CN114887632B - Cadmium indium selenide/zinc sulfide/iron-cobalt oxide photocatalyst and preparation method and application thereof - Google Patents
Cadmium indium selenide/zinc sulfide/iron-cobalt oxide photocatalyst and preparation method and application thereof Download PDFInfo
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- 239000005083 Zinc sulfide Substances 0.000 title claims abstract description 59
- 229910052984 zinc sulfide Inorganic materials 0.000 title claims abstract description 59
- 229910000428 cobalt oxide Inorganic materials 0.000 title claims abstract description 56
- HRMZHHVYXPJJLN-UHFFFAOYSA-N cadmium;selanylideneindium Chemical compound [Cd].[In]=[Se] HRMZHHVYXPJJLN-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000011941 photocatalyst Substances 0.000 title abstract description 17
- PCIREHBGYFWXKH-UHFFFAOYSA-N iron oxocobalt Chemical compound [Fe].[Co]=O PCIREHBGYFWXKH-UHFFFAOYSA-N 0.000 claims abstract description 26
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000001257 hydrogen Substances 0.000 claims abstract description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 230000001699 photocatalysis Effects 0.000 claims abstract description 17
- 238000001354 calcination Methods 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims description 51
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 30
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 25
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 239000013206 MIL-53 Substances 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 19
- 238000005406 washing Methods 0.000 claims description 19
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 claims description 12
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 12
- 229940044631 ferric chloride hexahydrate Drugs 0.000 claims description 12
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 11
- 238000010992 reflux Methods 0.000 claims description 11
- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical compound OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 claims description 11
- XURCIPRUUASYLR-UHFFFAOYSA-N Omeprazole sulfide Chemical compound N=1C2=CC(OC)=CC=C2NC=1SCC1=NC=C(C)C(OC)=C1C XURCIPRUUASYLR-UHFFFAOYSA-N 0.000 claims description 10
- 239000012298 atmosphere Substances 0.000 claims description 10
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 230000001105 regulatory effect Effects 0.000 claims description 9
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims description 8
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 8
- PMYDPQQPEAYXKD-UHFFFAOYSA-N 3-hydroxy-n-naphthalen-2-ylnaphthalene-2-carboxamide Chemical compound C1=CC=CC2=CC(NC(=O)C3=CC4=CC=CC=C4C=C3O)=CC=C21 PMYDPQQPEAYXKD-UHFFFAOYSA-N 0.000 claims description 5
- 239000003446 ligand Substances 0.000 claims description 5
- 239000011655 sodium selenate Substances 0.000 claims description 5
- 229960001881 sodium selenate Drugs 0.000 claims description 5
- 235000018716 sodium selenate Nutrition 0.000 claims description 5
- VPQBLCVGUWPDHV-UHFFFAOYSA-N sodium selenide Chemical compound [Na+].[Na+].[Se-2] VPQBLCVGUWPDHV-UHFFFAOYSA-N 0.000 claims description 5
- RWSXRVCMGQZWBV-WDSKDSINSA-N glutathione Chemical compound OC(=O)[C@@H](N)CCC(=O)N[C@@H](CS)C(=O)NCC(O)=O RWSXRVCMGQZWBV-WDSKDSINSA-N 0.000 claims description 4
- PWKSKIMOESPYIA-UHFFFAOYSA-N 2-acetamido-3-sulfanylpropanoic acid Chemical compound CC(=O)NC(CS)C(O)=O PWKSKIMOESPYIA-UHFFFAOYSA-N 0.000 claims description 2
- 108010024636 Glutathione Proteins 0.000 claims description 2
- 229960003180 glutathione Drugs 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 3
- 239000002105 nanoparticle Substances 0.000 abstract description 3
- 239000011248 coating agent Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract description 2
- 239000012621 metal-organic framework Substances 0.000 abstract description 2
- 229910017052 cobalt Inorganic materials 0.000 abstract 1
- 239000010941 cobalt Substances 0.000 abstract 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract 1
- 238000004090 dissolution Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 3
