- Prior art keywords
- composite material
- drying
- reaction
- nickel
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- 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 23
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 23
- 230000001699 photocatalysis Effects 0.000 claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 56
- 238000001035 drying Methods 0.000 claims description 44
- 239000000463 material Substances 0.000 claims description 44
- 239000000243 solution Substances 0.000 claims description 44
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 41
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 32
- 238000005406 washing Methods 0.000 claims description 31
- 238000003756 stirring Methods 0.000 claims description 30
- 239000012266 salt solution Substances 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 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 22
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 22
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 22
- 239000003446 ligand Substances 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- 238000001816 cooling Methods 0.000 claims description 19
- 150000002815 nickel Chemical class 0.000 claims description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 150000001661 cadmium Chemical class 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- 229910052717 sulfur Inorganic materials 0.000 claims description 16
- 239000011593 sulfur Substances 0.000 claims description 16
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 15
- LHQLJMJLROMYRN-UHFFFAOYSA-L cadmium acetate Chemical compound [Cd+2].CC([O-])=O.CC([O-])=O LHQLJMJLROMYRN-UHFFFAOYSA-L 0.000 claims description 15
- 239000013384 organic framework Substances 0.000 claims description 14
- 238000001291 vacuum drying Methods 0.000 claims description 14
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 13
- -1 polytetrafluoroethylene Polymers 0.000 claims description 11
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 11
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 11
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 10
- 229940078494 nickel acetate Drugs 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 9
- 238000010992 reflux Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 7
- RWSOTUBLDIXVET-UHFFFAOYSA-M hydrosulfide Chemical compound [SH-] RWSOTUBLDIXVET-UHFFFAOYSA-M 0.000 claims description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 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
- 238000005342 ion exchange Methods 0.000 abstract description 3
- 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 37
- 239000000203 mixture Substances 0.000 description 14
- 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 8
- 230000009977 dual effect Effects 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 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
- 238000012360 testing method 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
- 229910052793 cadmium Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000013110 organic ligand Substances 0.000 description 3
- 239000011941 photocatalyst 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
- 238000001228 spectrum 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
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000009286 beneficial effect Effects 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
- 238000004140 cleaning Methods 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
- 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
- 150000004763 sulfides Chemical class 0.000 description 2
- 238000004073 vulcanization Methods 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
- 239000007832 Na2SO4 Substances 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 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
- 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
- 238000005119 centrifugation 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
- 230000007547 defect Effects 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
- 230000002349 favourable effect Effects 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
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000011259 mixed solution Substances 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
- 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
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 238000000628 photoluminescence spectroscopy 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
- 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
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000527 sonication Methods 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
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
Images
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
-
- 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
- B01J35/33—Electric or magnetic properties
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention provides a preparation method of a double-sulfide composite material, the double-sulfide composite material prepared by the preparation method and application of the double-sulfide composite material in photocatalytic hydrogen evolution. The invention obtains the bisulphide composite material through coordination reaction, ion exchange and hydrothermal reaction, has simple preparation process and lower cost, and is easy for industrial application. In the double-sulfide 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 photon-generated carriers are promoted, and the double-sulfide composite material has good catalytic hydrogen production performance under visible light. In addition, the double-sulfide composite material obtained by the invention has higher stability and reproducibility.
Description
Technical Field
The invention relates to the field of photocatalytic hydrogen evolution, in particular to a bisulfide 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 fuels or biomass, and not only consumes a large amount of energy, but also causes serious environmental pollution. Solar-driven water splitting is considered a promising future method for hydrogen production. The key to this process is the preparation of highly efficient photocatalysts.
CdS has a suitable band position and is considered to be one of the most suitable water-splitting materials for visible light driving. However, the efficiency and stability of photocatalysis are greatly affected by problems such as rapid recombination of photo-induced carriers, limited photo-response and severe photo-corrosion. NiS is an easily available cocatalyst and is very suitable for improving the photocatalytic performance of CdS. However, in the current research, the NiS particles are only loaded on the surface of CdS, and the photocatalytic effect is greatly influenced due to the defect that the CdS is easy to fall off.