- 230000031700 light absorption Effects 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 239000002131 composite material Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- -1 Transition metal chalcogenides Chemical class 0.000 description 1
- QVYYOKWPCQYKEY-UHFFFAOYSA-N [Fe].[Co] Chemical compound [Fe].[Co] QVYYOKWPCQYKEY-UHFFFAOYSA-N 0.000 description 1
- 230000032900 absorption of visible light Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004868 gas analysis Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 229940079101 sodium sulfide Drugs 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- ZGHLCBJZQLNUAZ-UHFFFAOYSA-N sodium sulfide nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Na+].[Na+].[S-2] ZGHLCBJZQLNUAZ-UHFFFAOYSA-N 0.000 description 1
- 229940048181 sodium sulfide nonahydrate Drugs 0.000 description 1
- WMDLZMCDBSJMTM-UHFFFAOYSA-M sodium;sulfanide;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Na+].[SH-] WMDLZMCDBSJMTM-UHFFFAOYSA-M 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 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
- B01J27/057—Selenium or tellurium; Compounds thereof
- B01J27/0573—Selenium; Compounds thereof
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
-
- B01J35/39—
-
- 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 cadmium indium selenide/zinc sulfide/iron-cobalt oxide photocatalyst, a preparation method thereof and application of the photocatalyst in photocatalytic water hydrogen production. The preparation method of the cadmium indium selenide/zinc sulfide/iron-cobalt oxide comprises the following steps: (1) Preparation of cobalt doped NH 2 -MILs-53 (Fe) metal organic framework, obtaining iron-cobalt oxide by calcination; (2) coating a zinc sulfide shell layer on the outer layer of the iron-cobalt oxide; (3) And preparing cadmium indium selenide nano particles and compositing the cadmium indium selenide nano particles with zinc sulfide/iron-cobalt oxide to obtain the cadmium indium selenide/zinc sulfide/iron-cobalt oxide. The cadmium indium selenide/zinc sulfide/iron-cobalt oxide photocatalyst prepared by the method has the advantages that the photocatalytic hydrogen production performance is obviously improved, the photocatalytic hydrogen production amount for 5 hours can reach 51.50mmol/g, and the material has good stability in the photocatalytic hydrogen production process.
Description
Technical Field
The invention relates to the technical field of photocatalysis, in particular to a cadmium indium selenide/zinc sulfide/iron-cobalt oxide photocatalyst, a preparation method thereof and application of the photocatalyst in photocatalytic hydrogen production.
Background
The photocatalytic water splitting hydrogen production utilizes abundant solar energy to prepare high-heat, clean and pollution-free hydrogen, and is one of important means for solving the problems of environment and resources. The metal oxide is used as a novel photocatalyst, and is paid attention to by the advantages of stable physical and chemical properties, wide light absorption range, low toxicity, proper band gap energy and the like. At present, the photocatalytic performance of single-component metal oxides remains to be improved, due to their limited absorption of visible light and higher photo-generated electron-hole recombination rates. An effective way to solve these problems is by constructing a multicomponent composite.
Transition metal chalcogenides are considered ideal photocatalyst materials due to their suitable band gap width, good light absorption properties, high stability. The multicomponent composite photocatalyst is obtained by compounding the compound and the metal oxide, the band gap width and the light absorption range can be regulated and controlled by adjusting the components and the proportion, the photogenerated electron transfer efficiency is improved, the photogenerated electron-hole recombination rate is reduced, and the further improvement of the photocatalysis performance is facilitated.
In view of this, the present invention has been made.