Therefore, how to synthesize a tighter heterojunction interface between CdS and NiS is still a great challenge, and no more mature and complete solution exists at present.
Disclosure of Invention
The invention aims to provide a double-sulfide composite material and a preparation method and application thereof. The Ni and the Cd in the bimetallic framework material obtained by the preparation method 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 bisulfide composite material, comprising the steps of: (1) mixing a certain amount of nickel salt solution and 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 centrifuging, washing and drying to obtain the nickel metal organic framework material; (2) dispersing a certain amount of the nickel metal organic framework material in a certain amount of cadmium salt solution, uniformly stirring, reacting at a certain temperature for a certain time, cooling to room temperature, centrifuging, washing and drying to obtain a bimetallic organic framework material; (3) dispersing a certain amount of the bimetallic organic framework material in a certain amount of sulfur-containing organic solution, uniformly stirring, reacting at a certain temperature for a certain time, cooling to room temperature, centrifuging, washing and drying to obtain the bisulfide composite material.
Preferably, in step (1), the nickel salt solution is prepared by dissolving nickel salt in deionized water, and the ligand solution is prepared by dissolving ligand material in deionized water.
Preferably, the nickel salt comprises one or more of nickel acetate, nickel nitrate and 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-dihydroxy terephthalic acid (H)4DOBDC). Wherein, the nickel acetate is beneficial to better dissolving the ligand material.
Preferably, the mass ratio of the nickel salt to the ligand material is (5-10) to (2-4). The utilization rate of the metal salt of the material synthesized by the proportion is up to 91.6%.
Preferably, in the step (1), the reaction temperature of the oil bath reflux reaction is 80-100 ℃, and the reaction time is 1-2 h; the washing is at least twice by respectively washing with deionized water and methanol; the drying is vacuum drying, the drying temperature is 70-80 ℃, and the drying time is 8-10 h. In the step (1), nickel acetate and 2, 5-dihydroxy terephthalic acid are subjected to coordination reaction, acetate ions in an aqueous solution deprotonate the 2, 5-dihydroxy terephthalic acid so as to be well dissolved in a reaction solution, carboxylic acid groups of chains at two ends of a ligand respectively form ionic bond coordination with the nickel ions, and each nickel ion is respectively coordinated with five oxygen atoms to finally form a porous nano material with a one-dimensional channel, namely the nickel metal organic framework material (MOF-Ni) is obtained.
Preferably, in step (2), the cadmium salt solution is prepared by dissolving cadmium acetate in water, ethanol or DMF.
More preferably, in step (2), the cadmium salt solution is prepared by dissolving cadmium acetate in DMF. Cadmium acetate and DMF are adopted to prepare cadmium salt solution in the step (2), the solubility of cadmium acetate in DMF is high, and the preparation method is suitable for preparing cadmium salt solution with higher concentration, so that cadmium ions can enter the interior of the nickel metal organic framework material to replace part of nickel metal, and further 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 the higher proportion of cadmium ions is beneficial to entering the interior of the nickel metal organic framework material to replace part of nickel metal, so as to obtain the bimetal organic framework material.
Preferably, in the step (2), the reaction temperature is 130-150 ℃, the reaction time is 6-8h, and the reaction is carried out in a polytetrafluoroethylene reactor; the washing is at least twice by adopting DMF and ethanol respectively; the drying is vacuum drying, the drying temperature is 70-80 ℃, and the drying time is 8-10 h. The method comprises the following steps of (2) dispersing a nickel metal organic framework material in a high-concentration cadmium salt solution, enabling cadmium ions to continuously enter an MOF pore channel, breaking a bond with nickel oxygen, replacing part of nickel with cadmium, namely inserting the cadmium ions into MOF-Ni obtained in the step (1) through ion exchange to obtain a bimetallic organic framework material (MOF-Ni/Cd), and well mixing Ni and Cd in the MOF-Ni/Cd.
Preferably, in step (3), the sulfur-containing organic solution is prepared by dissolving 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 high mass, 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 6-8 h; the washing is carried out for 3-5 times by adopting an ethanol solution; the drying is vacuum drying, the drying temperature is 70-80 ℃, and the drying time is 8-10 h.
Preferably, in step (3), the reaction is carried out in a polytetrafluoroethylene reactor under solvothermal conditions. Step (3) of the present invention is carried out by a simple solvent heat treatment, andforming the CdS @ NiS composite material, wherein the boiling point of ethanol is low, and high-pressure activated reactants are generated in a reaction kettle, so that the sulfuration reaction is easier to perform; thioacetamide decomposes at high temperatures to give S2-Ionic, high concentration of S2-Continuously enter the interior of the bimetallic organic framework material, and S2-Compared with oxygen, the composite material has stronger bonding capability, so that a metal-oxygen bond is broken, the metal-sulfur bond is established, the CdS @ NiS composite material is formed, a compact p-n junction is formed inside the composite material, the migration of carriers and the photocatalytic hydrogen production process are greatly promoted, and the photocatalytic hydrogen production performance of the composite material is effectively improved.
The invention also provides the double sulfide composite material prepared by the preparation method. According to the double-sulfide composite material prepared by the preparation method, CdS and NiS are uniformly distributed in the composite material to form a large number of compact p-n heterojunction interfaces, so that the 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 an application of the double sulfide composite material in photocatalytic hydrogen evolution. The double-sulfide composite material has higher photocatalytic hydrogen evolution rate; at 450nm, the apparent quantum efficiency is as high as 13.23%; and the photocatalyst shows good photocatalytic recovery rate under visible light.
The invention obtains the bisulphide composite material through coordination reaction, ion exchange and hydrothermal reaction, has simple preparation process and lower cost, and is easy for industrial application. In the double-sulfide 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 photon-generated carriers are promoted, and the double-sulfide composite material has good catalytic hydrogen production performance under visible light. In addition, the double-sulfide composite material obtained by the invention has higher stability and reproducibility.
Drawings
To more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are required to be used in the embodiments will be briefly described below, and it should be 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 and its organic ligand obtained at each step of example 1 of the present invention;
FIG. 2 is an X-ray photoelectron spectrum of CdS @ NiS prepared according to example 1 of the present invention, wherein (a) the total spectrum; (b) cd 3 d; (c) ni 2 p; (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 dual sulfide composite materials obtained in example 1 of the present invention and comparative examples 1 to 2;
FIG. 5(a) is a graph showing hydrogen evolution rates of the dual sulfide composites of example 1 of the present invention and comparative examples 1-2; (b) the quantum yield and the ultraviolet-visible diffuse reflection spectrum of the CdS @ NiS prepared in the embodiment 1 are shown in the specification;
FIG. 6 is a graph showing (a) a UV-visible diffuse reflectance spectrum of a dual sulfide composite material obtained in example 1 of the present invention and in comparative examples 1 to 2; (b) photoluminescence spectroscopy; (c) fluorescence lifetime; (d) electrochemical impedance spectroscopy.
Detailed Description
The terms as used herein:
the terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, 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, process, method, article, or apparatus.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range 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 the range "1 ~ 5" is disclosed, the ranges described should be construed to include the ranges "1 ~ 4", "1 ~ 3", "1 ~ 2 and 4 ~ 5", "1 ~ 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.
One embodiment of the present invention provides a method for preparing a dual sulfide composite material, comprising the steps of:
(1) mixing a certain amount of nickel salt solution and 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 centrifuging, washing and drying to obtain the nickel metal organic framework material;
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-dihydroxy terephthalic acid in deionized water; wherein the mass ratio of the nickel acetate to the 2, 5-dihydroxy terephthalic acid is (5-10) to (2-4);
the reaction temperature of the oil bath reflux reaction is 80-100 ℃, and the reaction time is 1-2 h; the washing is at least twice by respectively washing with deionized water and methanol; the drying is vacuum drying, the drying temperature is 70-80 ℃, and the drying time is 8-10 h;
(2) dispersing a certain amount of the nickel metal organic framework material in a certain amount of cadmium salt solution, uniformly stirring, reacting at a certain temperature for a certain time, cooling to room temperature, centrifuging, washing and drying to obtain a bimetallic 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) to (1.5-2);
the reaction temperature is 130-150 ℃, the reaction time is 6-8h, and the reaction is carried out in a polytetrafluoroethylene reactor; the washing is at least twice by adopting DMF and ethanol respectively; the drying is vacuum drying, the drying temperature is 70-80 ℃, and the drying time is 8-10 h;
(3) dispersing a certain amount of the bimetallic organic framework material in a certain amount of sulfur-containing organic solution, uniformly stirring, reacting at a certain temperature for a certain time, cooling to room temperature, centrifuging, washing and drying to obtain the bisulfide 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) to 1;
the reaction temperature is 130-150 ℃, 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 an ethanol solution; the drying is vacuum drying, the drying temperature is 70-80 ℃, and the drying time is 8-10 h.