Disclosure of Invention
The invention provides a preparation method of a cadmium indium selenide/zinc sulfide/iron-cobalt oxide photocatalyst by taking an iron-cobalt metal organic framework derivative (iron-cobalt oxide) as a substrate and coating a zinc sulfide shell layer on an outer layer to obtain zinc sulfide/iron-cobalt oxide, and compositing cadmium indium selenide nano particles and zinc sulfide/iron-cobalt oxide to obtain the cadmium indium selenide/zinc sulfide/iron-cobalt oxide photocatalyst, and also provides an application of the cadmium indium selenide/zinc sulfide/iron-cobalt oxide photocatalyst in photocatalytic hydrogen production.
The invention aims to provide a preparation method of the cadmium indium selenide/zinc sulfide/iron-cobalt oxide photocatalyst, which specifically comprises the following steps:
(1) Respectively adding ferric chloride hexahydrate, cobalt nitrate hexahydrate and 2-amino terephthalic acid into dimethylformamide, ultrasonically dissolving, transferring into a reaction kettle, heating at 150 ℃ for 3 hours, cooling to room temperature, and sequentially centrifuging, washing and drying to obtain the NH 2 -MIL-53(Fe/Co x )；
(2) Subjecting the NH in step (1) 2 -MIL-53(Fe/Co x ) Heating to 500 ℃ to start calcination, and calcining for 2 hours to obtain the iron-cobalt oxide;
(3) Sequentially adding the iron-cobalt oxide and the zinc acetate dihydrate in the step (2) into ethylene glycol, uniformly stirring, adding thiourea, heating at 150 ℃ for reaction for 1 hour, and sequentially centrifuging, washing and drying to obtain the zinc sulfide/iron-cobalt oxide;
(4) Sequentially adding cadmium nitrate, indium nitrate and deionized water into a three-neck flask, adding a ligand under the nitrogen atmosphere, stirring uniformly, regulating the pH value by using a sodium hydroxide solution, quickly injecting a sodium selenide solution into the three-neck flask, fully stirring, and heating and refluxing to obtain the cadmium indium selenide solution;
(5) And mixing the cadmium indium selenide solution with the zinc sulfide/iron-cobalt oxide, and heating and refluxing to obtain the cadmium indium selenide/zinc sulfide/iron-cobalt oxide.
Preferably, in the step (1), the molar ratio of ferric chloride hexahydrate, cobalt nitrate hexahydrate and 2-amino terephthalic acid is 1 (0.25 to 1): 1.
Preferably, in the step (2), the heating reaction is performed in an air atmosphere, and the heating rate is 5 ℃/min.
Preferably, in the step (3), the mass ratio of the iron-cobalt oxide, the zinc acetate dihydrate and the thiourea is (0.05-0.1) 1:0.35.
Preferably, in the step (4), the molar ratio of cadmium nitrate, indium nitrate, ligand and sodium selenate is 1 (0.05-0.2): 2.4 (0.2-0.3), the pH is adjusted to 9.50-10.50 by using 1M sodium hydroxide solution, and the heating reflux is carried out for 3 hours at 100 ℃.
Preferably, in the step (4), the ligand is one of L-cysteine, glutathione, thioglycollic acid or mercaptopropionic acid.
Preferably, in the step (5), the mixture of the cadmium indium selenide solution and the zinc sulfide/iron-cobalt oxide is heated and refluxed for 4-8 hours at 100 ℃.
The invention further aims to provide application of the cadmium indium selenide/zinc sulfide/iron-cobalt oxide in photocatalytic hydrogen production, in particular to a full-glass automatic online trace gas analysis system (Labsolar-6A) for photocatalytic water hydrogen production test. The hydrogen evolution content was determined by on-line gas chromatography (GC-7806) using a xenon lamp (MICROSOLAR 300) as the light source, cadmium indium selenide/zinc sulfide/iron-cobalt oxide as the photocatalyst, 1wt% potassium chloroplatinate as the promoter, sodium sulfide and sodium sulfite as the sacrificial agents.