Another embodiment of the present invention provides a dual sulfide composite material prepared by the preparation method. According to the double-sulfide composite material prepared by the preparation method, CdS and NiS are uniformly distributed in the composite material to form a large number of compact p-n heterojunction interfaces, so that the 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 present invention provides a use of the bisulphide composite in photocatalytic hydrogen evolution. The double-sulfide composite material has higher photocatalytic hydrogen evolution rate; at 450nm, the apparent quantum efficiency is as high as 13.23%; and the photocatalyst shows good photocatalytic recovery rate under visible light.
Embodiments of the present invention will be described in detail below with reference to specific examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1
The embodiment provides a preparation method of a double sulfide composite material, which comprises the following steps:
(1) dissolving 10g of nickel acetate in 50mL of deionized water, and performing ultrasonic stirring to obtain a uniform nickel salt solution; dissolving 4g of 2, 5-dihydroxy terephthalic acid in 150mL of deionized water, and performing ultrasonic stirring to obtain a uniform ligand solution; mixing the prepared nickel salt solution and a ligand solution, pouring the mixture into a glass flask, carrying out oil bath reflux reaction at 100 ℃, stirring the mixture for reaction for 2 hours, cooling the mixture to room temperature, centrifuging the mixture to obtain solid precipitate, respectively washing the solid precipitate for 3 times by using deionized water and methanol, and carrying out vacuum drying at 80 ℃ for 8 hours to obtain a nickel metal organic framework material (MOF-Ni);
(2) dissolving 2g of cadmium acetate in 15mL of DMF, and ultrasonically stirring until the cadmium acetate is completely dissolved to obtain a clear cadmium salt solution; dispersing 200mg of MOF-Ni obtained in the step (1) in a 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 reacting for 8h, cooling to room temperature after the reaction is finished, centrifuging to obtain solid precipitate, washing for 3 times by adopting DMF and ethanol respectively, and drying in vacuum at 80 ℃ for 8h to obtain a bimetallic organic framework material (MOF-Ni/Cd);
(3) dissolving 1g Thioacetamide (TAA) in 15mL ethanol solution, and ultrasonically stirring until the thioacetamide is completely dissolved to obtain uniform sulfur-containing organic solution; dispersing 220mg of MOF-Ni/Cd obtained in the step (2) in a prepared sulfur-containing organic solution, and magnetically stirring for 30min to obtain a uniform suspension; and heating the suspension in a polytetrafluoroethylene reactor under a hydrothermal condition to 150 ℃ for reacting for 8h, cooling to room temperature, centrifuging to obtain a solid precipitate, washing for 3 times by using ethanol, and drying in vacuum at 80 ℃ for 8h to obtain the double sulfide composite material (CdS @ NiS).