Compared with the prior art, the preparation method of the cadmium indium selenide/zinc sulfide/iron-cobalt oxide has the advantages of low cost of raw materials, simplicity and easiness in operation. In addition, the cadmium indium selenide/zinc sulfide/iron-cobalt oxide prepared by the method is used as a photocatalyst to crack water to prepare hydrogen, the hydrogen preparation effect is obviously improved compared with that of the cadmium indium selenide, zinc sulfide or iron-cobalt oxide, the photocatalytic hydrogen preparation amount for 5 hours can reach 51.50mmol/g, and the material can keep good stability in the photocatalytic hydrogen preparation process.
Detailed Description
The invention is further described with reference to the following specific examples:
example 1
The embodiment provides a method for preparing iron-cobalt oxide, comprising the following steps:
(1) 1.0812g of ferric chloride hexahydrate, 0.8731g of cobalt nitrate hexahydrate and 0.7245g of 2-amino terephthalic acid are respectively added into 60mL of dimethylformamide, and the solution A is obtained by ultrasonic dissolution;
(2) Transferring the solution A into a reaction kettle, heating for 3 hours at 150 ℃, cooling to room temperature, and sequentially centrifuging, washing and drying to obtain the NH 2 -MIL-53(Fe/Co 0.75 )；
(3) Subjecting the NH in step (2) 2 -MIL-53(Fe/Co 0.75 ) And (3) placing the mixture into a muffle furnace, heating to 500 ℃ to start calcination at a heating rate of 5 ℃/min in an air atmosphere, and calcining for 2 hours to obtain the iron-cobalt oxide.
Example 2
The embodiment provides a preparation method of zinc sulfide/iron-cobalt oxide, which comprises the following steps:
(1) 1.0812g of ferric chloride hexahydrate, 0.8731g of cobalt nitrate hexahydrate and 0.7245g of 2-amino terephthalic acid are respectively added into 60mL of dimethylformamide, and the solution A is obtained by ultrasonic dissolution;
(2) Transferring the solution A into a reaction kettle, heating for 3 hours at 150 ℃, cooling to room temperature, and sequentially centrifuging, washing and drying to obtain the NH 2 -MIL-53(Fe/Co 0.75 )；
(3) Subjecting the NH in step (2) 2 -MIL-53(Fe/Co 0.75 ) Put into a muffle furnace under the atmosphere of airHeating to 500 ℃ at a heating rate of 5 ℃/min to start calcination, and calcining for 2 hours to obtain the iron-cobalt oxide;
(4) 0.025g of iron-cobalt oxide and 0.34g of zinc acetate dihydrate are added into 40mL of ethylene glycol, after stirring for 1 hour, 0.12g of thiourea is added, and heating reaction is carried out for 1 hour at 150 ℃, and centrifugation, washing and drying are carried out in sequence, so as to obtain the zinc sulfide/iron-cobalt oxide.
Example 3
The embodiment provides a preparation method of cadmium indium selenide/zinc sulfide/iron-cobalt oxide, which comprises the following steps:
(1) 1.0812g of ferric chloride hexahydrate, 0.8731g of cobalt nitrate hexahydrate and 0.7245g of 2-amino terephthalic acid are respectively added into 60mL of dimethylformamide, and the solution A is obtained by ultrasonic dissolution;
(2) Transferring the solution A into a reaction kettle, heating for 3 hours at 150 ℃, cooling to room temperature, and sequentially centrifuging, washing and drying to obtain the NH 2 -MIL-53(Fe/Co 0.75 )；
(3) Subjecting the NH in step (2) 2 -MIL-53(Fe/Co 0.75 ) Placing the mixture into a muffle furnace, heating to 500 ℃ and calcining for 2 hours under the air atmosphere at a heating rate of 5 ℃/min to obtain the iron-cobalt oxide;
(4) Adding 0.025g of iron-cobalt oxide and 0.34g of zinc acetate dihydrate into 40mL of ethylene glycol, stirring for 1 hour, adding 0.12g of thiourea, heating at 150 ℃ for reaction for 1 hour, and sequentially centrifuging, washing and drying to obtain zinc sulfide/iron-cobalt oxide;
(5) Adding 0.5553g of cadmium nitrate, 0.0602g of indium nitrate and 200mL of deionized water into a three-necked flask in sequence, adding 421.8 mu L of 3-mercaptopropionic acid under nitrogen atmosphere, stirring uniformly, regulating the pH to 10.00 by using 1M sodium hydroxide solution, quickly injecting 0.6mL of sodium selenide solution into the three-necked flask, heating and refluxing for 3 hours at 100 ℃ after full stirring, and obtaining the cadmium indium selenide solution;
(6) 20mg of the zinc sulfide/iron-cobalt oxide and 50mL of the cadmium indium selenide solution are added into a flask, uniformly stirred, heated and refluxed at 100 ℃ for 6 hours, and the cadmium indium selenide/zinc sulfide/iron-cobalt oxide is obtained.
The product obtained in example 3 was used as a photocatalyst to perform a photocatalytic hydrogen production performance test. The specific method comprises the following steps: 100mL of deionized water, 20mg of catalyst powder, 1wt% K were each charged into a glass reactor 2 PtCl 4 0.035mol sodium sulfite and 0.025mol sodium sulfide nonahydrate. The reaction apparatus was sealed and evacuated with a vacuum pump for 10min to remove air before light irradiation. In the photocatalytic hydrogen production experiment, a 300W xenon lamp is used as a light source, a magnetic stirring stable suspension is adopted in the whole process, and an online gas chromatograph (GC-7806) -Thermal Conductivity Detector (TCD) is used for measuring the hydrogen content.
Example 4
The embodiment provides a preparation method of cadmium indium selenide/zinc sulfide/iron-cobalt oxide, which comprises the following steps:
(1) 1.0812g of ferric chloride hexahydrate, 0.5821g of cobalt nitrate hexahydrate and 0.7245g of 2-amino terephthalic acid are respectively added into 60mL of dimethylformamide, and the solution A is obtained by ultrasonic dissolution;
(2) Transferring the solution A into a reaction kettle, heating for 3 hours at 150 ℃, cooling to room temperature, and sequentially centrifuging, washing and drying to obtain the NH 2 -MIL-53(Fe/Co 0.5 )；
(3) Subjecting the NH in step (2) 2 -MIL-53(Fe/Co 0.5 ) Placing the mixture into a muffle furnace, heating to 500 ℃ and calcining for 2 hours under the air atmosphere at a heating rate of 5 ℃/min to obtain the iron-cobalt oxide;
(4) Adding 0.025g of iron-cobalt oxide and 0.34g of zinc acetate dihydrate into 40mL of ethylene glycol, stirring for 1 hour, adding 0.12g of thiourea, heating at 150 ℃ for reaction for 1 hour, and sequentially centrifuging, washing and drying to obtain zinc sulfide/iron-cobalt oxide;
(5) Adding 0.5553g of cadmium nitrate, 0.0602g of indium nitrate and 200mL of deionized water into a three-necked flask in sequence, adding 421.8 mu L of 3-mercaptopropionic acid under nitrogen atmosphere, stirring uniformly, regulating the pH to 10.00 by using 1M sodium hydroxide solution, quickly injecting 0.6mL of sodium selenide solution into the three-necked flask, heating and refluxing for 3 hours at 100 ℃ after full stirring, and obtaining the cadmium indium selenide solution;
(6) 20mg of the zinc sulfide/iron-cobalt oxide and 50mL of the cadmium indium selenide solution are added into a flask, uniformly stirred, heated and refluxed at 100 ℃ for 6 hours, and the cadmium indium selenide/zinc sulfide/iron-cobalt oxide is obtained.