The product obtained in each step of this example and the organic ligand H4All DOBDC were tested by Fourier transform infrared spectroscopy (see attached FIG. 1), and from the graph, it can be seen that CdS @ NiS no longer have organic ligand H4The characteristic peak of DOBDC has been substantially converted to cadmium sulfide material. And the X-ray photoelectron spectrum (figure 2) proves that CdS @ NiS has valence state characteristic peaks of cadmium, nickel and sulfur elements. By testing the transmission electron microscope, the scanning electron microscope, the element mapping chart and the electron diffraction chart (figure 3) of the CdS @ NiS, the internal structure of the CdS @ NiS can be seen, and the particle size of the CdS @ NiS is obviously reducedThe catalyst has larger specific surface area for catalytic reaction; and obvious lattice lines exist around the amorphous nickel sulfide, the p-type semiconductor nickel sulfide and the n-type semiconductor cadmium sulfide are in tight contact, valence band and conduction band electrons are gradually complemented and tend to be balanced, 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 double sulfide composite material, which comprises the following steps:
(1) dissolving 5g of nickel acetate in 60mL of deionized water, and performing ultrasonic stirring to obtain a uniform nickel salt solution; 2g of 2, 5-dihydroxy terephthalic acid is dissolved in 120mL of deionized water, and the solution is ultrasonically stirred to obtain a uniform ligand solution; mixing the prepared nickel salt solution and a ligand solution, pouring the mixture into a glass flask, carrying out oil bath reflux reaction at the temperature of 80 ℃, stirring the mixture for reaction for 1 hour, cooling the mixture to room temperature, centrifuging the mixture to obtain solid precipitate, washing the solid precipitate for 3 times by using deionized water and methanol respectively, and carrying out vacuum drying at the temperature of 70 ℃ for 10 hours to obtain MOF-Ni;
(2) dissolving 1g of cadmium acetate in 25mL of DMF, and ultrasonically stirring until the cadmium acetate is completely dissolved to obtain a clear cadmium salt solution; dispersing 200mg of MOF-Ni obtained in the step (1) in a prepared cadmium salt solution, and stirring for 0.5h to obtain a uniformly mixed suspension; placing the suspension in a polytetrafluoroethylene reactor, heating to 130 ℃ for reaction for 7h, cooling to room temperature after the reaction is finished, centrifuging to obtain solid precipitate, washing for 3 times by adopting DMF and ethanol respectively, and drying in vacuum at 70 ℃ for 10h to obtain MOF-Ni/Cd;
(3) dissolving 0.8g Thioacetamide (TAA) in 25mL ethanol solution, and ultrasonically stirring until the thioacetamide is completely dissolved to obtain a uniform sulfur-containing organic solution; dispersing 200mg of MOF-Ni/Cd obtained in the step (2) in a prepared sulfur-containing organic solution, and magnetically stirring for 60min to obtain a uniform suspension; and heating the suspension in a polytetrafluoroethylene reactor under a hydrothermal condition to 130 ℃ for reaction for 7h, cooling to room temperature, centrifuging to obtain a solid precipitate, washing for 5 times by using ethanol, and drying in vacuum at 70 ℃ for 10h to obtain CdS @ NiS.
Example 3
The embodiment provides a preparation method of a double sulfide composite material, which comprises the following steps:
(1) dissolving 8g of nickel acetate in 50mL of deionized water, and performing ultrasonic stirring to obtain a uniform nickel salt solution; dissolving 3g of 2, 5-dihydroxy terephthalic acid in 130mL of deionized water, and performing ultrasonic stirring to obtain a uniform ligand solution; mixing the prepared nickel salt solution and a ligand solution, pouring the mixture into a glass flask, carrying out oil bath reflux reaction at 90 ℃, stirring the mixture for reaction for 1.5h, cooling the mixture to room temperature, centrifuging the mixture to obtain solid precipitate, washing the solid precipitate for 3 times by using deionized water and methanol respectively, and carrying out vacuum drying at 70 ℃ for 9h to obtain MOF-Ni;
(2) dissolving 2g of cadmium acetate in 20mL of DMF, and ultrasonically stirring until the cadmium acetate is completely dissolved to obtain a clear cadmium salt solution; dispersing 150mg of MOF-Ni obtained in the step (1) in a prepared cadmium salt solution, and stirring for 0.5h to obtain a uniformly mixed suspension; placing the suspension in a polytetrafluoroethylene reactor, heating to 140 ℃ for reaction for 6h, cooling to room temperature after the reaction is finished, centrifuging to obtain solid precipitate, washing for 3 times by adopting DMF and ethanol respectively, and vacuum-drying for 9h at 70 ℃ to obtain MOF-Ni/Cd;