Example 5
The embodiment provides a preparation method of cadmium indium selenide/zinc sulfide/iron-cobalt oxide, which comprises the following steps:
(1) 1.0812g of ferric chloride hexahydrate, 0.8731g of cobalt nitrate hexahydrate and 0.7245g of 2-amino terephthalic acid are respectively added into 60mL of dimethylformamide, and the solution A is obtained by ultrasonic dissolution;
(2) Transferring the solution A into a reaction kettle, heating for 3 hours at 150 ℃, cooling to room temperature, and sequentially centrifuging, washing and drying to obtain the NH 2 -MIL-53(Fe/Co 0.75 )；
(3) Subjecting the NH in step (2) 2 -MIL-53(Fe/Co 0.75 ) Placing the mixture into a muffle furnace, heating to 500 ℃ and calcining for 2 hours under the air atmosphere at a heating rate of 5 ℃/min to obtain the iron-cobalt oxide;
(4) Adding 0.034g of iron-cobalt oxide and 0.34g of zinc acetate dihydrate into 40mL of ethylene glycol, stirring for 1 hour, adding 0.12g of thiourea, heating at 150 ℃ for reaction for 1 hour, and sequentially centrifuging, washing and drying to obtain zinc sulfide/iron-cobalt oxide;
(5) Adding 0.5553g of cadmium nitrate, 0.0602g of indium nitrate and 200mL of deionized water into a three-necked flask in sequence, adding 421.8 mu L of 3-mercaptopropionic acid under nitrogen atmosphere, stirring uniformly, regulating the pH to 10.00 by using 1M sodium hydroxide solution, quickly injecting 0.6mL of sodium selenide solution into the three-necked flask, heating and refluxing for 3 hours at 100 ℃ after full stirring, and obtaining the cadmium indium selenide solution;
(6) 20mg of the zinc sulfide/iron-cobalt oxide and 50mL of the cadmium indium selenide solution are added into a flask, uniformly stirred, heated and refluxed at 100 ℃ for 6 hours, and the cadmium indium selenide/zinc sulfide/iron-cobalt oxide is obtained.
Example 6
The embodiment provides a preparation method of cadmium indium selenide/zinc sulfide/iron-cobalt oxide, which comprises the following steps:
(1) 1.0812g of ferric chloride hexahydrate, 0.8731g of cobalt nitrate hexahydrate and 0.7245g of 2-amino terephthalic acid are respectively added into 60mL of dimethylformamide, and the solution A is obtained by ultrasonic dissolution;
(2) Transferring the solution A into a reaction kettle, heating for 3 hours at 150 ℃, cooling to room temperature, and sequentially centrifuging, washing and drying to obtain the NH 2 -MIL-53(Fe/Co 0.75 )；
(3) Subjecting the NH in step (2) 2 -MIL-53(Fe/Co 0.75 ) Placing the mixture into a muffle furnace, heating to 500 ℃ and calcining for 2 hours under the air atmosphere at a heating rate of 5 ℃/min to obtain the iron-cobalt oxide;
(4) Adding 0.025g of iron-cobalt oxide and 0.34g of zinc acetate dihydrate into 40mL of ethylene glycol, stirring for 1 hour, adding 0.12g of thiourea, heating at 150 ℃ for reaction for 1 hour, and sequentially centrifuging, washing and drying to obtain zinc sulfide/iron-cobalt oxide;
(5) Adding 0.5553g of cadmium nitrate, 0.0271g of indium nitrate and 200mL of deionized water into a three-necked flask in sequence, adding 421.8 mu L of 3-mercaptopropionic acid under nitrogen atmosphere, stirring uniformly, regulating the pH to 10.00 by using 1M sodium hydroxide solution, quickly injecting 0.6mL of sodium selenate solution into the three-necked flask, heating and refluxing for 3 hours at 100 ℃ after full stirring to obtain the cadmium indium selenide solution;
(6) 20mg of the zinc sulfide/iron-cobalt oxide and 50mL of the cadmium indium selenide solution are added into a flask, uniformly stirred, heated and refluxed at 100 ℃ for 6 hours, and the cadmium indium selenide/zinc sulfide/iron-cobalt oxide is obtained.
Example 7
The embodiment provides a preparation method of cadmium indium selenide/zinc sulfide/iron-cobalt oxide, which comprises the following steps:
(1) 1.0812g of ferric chloride hexahydrate, 0.8731g of cobalt nitrate hexahydrate and 0.7245g of 2-amino terephthalic acid are respectively added into 60mL of dimethylformamide, and the solution A is obtained by ultrasonic dissolution;
(2) Transferring the solution A into a reaction kettle, heating for 3 hours at 150 ℃, cooling to room temperature, and sequentially centrifuging, washing and drying to obtain the NH 2 -MIL-53(Fe/Co 0.75 )；
(3) Subjecting the NH in step (2) 2 -MIL-53(Fe/Co 0.75 ) Placing the mixture into a muffle furnace, heating to 500 ℃ and calcining for 2 hours under the air atmosphere at a heating rate of 5 ℃/min to obtain the iron-cobalt oxide;
(4) Adding 0.025g of iron-cobalt oxide and 0.34g of zinc acetate dihydrate into 40mL of ethylene glycol, stirring for 1 hour, adding 0.12g of thiourea, heating at 150 ℃ for reaction for 1 hour, and sequentially centrifuging, washing and drying to obtain zinc sulfide/iron-cobalt oxide;
(5) Adding 2.7765g of cadmium nitrate, 0.3010g of indium nitrate and 200mL of deionized water into a three-neck flask in sequence, adding 2.11mL of 3-mercaptopropionic acid under nitrogen atmosphere, stirring uniformly, regulating the pH to 10.00 by using a 1M sodium hydroxide solution, quickly injecting 3mL of sodium selenate solution into the three-neck flask, heating and refluxing for 3 hours at 100 ℃ after full stirring, and obtaining the cadmium indium selenide solution;
(6) 20mg of the zinc sulfide/iron-cobalt oxide and 50mL of the cadmium indium selenide solution are added into a flask, uniformly stirred, heated and refluxed at 100 ℃ for 6 hours, and the cadmium indium selenide/zinc sulfide/iron-cobalt oxide is obtained.
Example 8
The embodiment provides a preparation method of cadmium indium selenide/zinc sulfide/iron-cobalt oxide, which comprises the following steps:
(1) 1.0812g of ferric chloride hexahydrate, 0.8731g of cobalt nitrate hexahydrate and 0.7245g of 2-amino terephthalic acid are respectively added into 60mL of dimethylformamide, and the solution A is obtained by ultrasonic dissolution;
(2) Transferring the solution A into a reaction kettle, heating for 3 hours at 150 ℃, cooling to room temperature, and sequentially centrifuging, washing and drying to obtain the NH 2 -MIL-53(Fe/Co 0.75 )；
(3) Subjecting the NH in step (2) 2 -MIL-53(Fe/Co 0.75 ) Placing the mixture into a muffle furnace, heating to 500 ℃ and calcining for 2 hours under the air atmosphere at a heating rate of 5 ℃/min to obtain the iron-cobalt oxide;
(4) Adding 0.025g of iron-cobalt oxide and 0.34g of zinc acetate dihydrate into 40mL of ethylene glycol, stirring for 1 hour, adding 0.12g of thiourea, heating at 150 ℃ for reaction for 1 hour, and sequentially centrifuging, washing and drying to obtain zinc sulfide/iron-cobalt oxide;
(5) Sequentially adding 0.1111g of cadmium nitrate, 0.012g of indium nitrate and 200mL of deionized water into a three-necked flask, adding 84.5 mu L of 3-mercaptopropionic acid under nitrogen atmosphere, stirring uniformly, regulating the pH to 10.00 by using 1M sodium hydroxide solution, quickly injecting 0.12mL of sodium selenate solution into the three-necked flask, fully stirring, and heating and refluxing at 100 ℃ for 3 hours to obtain the cadmium indium selenide solution;
(6) 20mg of the zinc sulfide/iron-cobalt oxide and 50mL of the cadmium indium selenide solution are added into a flask, uniformly stirred, heated and refluxed at 100 ℃ for 6 hours, and the cadmium indium selenide/zinc sulfide/iron-cobalt oxide is obtained.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the invention in any way, and any person skilled in the art may make modifications or alterations to the disclosed technical content to the equivalent embodiments. However, any simple modification, equivalent variation and variation of the above embodiments according to the technical substance of the present invention are still included in the protection scope of the technical solution of the present invention.