(3) dissolving 0.9g Thioacetamide (TAA) in 20mL ethanol solution, and ultrasonically stirring until the thioacetamide is completely dissolved to obtain a uniform sulfur-containing organic solution; dispersing 180mg of MOF-Ni/Cd obtained in the step (2) in a prepared sulfur-containing organic solution, and magnetically stirring for 50min to obtain a uniform suspension; and heating the suspension in a polytetrafluoroethylene reactor under a hydrothermal condition to 130 ℃ for reaction for 6h, cooling to room temperature, centrifuging to obtain a solid precipitate, washing for 5 times by using ethanol, and drying in vacuum at 70 ℃ for 10h 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 of Cd (NO)3)2·4H2Dissolving O and 2.5-3g thioacetamide in 50-70mL 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 by centrifugation, washing with deionized water and ethanol for 3-5 times respectively, and then drying in vacuumDrying for 8-10 hours in a box at 70-80 ℃ to obtain CdS nano particles;
(2) and (2) dissolving 200mg of CdS nano particles obtained in the step (1) together with 45mg of nickel nitrate and 12mg of TAA in 15-25mL of water, stirring for 0.5-1h, transferring to a reaction kettle, reacting for 20-22h at the temperature of 130-150 ℃, cleaning for 3 times by using water, and drying 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:
dissolving 0.277g of cadmium nitrate, 0.174g of nickel nitrate and 0.113g of TAA in 15-25mL of ethanol, stirring for 0.5-1h, transferring to a reaction kettle, reacting at 130-150 ℃ for 20-22h, cleaning for 3 times by using ethanol, and drying in vacuum to obtain CdS/NiS.
The CdS @ NiS obtained in example 1, CdS-NiS obtained in comparative example 1, and CdS/NiS obtained in comparative example 2 were subjected to performance tests, the test results of which are shown in fig. 4-6, wherein,
hydrogen production test: the photocatalytic hydrogen evolution test was performed in a 60mL closed quartz container. 5mg of each material to be tested was dispersed in 16mL of water, and 4mL of lactic acid was added to the above solution. After sonication for 15min, the air in the bottle was removed by nitrogen bubbling. The reaction suspension was illuminated under stirring under a 300 watt xenon lamp. The hydrogen gas produced was detected by gas chromatography. The Apparent Quantum Yield (AQY) was performed under 450nm monochromatic light, obtained by illuminating a 450nm filter with a 300 watt xenon lamp. The apparent quantum yield was calculated as follows:
AQY ═ ((number of hydrogen molecules. times.2)/number of incident photons). times.100%
Photocurrent measurement: on a CHI-660 electrochemical workstation (chenhua instruments ltd, shanghai, china) with a conventional three-electrode configuration with Pt foil as counter electrode and Ag/AgCl (saturated KCl) as reference electrode. 300W xenon lamp as light source, using 0.5M Na2SO4The aqueous solution serves as an electrolyte. The working electrode was prepared as follows: dispersing 2mg material to be measured in 5mL ethanol solution, performing ultrasonic treatment for 15min to obtain uniform mixed solution, uniformly coating on conductive glass (FTO) thin plate by using plastic dropper, and placing onDrying in an oven; the obtained thin plate with the material to be measured is clamped in a platinum sheet electrode clamp to obtain a working electrode.
As can be seen from FIG. 4, cadmium sulfide was synthesized well in both example 1 and comparative examples 1-2, both matching the CdS standard X-ray diffraction spectra (JCPDS # 65-3414); according to the attached figure 5, the hydrogen evolution rate of CdS @ NiS is the highest, and the apparent quantum efficiency at 450nm is as high as 13.23%; in FIG. 6(a), CdS @ NiS has the best light absorption in the visible-infrared region; photoluminescence intensity is the degree of electron-hole recombination, the higher the intensity is, the more serious the recombination is, and as can be seen from the attached figure 6(b), CdS @ NiS has the weakest intensity and the lowest 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, and it can be seen that CdS @ NiS has the longest fluorescence lifetime and the best performance; in FIG. 6(d), the electrochemical impedance spectrum radius of CdS @ NiS is the smallest, which indicates that the impedance is the smallest and the conductive effect is the best.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Furthermore, those skilled in the art will appreciate that while some embodiments herein include some features included in other embodiments, rather than other features, 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 above, 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 (10)
1. A preparation method of a double sulfide composite material is characterized by comprising the following steps:
(1) mixing a certain amount of nickel salt solution and 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 centrifuging, washing and drying to obtain the nickel metal organic framework material;
(2) dispersing a certain amount of the nickel metal organic framework material in a certain amount of cadmium salt solution, uniformly stirring, reacting at a certain temperature for a certain time, cooling to room temperature, centrifuging, washing and drying to obtain a bimetallic organic framework material;
(3) dispersing a certain amount of the bimetallic organic framework material in a certain amount of sulfur-containing organic solution, uniformly stirring, reacting at a certain temperature for a certain time, cooling to room temperature, centrifuging, washing and drying to obtain the bisulfide composite material.