Claims (6)
1. The preparation method of the cadmium indium selenide/zinc sulfide/iron-cobalt oxide is characterized by comprising the following steps:
(1) Respectively adding ferric chloride hexahydrate, cobalt nitrate hexahydrate and 2-amino terephthalic acid into dimethylformamide, ultrasonically dissolving, transferring into a reaction kettle, heating at 150deg.C for 3 hr, cooling to room temperature, centrifuging, washing, and drying to obtain NH 2 -MIL-53(Fe/Co x )；
(2) Will step by stepThe NH in step (1) 2 -MIL-53(Fe/Co x ) Heating to 500 ℃ to start calcination, and calcining for 2 hours to obtain the iron-cobalt oxide;
(3) Sequentially adding the iron-cobalt oxide and zinc acetate dihydrate in the step (2) into ethylene glycol, uniformly stirring, adding thiourea, heating at 150 ℃ for reaction for 1 hour, and sequentially centrifuging, washing and drying to obtain zinc sulfide/iron-cobalt oxide;
(4) Sequentially adding cadmium nitrate, indium nitrate and deionized water into a three-neck flask, adding a ligand which is one of L-cysteine, glutathione, thioglycollic acid or mercaptopropionic acid under nitrogen atmosphere, stirring uniformly, regulating pH with sodium hydroxide solution, quickly injecting sodium selenide solution into the three-neck flask, stirring fully, and heating and refluxing to obtain cadmium indium selenide solution;
(5) And mixing the cadmium indium selenide solution with the zinc sulfide/iron-cobalt oxide, and heating and refluxing to obtain the cadmium indium selenide/zinc sulfide/iron-cobalt oxide.
2. The method for preparing cadmium indium selenide/zinc sulfide/iron-cobalt oxide according to claim 1, wherein in the step (1), the molar ratio of ferric chloride hexahydrate, cobalt nitrate hexahydrate and 2-amino terephthalic acid is 1 (0.25-1): 1.
3. The method of claim 1, wherein in step (2), the heating is performed in an air atmosphere at a heating rate of 5 ℃/min.
4. The method for preparing cadmium indium selenide/zinc sulfide/iron-cobalt oxide according to claim 1, wherein in the step (3), the mass ratio of the iron-cobalt oxide, zinc acetate dihydrate and thiourea is (0.05-0.1): 1:0.35.
5. The method of claim 1, wherein in the step (4), the molar ratio of cadmium nitrate, indium nitrate, ligand to sodium selenate is 1 (0.05-0.2): 2.4 (0.2-0.3).
6. The use of cadmium indium selenide/zinc sulfide/iron-cobalt oxide in photocatalytic hydrogen production, characterized in that the cadmium indium selenide/zinc sulfide/iron-cobalt oxide is prepared by the preparation method of claim 1.
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| US20140174905A1 (en) * | 2012-12-20 | 2014-06-26 | Sunpower Technologies Llc | Photo-catalytic systems for the production of hydrogen |
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Effective date of registration: 20240308 Address after: 1478-1 Wangsha Road, Chengyang District, Qingdao City, Shandong Province, 266000 Patentee after: Qingdao Yuneng Sodium Lithium Battery New Materials Co.,Ltd. Country or region after: China Address before: 266000 Songling Road, Laoshan District, Qingdao, Shandong Province, No. 99 Patentee before: QINGDAO University OF SCIENCE AND TECHNOLOGY Country or region before: China |