2. The method of preparing the bis-sulfide composite material of claim 1, wherein 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 and nickel chloride, and the ligand material comprises one or more of 2, 5-dihydroxyterephthalic acid, ethanol, N-dimethylformamide and tetrahydrofuran;
preferably, the mass ratio of the nickel salt to the ligand material is (5-10) to (2-4).
3. The process for producing the bissulfide composite material according to claim 1 or 2, 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 at least twice by respectively washing with deionized water and methanol; the drying is vacuum drying, the drying temperature is 70-80 ℃, and the drying time is 8-10 h.
4. The method of preparing the bissulfide composite material according to claim 1, wherein in the step (2), the cadmium salt solution is prepared by dissolving cadmium acetate in DMF;
preferably, the mass ratio of the cadmium acetate to the nickel metal organic framework material is (10-20): (1.5-2).
5. The method for preparing the double sulfide composite material as claimed in claim 1 or 4, wherein in the step (2), the reaction temperature is 130-150 ℃ and the reaction time is 6-8 h; the washing is at least twice by adopting DMF and ethanol respectively; the drying is vacuum drying, the drying temperature is 70-80 ℃, and the drying time is 8-10 h.
6. The method for preparing the bis-sulfide composite material according to claim 1, wherein in the step (3), the sulfur-containing organic solution is prepared by dissolving 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.
7. The method for preparing the double sulfide composite material as claimed in claim 1 or 6, wherein in the step (3), the reaction temperature is 130-150 ℃ and the reaction time is 6-8 h; the washing is carried out for 3-5 times by adopting an ethanol solution; the drying is vacuum drying, the drying temperature is 70-80 ℃, and the drying time is 8-10 h.
8. The method of preparing the bissulfide composite material of claim 7, wherein in step (3), the reaction is carried out in a polytetrafluoroethylene reactor under solvothermal conditions.
9. The bisulphide composite material obtained by the production method according to any one of claims 1 to 8.
10. Use of the bissulfide composite material according to claim 9 for photocatalytic hydrogen evolution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110276555.9A CN112958118B (en) | 2021-03-15 | 2021-03-15 | Double sulfide composite material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110276555.9A CN112958118B (en) | 2021-03-15 | 2021-03-15 | Double sulfide composite material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112958118A true CN112958118A (en) | 2021-06-15 |
| CN112958118B CN112958118B (en) | 2023-07-25 |
Family
ID=76279106
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110276555.9A Active CN112958118B (en) | 2021-03-15 | 2021-03-15 | Double sulfide composite material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112958118B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114950485A (en) * | 2022-04-11 | 2022-08-30 | 齐鲁理工学院 | NiS/VS (NiS/VS) synthesized by aid of eutectic solvent 2 Composite material and use thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106994356A (en) * | 2017-06-02 | 2017-08-01 | 南京工程学院 | The preparation method of photochemical catalyst CdS NiS nano composite materials |
| 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 |
| CN110652988A (en) * | 2019-09-25 | 2020-01-07 | 三峡大学 | Preparation method and application of superfine bimetal sulfide microsphere loaded NiS film |
-
2021
- 2021-03-15 CN CN202110276555.9A patent/CN112958118B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106994356A (en) * | 2017-06-02 | 2017-08-01 | 南京工程学院 | The preparation method of photochemical catalyst CdS NiS nano composite materials |
| 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 |
| CN110652988A (en) * | 2019-09-25 | 2020-01-07 | 三峡大学 | Preparation method and application of superfine bimetal sulfide microsphere loaded NiS film |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114950485A (en) * | 2022-04-11 | 2022-08-30 | 齐鲁理工学院 | NiS/VS (NiS/VS) synthesized by aid of eutectic solvent 2 Composite material and use thereof |
| CN114950485B (en) * | 2022-04-11 | 2023-05-09 | 齐鲁理工学院 | NiS/VS synthesized with assistance of eutectic solvent 2 Composite material and use thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112958118B (en) | 2023-07-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Jin et al. | Ni, Co-based selenide anchored g-C3N4 for boosting photocatalytic hydrogen evolution | |
| Wang et al. | Photocatalytic reduction of CO2 with H2O mediated by Ce-tailored bismuth oxybromide surface frustrated lewis pairs | |
| Xue et al. | Efficient photocatalytic nitrogen fixation under ambient conditions enabled by the heterojunctions of n-type Bi 2 MoO 6 and oxygen-vacancy-rich p-type BiOBr | |
| CN107649150B (en) | A kind of preparation method and applications of the Cd/CdS hetero-junctions visible light catalyst rich in sulphur vacancy | |
| Hao et al. | Zn‐Vacancy Engineered S‐Scheme ZnCdS/ZnS Photocatalyst for Highly Efficient Photocatalytic H2 Evolution | |
| CN106622322B (en) | It is a kind of using bimetal nano particles as two-dimensional nano piece composite photo-catalyst of hetero-junctions and preparation method thereof | |
| CN105833885B (en) | Base metal MoS2CdS nano-rod photo-catalysts of modification and its preparation method and application | |
| Xu et al. | The enhanced photocatalytic properties for water oxidation over Bi/BiVO4/V2O5 composite | |
| Chao et al. | Visible light-driven methanol dehydrogenation and conversion into 1, 1-dimethoxymethane over a non-noble metal photocatalyst under acidic conditions | |
| CN106622318B (en) | It is a kind of using bimetal nano particles as lamellar composite photochemical catalyst of hetero-junctions and preparation method thereof | |
| Zhang et al. | Mechanism investigation of PtPd decorated Zn0. 5Cd0. 5S nanorods with efficient photocatalytic hydrogen production combining with kinetics and thermodynamics | |
| CN110560105A (en) | Preparation of nickel phosphide-loaded sulfur indium zinc nano microsphere composite material and application of composite material in photocatalytic hydrogen production | |
| Kang et al. | In situ formation of defect-engineered N-doped TiO 2 porous mesocrystals for enhanced photo-degradation and PEC performance | |
| She et al. | Preparation of Zn0. 5Cd0. 5S/nickel acetate hydroxide composite for ameliorated water splitting performance under visible light | |
| CN114849785B (en) | Preparation of triazine ring covalent organic framework material doped cobalt porphyrin photocatalyst | |
| Chang et al. | Electron transfer dynamics and enhanced H2 production activity of hydrangea-like BiOBr/Bi2S3-based photocatalysts with Cu-complex as a redox mediator | |
| Yang et al. | 3D mesoporous ultra-thin g-C3N4 coupled with monoclinic β-AgVO3 as pn heterojunction for photocatalytic hydrogen evolution | |
| CN110026207B (en) | CaTiO3@ZnIn2S4Nano composite material and preparation method and application thereof | |
| CN112023947A (en) | Composite material and preparation method and application thereof | |
| Chen et al. | Ti3C2‐modified g‐C3N4/MoSe2 S‐Scheme Heterojunction with Full‐Spectrum Response for CO2 Photoreduction to CO and CH4 | |
| CN112958118B (en) | Double sulfide composite material and preparation method and application thereof | |
| Wang et al. | Efficient photothermal catalytic CO2 reduction over in situ construction ZnIn2S4@ Ni (OH) 2/NiO Z-scheme heterojunction | |
| Jiang et al. | Construction of CoS/Cd 0.5 Zn 0.5 S ohmic heterojunctions for improving photocatalytic hydrogen production activity | |
| CN114160169A (en) | Preparation method and application of molybdenum-sulfur cluster packaged by covalent organic framework material | |
| Zhang et al. | The photogenerated charge characteristics in Ni@ NiO/CdS hybrids for increased photocatalytic H 2 generation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |