CN112791735B - Cadmium sulfide material for anaerobic dehydrogenation of photocatalytic alcohol, and preparation and application thereof - Google Patents
Cadmium sulfide material for anaerobic dehydrogenation of photocatalytic alcohol, and preparation and application thereof Download PDFInfo
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- CN112791735B CN112791735B CN201911105407.XA CN201911105407A CN112791735B CN 112791735 B CN112791735 B CN 112791735B CN 201911105407 A CN201911105407 A CN 201911105407A CN 112791735 B CN112791735 B CN 112791735B
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- 229910052980 cadmium sulfide Inorganic materials 0.000 title claims abstract description 178
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 title claims abstract description 176
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 123
- 239000000463 material Substances 0.000 title claims abstract description 23
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 10
- 238000005342 ion exchange Methods 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000011065 in-situ storage Methods 0.000 claims abstract description 8
- 230000008021 deposition Effects 0.000 claims abstract description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 119
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 78
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 66
- 239000008367 deionised water Substances 0.000 claims description 55
- 229910021641 deionized water Inorganic materials 0.000 claims description 55
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 42
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 39
- 150000002500 ions Chemical class 0.000 claims description 25
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 23
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 22
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 21
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 21
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 19
- 229910021645 metal ion Inorganic materials 0.000 claims description 19
- 239000001301 oxygen Substances 0.000 claims description 19
- 229910052760 oxygen Inorganic materials 0.000 claims description 19
- 229910052697 platinum Inorganic materials 0.000 claims description 17
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 229910052707 ruthenium Inorganic materials 0.000 claims description 11
- 238000000151 deposition Methods 0.000 claims description 5
- 229910052737 gold Inorganic materials 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 229910052793 cadmium Inorganic materials 0.000 claims description 4
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052741 iridium Inorganic materials 0.000 claims description 4
- 229910052703 rhodium Inorganic materials 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 239000011593 sulfur Substances 0.000 claims description 4
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 claims description 3
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 claims description 3
- 239000002086 nanomaterial Substances 0.000 claims description 3
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- 238000002256 photodeposition Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 19
- 239000001257 hydrogen Substances 0.000 abstract description 19
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 19
- 238000011068 loading method Methods 0.000 abstract description 18
- 239000003054 catalyst Substances 0.000 abstract description 4
- 239000002131 composite material Substances 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- FRLJSGOEGLARCA-UHFFFAOYSA-N cadmium sulfide Chemical class [S-2].[Cd+2] FRLJSGOEGLARCA-UHFFFAOYSA-N 0.000 abstract 1
- 239000002082 metal nanoparticle Substances 0.000 abstract 1
- 238000004729 solvothermal method Methods 0.000 abstract 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 188
- 239000000243 solution Substances 0.000 description 55
- -1 polytetrafluoroethylene Polymers 0.000 description 51
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 36
- 238000001035 drying Methods 0.000 description 35
- 238000005406 washing Methods 0.000 description 35
- 239000007864 aqueous solution Substances 0.000 description 34
- 229910052786 argon Inorganic materials 0.000 description 18
- QOYRNHQSZSCVOW-UHFFFAOYSA-N cadmium nitrate tetrahydrate Chemical compound O.O.O.O.[Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QOYRNHQSZSCVOW-UHFFFAOYSA-N 0.000 description 18
- 238000001816 cooling Methods 0.000 description 18
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 18
- 239000004810 polytetrafluoroethylene Substances 0.000 description 18
- 238000007789 sealing Methods 0.000 description 18
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 17
- 238000009210 therapy by ultrasound Methods 0.000 description 17
- 239000004065 semiconductor Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000005341 cation exchange Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 150000004763 sulfides Chemical class 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- ZRSDQBKGDNPFLT-UHFFFAOYSA-N ethanol;oxolane Chemical compound CCO.C1CCOC1 ZRSDQBKGDNPFLT-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/043—Sulfides with iron group metals or platinum group metals
- B01J27/045—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
- B01J35/39—Photocatalytic properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
- C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1064—Platinum group metal catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1217—Alcohols
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1217—Alcohols
- C01B2203/1223—Methanol
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1217—Alcohols
- C01B2203/1229—Ethanol
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- 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)
- Catalysts (AREA)
Abstract
The invention relates to a preparation method and application of a cadmium sulfide material for photocatalytic alcohol anaerobic dehydrogenation. The method comprises the steps of firstly preparing nano cadmium sulfide by a solvothermal method, then modifying the surface of the cadmium sulfide by an ion exchange method, finally loading metal nano particles on a modified cadmium sulfide material by in-situ light deposition, and simultaneously generating hydrogen. The metal-cadmium sulfide composite catalyst prepared by the method has the advantages of high catalytic activity, good stability and the like in the anaerobic dehydrogenation reaction of the photocatalytic alcohol.
Description
Technical Field
The invention belongs to the technical field of material synthesis, and particularly relates to a preparation method and application of a cadmium sulfide material for photocatalytic alcohol anaerobic dehydrogenation.
Background
Cadmium sulfide is a semiconductor sulfide material with excellent visible light absorption, and has wide application in photocatalysis, photoelectrocatalysis, luminescent materials and sensing devices. However, cadmium sulfide is a direct band gap semiconductor, so that the problem of high recombination rate of photo-generated electrons and holes exists when the cadmium sulfide is used as a photocatalyst, and the utilization rate of photo-generated carriers is greatly influenced. In addition, cadmium sulfide in photocatalysis is easily corroded by light, so that the catalyst is seriously deactivated. Therefore, it is one of the major researches of researchers to improve the utilization rate of electron holes in cadmium sulfide and reduce the influence of photo-corrosion.
The cadmium sulfide and other semiconductor materials are compounded to form a heterojunction, which is an important means for improving the photocatalytic performance of the cadmium sulfide. Limited by the influence of interface charges, the band position of the semiconductor, and the like, the choice of semiconductor materials is limited, and commonly used materials are titanium dioxide (CN104646031A), carbon nitride (Applied Catalysis B: Environmental 2019,256,117848), and molybdenum disulfide (nat. Commun.2018,9,1181). The preparation method of the composite material is complex, and the stability of the formed interface heterojunction in the actual reaction is not high.
The solubility of different sulfides is different, and cation exchange can be realized according to the difference of the solubility. The promotion of the photocatalytic performance of cadmium sulfide by precipitating a second sulfide onto cadmium sulfide has been studied before (j.catal.2009,266,165), but no method for adjusting the photocatalytic activity of cadmium sulfide by ion exchange has been reported.
Disclosure of Invention
The invention provides a preparation method and application of a cadmium sulfide material for anaerobic dehydrogenation of photocatalytic alcohol. By carrying out cation exchange on the surface of the cadmium sulfide, the utilization rate of photo-generated carriers of the cadmium sulfide is improved, and the stability of the catalyst is enhanced.
The technical scheme is as follows:
firstly, thermally synthesizing a cadmium sulfide nano material by using cadmium nitrate and thiourea as raw materials under the condition of 120-180 ℃ (preferably 140-160 ℃), wherein the concentration of cadmium ions is 0.01-1 mmol/mL (preferably 0.1-0.5 mmol/mL), and using an ethylenediamine solvent; dispersing the obtained cadmium sulfide in deionized water, adding a metal ion solution, stirring at room temperature for 10-48 h, exchanging metal ions onto the cadmium sulfide in a positive ion form, and adjusting the ion doping amount in the exchanged material by controlling the amount of the added metal ion solution; finally, dispersing the cadmium sulfide after ion exchange in alcohol-containing liquid, adding a metal ion solution, and carrying out in-situ light deposition on the metal on the material in a zero-valent form.
The mol ratio of cadmium element to sulfur element in the solvothermal preparation of cadmium sulfide is 1: 1-1: 10, and the heating time is 6-48 hours.
The mol ratio of cadmium element to sulfur element in the solvothermal preparation of cadmium sulfide is preferably 1: 1-1: 4, and the heating time is preferably 12-36 hours.
During ion exchange, the selected ions are one or more of Pt, Pd and Ru, the concentration of the added cadmium sulfide is 1-10 mg/mL, and the mass of the added metal ions is 0.1-1% of that of the cadmium sulfide.
The concentration of cadmium sulfide added during ion exchange is preferably 2-5 mg/mL, the mass of metal ions added is 0.1-0.5% of that of the cadmium sulfide, and the stirring time at room temperature is preferably 12-24 h.
The metal subjected to in-situ photo-deposition is one or more of Pt, Pd, Ru, Rh, Au and Ir, and the mass of the metal is 0.1-2% of that of the ion-exchange cadmium sulfide; the liquid containing alcohol is a mixed system only containing one or more of methanol, ethanol and isopropanol, or one or more of methanol, ethanol and isopropanol and one or more of water, acetonitrile and tetrahydrofuran, and the volume content of one or more of water, acetonitrile and tetrahydrofuran in the mixed system is 1-99%, preferably 10-60%.
The metal subjected to in-situ light deposition is one or more of Pt, Pd and Ru, and the mass of the metal is 0.1-0.5% of that of the ion exchange cadmium sulfide.
The cadmium sulfide material prepared by the preparation method is used for the anaerobic dehydrogenation of photocatalytic alcohol.
The alcohol is a mixed system containing one or more of methanol, ethanol and isopropanol, or one or more of methanol, ethanol and isopropanol and one or more of water, acetonitrile and tetrahydrofuran, the volume content of one or more of water, acetonitrile and tetrahydrofuran in the mixed system is 1-99%, preferably 10-60%, and the selected light wavelength is 300-700 nm, preferably 400-550 nm.
Compared with other modification methods aiming at cadmium sulfide photocatalyst, the method has the advantages and beneficial effects that:
the preparation method is simple. The doping can be realized by stirring at room temperature by utilizing the difference of solubility products among different sulfides.
Compared with a loading type modification mode, metal ions in the doped cadmium sulfide formed by ion exchange enter a crystal lattice of the cadmium sulfide, contact is tighter, and the metal ions are not easy to lose in subsequent treatment or actual reaction.
The performance can be effectively enhanced by the required metal ion doping amount of less than 0.5 wt%, and the consumption of noble metal is saved.
The invention relates to a preparation method and application of a cadmium sulfide material for photocatalytic alcohol anaerobic dehydrogenation. The metal-cadmium sulfide composite catalyst prepared by the method has the advantages of high catalytic activity, good stability and the like in the anaerobic dehydrogenation reaction of the photocatalytic alcohol.
The specific implementation mode is as follows:
in order to further explain the present invention in detail, several specific embodiments are given below, but the present invention is not limited to these embodiments.
Example 1:
dissolving 2mmol of cadmium nitrate tetrahydrate and 8mmol of thiourea in 20mL of ethylenediamine, transferring the solution to a 50mL hydrothermal kettle with a polytetrafluoroethylene lining, sealing the kettle, and heating the kettle in an oven at 160 ℃ for 20 hours. And then taking out, cooling to room temperature, washing the product with deionized water and ethanol for three times respectively, and drying to obtain bright yellow cadmium sulfide (rod-shaped, with the diameter of 20-30 nm and the length of 50-100 nm). Dispersing 50mg of prepared cadmium sulfide in 50mL of deionized water, adding a certain amount of chloropalladate aqueous solution to ensure that the mass of palladium is 0.5 wt% of that of the cadmium sulfide, stirring at room temperature in a dark place for 12 hours, washing with deionized water and ethanol for three times respectively, and drying to obtain the ion-exchanged cadmium sulfide. Wherein the palladium is present as a positive ion, the ICP results show an ion-exchanged palladium content of 0.23 wt%. Dispersing 5mg of ion-exchanged cadmium sulfide in 1mL of methanol solution, adding a certain amount of chloropalladate aqueous solution to ensure that the mass of palladium is 1 wt% of that of the cadmium sulfide, removing oxygen in the solution by ultrasonic treatment, replacing air in the system with argon in a glove box, placing the system under a 455nm LED lamp for irradiation for 10 hours, reducing added palladium ions into zero-valent palladium and loading the palladium ions on the cadmium sulfide, and generating 25.9mL of hydrogen simultaneously.
Example 2:
dissolving 2mmol of cadmium nitrate tetrahydrate and 4mmol of thiourea in 20mL of ethylenediamine, transferring the solution to a 50mL hydrothermal kettle with a polytetrafluoroethylene lining, sealing the kettle, and heating the kettle in an oven at 160 ℃ for 20 hours. And then taking out, cooling to room temperature, washing the product with deionized water and ethanol for three times respectively, and drying to obtain bright yellow cadmium sulfide. Dispersing 50mg of prepared cadmium sulfide in 50mL of deionized water, adding a certain amount of chloropalladate aqueous solution to ensure that the mass of palladium is 0.5 wt% of that of the cadmium sulfide, stirring at room temperature in a dark place for 12 hours, washing with deionized water and ethanol for three times respectively, and drying to obtain the ion-exchanged cadmium sulfide. Wherein the palladium is present as a positive ion, the ICP results show an ion-exchanged palladium content of 0.21 wt%. Dispersing 5mg of ion-exchanged cadmium sulfide in 1mL of methanol solution, adding a certain amount of chloropalladate aqueous solution to ensure that the mass of palladium is 1 wt% of that of the cadmium sulfide, removing oxygen in the solution by ultrasonic treatment, replacing air in the system with argon in a glove box, placing the system under a 455nm LED lamp for irradiation for 10 hours, reducing added palladium ions into zero-valent palladium and loading the palladium ions on the cadmium sulfide, and generating 24.0mL of hydrogen simultaneously.
Example 3:
dissolving 2mmol of cadmium nitrate tetrahydrate and 2mmol of thiourea in 20mL of ethylenediamine, transferring the solution to a 50mL hydrothermal kettle with a polytetrafluoroethylene lining, sealing the kettle, and heating the kettle in an oven at 160 ℃ for 20 hours. And then taking out, cooling to room temperature, washing the product with deionized water and ethanol for three times respectively, and drying to obtain bright yellow cadmium sulfide. Dispersing 50mg of prepared cadmium sulfide in 50mL of deionized water, adding a certain amount of chloropalladate aqueous solution to ensure that the mass of palladium is 0.5 wt% of that of the cadmium sulfide, stirring at room temperature in a dark place for 12 hours, washing with deionized water and ethanol for three times respectively, and drying to obtain the ion-exchanged cadmium sulfide. Wherein the palladium is present as a positive ion, the ICP results show an ion-exchanged palladium content of 0.26 wt%. Dispersing 5mg of ion-exchanged cadmium sulfide in 1mL of methanol solution, adding a certain amount of chloropalladate aqueous solution to ensure that the mass of palladium is 1 wt% of that of the cadmium sulfide, removing oxygen in the solution by ultrasonic treatment, replacing air in the system with argon in a glove box, placing the system under a 455nm LED lamp for irradiation for 10 hours, reducing added palladium ions into zero-valent palladium and loading the palladium ions on the cadmium sulfide, and generating 22.3mL of hydrogen simultaneously.
Example 4:
dissolving 2mmol of cadmium nitrate tetrahydrate and 8mmol of thiourea in 20mL of ethylenediamine, transferring the solution to a 50mL hydrothermal kettle with a polytetrafluoroethylene lining, sealing the kettle, and heating the kettle in an oven at 160 ℃ for 36 hours. And then taking out, cooling to room temperature, washing the product with deionized water and ethanol for three times respectively, and drying to obtain bright yellow cadmium sulfide. Dispersing 50mg of prepared cadmium sulfide in 50mL of deionized water, adding a certain amount of chloropalladate aqueous solution to ensure that the mass of palladium is 0.5 wt% of that of the cadmium sulfide, stirring at room temperature in a dark place for 12 hours, washing with deionized water and ethanol for three times respectively, and drying to obtain the ion-exchanged cadmium sulfide. Wherein the palladium is present as a positive ion, the ICP results show an ion-exchanged palladium content of 0.19 wt%. Dispersing 5mg of ion-exchanged cadmium sulfide in 1mL of methanol solution, adding a certain amount of chloropalladate aqueous solution to ensure that the mass of palladium is 1 wt% of that of the cadmium sulfide, removing oxygen in the solution by ultrasonic treatment, replacing air in the system with argon in a glove box, placing the system under a 455nm LED lamp for irradiation for 10 hours, reducing added palladium ions into zero-valent palladium and loading the palladium ions on the cadmium sulfide, and generating 21.5mL of hydrogen simultaneously.
Example 5:
dissolving 2mmol of cadmium nitrate tetrahydrate and 8mmol of thiourea in 20mL of ethylenediamine, transferring the solution to a 50mL hydrothermal kettle with a polytetrafluoroethylene lining, sealing the kettle, and heating the kettle in an oven at 160 ℃ for 20 hours. And then taking out, cooling to room temperature, washing the product with deionized water and ethanol for three times respectively, and drying to obtain bright yellow cadmium sulfide. Dispersing 50mg of prepared cadmium sulfide in 50mL of deionized water, adding a certain amount of chloropalladate aqueous solution to ensure that the mass of palladium is 0.3 wt% of that of the cadmium sulfide, stirring at room temperature in a dark place for 12 hours, washing with deionized water and ethanol for three times respectively, and drying to obtain the ion-exchanged cadmium sulfide. Wherein the palladium is present as a positive ion, the ICP results show an ion-exchanged palladium content of 0.1 wt%. Dispersing 5mg of ion-exchanged cadmium sulfide in 1mL of methanol solution, adding a certain amount of chloropalladate aqueous solution to ensure that the mass of palladium is 1 wt% of that of cadmium sulfide, removing oxygen in the solution by ultrasonic treatment, replacing air in a system with argon in a glove box, placing the system under a 455nm LED lamp for irradiation for 10 hours, reducing added palladium ions into zero-valent palladium and loading the palladium ions on cadmium sulfide, and generating 22mL of hydrogen simultaneously.
Example 6:
dissolving 2mmol of cadmium nitrate tetrahydrate and 8mmol of thiourea in 20mL of ethylenediamine, transferring the solution to a 50mL hydrothermal kettle with a polytetrafluoroethylene lining, sealing the kettle, and heating the kettle in an oven at 140 ℃ for 20 hours. And then taking out, cooling to room temperature, washing the product with deionized water and ethanol for three times respectively, and drying to obtain bright yellow cadmium sulfide. Dispersing 50mg of prepared cadmium sulfide in 50mL of deionized water, adding a certain amount of chloropalladate aqueous solution to ensure that the mass of palladium is 0.5 wt% of that of the cadmium sulfide, stirring at room temperature in a dark place for 12 hours, washing with deionized water and ethanol for three times respectively, and drying to obtain the ion-exchanged cadmium sulfide. Wherein the palladium is present as a positive ion, the ICP results show an ion-exchanged palladium content of 0.3 wt%. Dispersing 5mg of ion-exchanged cadmium sulfide in 1mL of methanol solution, adding a certain amount of chloropalladate aqueous solution to ensure that the mass of palladium is 1 wt% of that of the cadmium sulfide, removing oxygen in the solution by ultrasonic treatment, replacing air in the system with argon in a glove box, placing the system under a 455nm LED lamp for irradiation for 10 hours, reducing added palladium ions into zero-valent palladium and loading the palladium ions on the cadmium sulfide, and generating 18.5mL of hydrogen simultaneously.
Example 7:
dissolving 2mmol of cadmium nitrate tetrahydrate and 8mmol of thiourea in 20mL of ethylenediamine, transferring the solution to a 50mL hydrothermal kettle with a polytetrafluoroethylene lining, sealing the kettle, and heating the kettle in an oven at 160 ℃ for 20 hours. And then taking out, cooling to room temperature, washing the product with deionized water and ethanol for three times respectively, and drying to obtain bright yellow cadmium sulfide. Dispersing 50mg of prepared cadmium sulfide in 50mL of deionized water, adding a certain amount of chloropalladate aqueous solution to ensure that the mass of palladium is 0.5 wt% of that of the cadmium sulfide, stirring at room temperature in a dark place for 12 hours, washing with deionized water and ethanol for three times respectively, and drying to obtain the ion-exchanged cadmium sulfide. Wherein the palladium is present as a positive ion, the ICP results show an ion-exchanged palladium content of 0.23 wt%. Dispersing 5mg of ion-exchanged cadmium sulfide in 1mL of methanol solution, adding a certain amount of chloropalladate aqueous solution to ensure that the mass of palladium is 0.5 wt% of that of cadmium sulfide, removing oxygen in the solution by ultrasonic treatment, replacing air in the system with argon in a glove box, placing the system under a 455nm LED lamp for irradiation for 10 hours, reducing added palladium ions into zero-valent palladium and loading the palladium ions on cadmium sulfide, and generating 14.4mL of hydrogen simultaneously.
Example 8:
dissolving 2mmol of cadmium nitrate tetrahydrate and 8mmol of thiourea in 20mL of ethylenediamine, transferring the solution to a 50mL hydrothermal kettle with a polytetrafluoroethylene lining, sealing the kettle, and heating the kettle in an oven at 160 ℃ for 20 hours. And then taking out, cooling to room temperature, washing the product with deionized water and ethanol for three times respectively, and drying to obtain bright yellow cadmium sulfide. Dispersing 50mg of prepared cadmium sulfide in 50mL of deionized water, adding a certain amount of chloroplatinic acid aqueous solution to ensure that the mass of platinum is 0.5 wt% of the mass of the cadmium sulfide, stirring at room temperature in a dark place for 12 hours, washing with deionized water and ethanol for three times respectively, and drying to obtain the ion-exchanged cadmium sulfide. Where platinum is present as a positive ion, the ICP results show an ion-exchanged platinum content of 0.18 wt%. Dispersing 5mg of ion-exchanged cadmium sulfide in 1mL of methanol solution, adding a certain amount of chloroauric acid aqueous solution to enable the mass of gold to be 1 wt% of that of the cadmium sulfide, removing oxygen in the solution by ultrasonic treatment, replacing air in the system with argon in a glove box, placing the system under a 455nm LED lamp for irradiation for 10 hours, reducing added palladium ions into zero-valent palladium and loading the palladium ions on the cadmium sulfide, and generating 4.5mL of hydrogen simultaneously.
Example 9:
dissolving 2mmol of cadmium nitrate tetrahydrate and 8mmol of thiourea in 20mL of ethylenediamine, transferring the solution to a 50mL hydrothermal kettle with a polytetrafluoroethylene lining, sealing the kettle, and heating the kettle in an oven at 160 ℃ for 20 hours. And then taking out, cooling to room temperature, washing the product with deionized water and ethanol for three times respectively, and drying to obtain bright yellow cadmium sulfide. Dispersing 50mg of prepared cadmium sulfide in 50mL of deionized water, adding a certain amount of chloroplatinic acid aqueous solution to ensure that the mass of platinum is 0.5 wt% of the mass of the cadmium sulfide, stirring at room temperature in a dark place for 12 hours, washing with deionized water and ethanol for three times respectively, and drying to obtain the ion-exchanged cadmium sulfide. Where platinum is present as a positive ion, the ICP results show an ion-exchanged platinum content of 0.11 wt%. Dispersing 5mg of ion-exchanged cadmium sulfide in 1mL of methanol solution, adding a certain amount of chloropalladate aqueous solution to ensure that the mass of palladium is 1 wt% of that of cadmium sulfide, removing oxygen in the solution by ultrasonic treatment, replacing air in a system with argon in a glove box, placing the system under a 455nm LED lamp for irradiation for 10 hours, reducing added palladium ions into zero-valent palladium and loading the palladium ions on cadmium sulfide, and generating 16.8mL of hydrogen simultaneously
Example 10:
dissolving 2mmol of cadmium nitrate tetrahydrate and 8mmol of thiourea in 20mL of ethylenediamine, transferring the solution to a 50mL hydrothermal kettle with a polytetrafluoroethylene lining, sealing the kettle, and heating the kettle in an oven at 160 ℃ for 20 hours. And then taking out, cooling to room temperature, washing the product with deionized water and ethanol for three times respectively, and drying to obtain bright yellow cadmium sulfide. Dispersing 50mg of prepared cadmium sulfide in 50mL of deionized water, adding a certain amount of chloropalladate aqueous solution to ensure that the mass of palladium is 0.5 wt% of that of the cadmium sulfide, stirring at room temperature in a dark place for 12 hours, washing with deionized water and ethanol for three times respectively, and drying to obtain the ion-exchanged cadmium sulfide. Wherein the palladium is present as a positive ion, the ICP results show an ion-exchanged palladium content of 0.23 wt%. Dispersing 5mg of ion-exchanged cadmium sulfide in 1mL of methanol solution, adding a certain amount of chloroplatinic acid aqueous solution to ensure that the mass of platinum is 0.5 wt% of the mass of cadmium sulfide, removing oxygen in the solution by ultrasonic treatment, replacing air in a system with argon in a glove box, placing under a 455nm LED lamp for irradiation for 10 hours, reducing added palladium ions into zero-valent palladium and loading the palladium ions on cadmium sulfide, and generating 10.8mL of hydrogen simultaneously.
Example 11:
dissolving 2mmol of cadmium nitrate tetrahydrate and 8mmol of thiourea in 20mL of ethylenediamine, transferring the solution to a 50mL hydrothermal kettle with a polytetrafluoroethylene lining, sealing the kettle, and heating the kettle in an oven at 160 ℃ for 20 hours. And then taking out, cooling to room temperature, washing the product with deionized water and ethanol for three times respectively, and drying to obtain bright yellow cadmium sulfide. Dispersing 50mg of prepared cadmium sulfide in 50mL of deionized water, adding a certain amount of chloropalladate aqueous solution to ensure that the mass of palladium is 0.5 wt% of that of the cadmium sulfide, stirring at room temperature in a dark place for 12 hours, washing with deionized water and ethanol for three times respectively, and drying to obtain the ion-exchanged cadmium sulfide. Wherein the palladium is present as a positive ion, the ICP results show an ion-exchanged palladium content of 0.23 wt%. Dispersing 5mg of ion-exchanged cadmium sulfide in 1mL of methanol solution, adding a certain amount of ruthenium trichloride aqueous solution to ensure that the mass of ruthenium is 1 wt% of that of cadmium sulfide, removing oxygen in the solution by ultrasonic treatment, replacing air in a system with argon in a glove box, placing the system under a 455nm LED lamp for irradiation for 10 hours, reducing added palladium ions into zero-valent palladium and loading the palladium ions on cadmium sulfide, and generating 11.6mL of hydrogen simultaneously.
Example 12:
dissolving 2mmol of cadmium nitrate tetrahydrate and 8mmol of thiourea in 20mL of ethylenediamine, transferring the solution to a 50mL hydrothermal kettle with a polytetrafluoroethylene lining, sealing the kettle, and heating the kettle in an oven at 160 ℃ for 20 hours. And then taking out, cooling to room temperature, washing the product with deionized water and ethanol for three times respectively, and drying to obtain bright yellow cadmium sulfide. Dispersing 50mg of prepared cadmium sulfide in 50mL of deionized water, adding a certain amount of chloropalladate aqueous solution to ensure that the mass of palladium is 0.5 wt% of that of the cadmium sulfide, stirring at room temperature in a dark place for 12 hours, washing with deionized water and ethanol for three times respectively, and drying to obtain the ion-exchanged cadmium sulfide. Wherein the palladium is present as a positive ion, the ICP results show an ion-exchanged palladium content of 0.23 wt%. Dispersing 5mg of ion-exchanged cadmium sulfide in 1mL of ethanol solution, adding a certain amount of chloropalladate aqueous solution to ensure that the mass of palladium is 1 wt% of that of cadmium sulfide, removing oxygen in the solution by ultrasonic treatment, replacing air in a system with argon in a glove box, placing the system under a 455nm LED lamp for irradiation for 10 hours, reducing added palladium ions into zero-valent palladium and loading the palladium ions on cadmium sulfide, and generating 32.1mL of hydrogen simultaneously.
Example 13:
dissolving 2mmol of cadmium nitrate tetrahydrate and 8mmol of thiourea in 20mL of ethylenediamine, transferring the solution to a 50mL hydrothermal kettle with a polytetrafluoroethylene lining, sealing the kettle, and heating the kettle in an oven at 160 ℃ for 20 hours. And then taking out, cooling to room temperature, washing the product with deionized water and ethanol for three times respectively, and drying to obtain bright yellow cadmium sulfide. Dispersing 50mg of prepared cadmium sulfide in 50mL of deionized water, adding a certain amount of chloropalladate aqueous solution to ensure that the mass of palladium is 0.5 wt% of that of the cadmium sulfide, stirring at room temperature in a dark place for 12 hours, washing with deionized water and ethanol for three times respectively, and drying to obtain the ion-exchanged cadmium sulfide. Wherein the palladium is present as a positive ion, the ICP results show an ion-exchanged palladium content of 0.23 wt%. Dispersing 5mg of ion-exchanged cadmium sulfide in 1mL of isopropanol solution, adding a certain amount of chloropalladate aqueous solution to ensure that the mass of palladium is 1 wt% of that of the cadmium sulfide, removing oxygen in the solution by ultrasonic treatment, replacing air in a system with argon in a glove box, placing the system under a 455nm LED lamp for irradiation for 10 hours, reducing added palladium ions into zero-valent palladium and loading the palladium ions on the cadmium sulfide, and generating 44.7mL of hydrogen simultaneously.
Example 14:
dissolving 2mmol of cadmium nitrate tetrahydrate and 8mmol of thiourea in 20mL of ethylenediamine, transferring the solution to a 50mL hydrothermal kettle with a polytetrafluoroethylene lining, sealing the kettle, and heating the kettle in an oven at 160 ℃ for 20 hours. And then taking out, cooling to room temperature, washing the product with deionized water and ethanol for three times respectively, and drying to obtain bright yellow cadmium sulfide. Dispersing 50mg of prepared cadmium sulfide in 50mL of deionized water, adding a certain amount of chloropalladate aqueous solution to ensure that the mass of palladium is 0.5 wt% of that of the cadmium sulfide, stirring at room temperature in a dark place for 12 hours, washing with deionized water and ethanol for three times respectively, and drying to obtain the ion-exchanged cadmium sulfide. Wherein the palladium is present as a positive ion, the ICP results show an ion-exchanged palladium content of 0.23 wt%. 5mg of ion-exchanged cadmium sulfide was dispersed in 1mL of a mixed solution of methanol and acetonitrile (methanol/acetonitrile volume ratio 1/1), a certain amount of chloropalladate aqueous solution was added so that the mass of palladium was 1 wt% of the mass of cadmium sulfide, oxygen in the solution was removed by ultrasonic treatment, air in the system was replaced with argon gas in a glove box, and then the system was placed under a 455nm LED lamp and irradiated for 10 hours, to reduce the added palladium ions to zero-valent palladium and load the palladium ions on cadmium sulfide, while generating 19.4mL of hydrogen.
Example 15:
dissolving 2mmol of cadmium nitrate tetrahydrate and 8mmol of thiourea in 20mL of ethylenediamine, transferring the solution to a 50mL hydrothermal kettle with a polytetrafluoroethylene lining, sealing the kettle, and heating the kettle in an oven at 160 ℃ for 20 hours. And then taking out, cooling to room temperature, washing the product with deionized water and ethanol for three times respectively, and drying to obtain bright yellow cadmium sulfide. Dispersing 50mg of prepared cadmium sulfide in 50mL of deionized water, adding a certain amount of chloropalladate aqueous solution to ensure that the mass of palladium is 0.5 wt% of that of the cadmium sulfide, stirring at room temperature in a dark place for 12 hours, washing with deionized water and ethanol for three times respectively, and drying to obtain the ion-exchanged cadmium sulfide. Wherein the palladium is present as a positive ion, the ICP results show an ion-exchanged palladium content of 0.23 wt%. Dispersing 5mg of ion-exchanged cadmium sulfide in 1mL of ethanol-tetrahydrofuran mixed solution (ethanol/tetrahydrofuran volume ratio of 1/1), adding a certain amount of chloropalladate aqueous solution to ensure that the mass of palladium is 1 wt% of the mass of cadmium sulfide, removing oxygen in the solution by ultrasonic treatment, replacing air in the system with argon in a glove box, placing under a 455nm LED lamp for irradiation for 10 hours, reducing added palladium ions into zero-valent palladium and loading the palladium ions on cadmium sulfide, and generating 16.7mL of hydrogen simultaneously.
Example 16:
dissolving 2mmol of cadmium nitrate tetrahydrate and 8mmol of thiourea in 20mL of ethylenediamine, transferring the solution to a 50mL hydrothermal kettle with a polytetrafluoroethylene lining, sealing the kettle, and heating the kettle in an oven at 160 ℃ for 20 hours. And then taking out, cooling to room temperature, washing the product with deionized water and ethanol for three times respectively, and drying to obtain bright yellow cadmium sulfide. Dispersing 50mg of prepared cadmium sulfide in 50mL of deionized water, adding a certain amount of chloropalladate aqueous solution to ensure that the mass of palladium is 0.5 wt% of that of the cadmium sulfide, stirring at room temperature in a dark place for 12 hours, washing with deionized water and ethanol for three times respectively, and drying to obtain the ion-exchanged cadmium sulfide. Wherein the palladium is present as a positive ion, the ICP results show an ion-exchanged palladium content of 0.23 wt%. Dispersing 5mg of ion-exchanged cadmium sulfide in 1mL of methanol solution, adding a certain amount of chloropalladate aqueous solution to ensure that the mass of palladium is 2 wt% of that of the cadmium sulfide, removing oxygen in the solution by ultrasonic treatment, replacing air in the system with argon in a glove box, placing the system under a 455nm LED lamp for irradiation for 10 hours, reducing added palladium ions into zero-valent palladium and loading the palladium ions on the cadmium sulfide, and generating 23.1mL of hydrogen simultaneously.
Comparative example 1:
dissolving 2mmol of cadmium nitrate tetrahydrate and 8mmol of thiourea in 20mL of ethylenediamine, transferring the solution to a 50mL hydrothermal kettle with a polytetrafluoroethylene lining, sealing the kettle, and heating the kettle in an oven at 160 ℃ for 20 hours. And then taking out, cooling to room temperature, washing the product with deionized water and ethanol for three times respectively, and drying to obtain bright yellow cadmium sulfide (rod-shaped, with the diameter of 20-30 nm and the length of 50-100 nm). Dispersing 5mg of the cadmium sulfide prepared above in 1mL of methanol solution, adding a certain amount of chloropalladate aqueous solution to ensure that the mass of palladium is 1 wt% of that of the cadmium sulfide, removing oxygen in the solution by ultrasonic treatment, replacing air in the system with argon in a glove box, placing under a 455nm LED lamp for irradiation for 10 hours, reducing added palladium ions into zero-valent palladium and loading on the cadmium sulfide, and generating 13.2mL of hydrogen simultaneously.
Comparative example 2:
dissolving 2mmol of cadmium nitrate tetrahydrate and 8mmol of thiourea in 20mL of ethylenediamine, transferring the solution to a 50mL hydrothermal kettle with a polytetrafluoroethylene lining, sealing the kettle, and heating the kettle in an oven at 160 ℃ for 20 hours. And then taking out, cooling to room temperature, washing the product with deionized water and ethanol for three times respectively, and drying to obtain bright yellow cadmium sulfide (rod-shaped, with the diameter of 20-30 nm and the length of 50-100 nm). Dispersing 50mg of prepared cadmium sulfide in 50mL of deionized water, adding a certain amount of chloropalladate aqueous solution to ensure that the mass of palladium is 0.5 wt% of that of the cadmium sulfide, stirring at room temperature in a dark place for 12 hours, washing with deionized water and ethanol for three times respectively, and drying to obtain the ion-exchanged cadmium sulfide. Wherein the palladium is present as a positive ion, the ICP results show an ion-exchanged palladium content of 0.23 wt%. 5mg of ion-exchanged cadmium sulfide was dispersed in 1mL of a methanol solution, oxygen in the solution was removed by ultrasonic wave, and after replacing the air in the system with argon gas in a glove box, the system was placed under a 455nm LED lamp and irradiated for 10 hours to generate 1.2mL of hydrogen.
Claims (13)
1. A preparation method of cadmium sulfide material for anaerobic dehydrogenation of photocatalytic alcohol is characterized by comprising the following steps:
firstly, thermally synthesizing a cadmium sulfide nano material by using cadmium nitrate and thiourea as raw materials at 120-180 ℃ in an ethylenediamine solvent, wherein the concentration of cadmium ions is 0.01-1 mmol/mL; dispersing the obtained cadmium sulfide in deionized water, adding one or more metal ion solutions of Pt, Pd and Ru, stirring at room temperature for 10-48 h, exchanging metal ions onto the cadmium sulfide in the form of positive ions, and adjusting the ion doping amount in the exchanged material by controlling the amount of the added metal ion solution; finally, dispersing the cadmium sulfide after ion exchange in alcohol-containing liquid, adding one or more metal ion solutions of Pt, Pd, Ru, Rh, Au and Ir, and carrying out in-situ light deposition on the metal on the material in a zero-valent form.
2. The method of claim 1, wherein: firstly, thermally synthesizing a cadmium sulfide nano material by using cadmium nitrate and thiourea as raw materials under the condition of 140-160 ℃, wherein the concentration of cadmium ions is 0.1-0.5 mmol/mL, and using an ethylenediamine solvent; dispersing the obtained cadmium sulfide in deionized water, adding one or more metal ion solutions of Pt, Pd and Ru, stirring at room temperature for 10-48 h, exchanging metal ions onto the cadmium sulfide in the form of positive ions, and adjusting the ion doping amount in the exchanged material by controlling the amount of the added metal ion solution; finally, dispersing the cadmium sulfide after ion exchange in alcohol-containing liquid, adding one or more metal ion solutions of Pt, Pd, Ru, Rh, Au and Ir, and carrying out in-situ light deposition on the metal on the material in a zero-valent form.
3. The method of claim 1, wherein: the mol ratio of cadmium element to sulfur element in the solvothermal preparation of cadmium sulfide is 1: 1-1: 10, and the heating time is 6-48 hours.
4. The production method according to claim 1 or 3, characterized in that: the mol ratio of cadmium element to sulfur element in the solvothermal preparation of cadmium sulfide is 1: 1-1: 4, and the heating time is 12-36 hours.
5. The method of claim 1, wherein: during ion exchange, the selected ions are one or more of Pt, Pd and Ru, the concentration of the added cadmium sulfide is 1-10 mg/mL, and the mass of the added metal ions is 0.1-1% of that of the cadmium sulfide.
6. The production method according to claim 1 or 5, characterized in that: the concentration of the added cadmium sulfide during ion exchange is 2-5 mg/mL, the mass of the added metal ions is 0.1-0.5% of that of the cadmium sulfide, and the stirring time at room temperature is 12-24 h.
7. The method of claim 1, wherein: the metal subjected to in-situ photo-deposition is one or more of Pt, Pd, Ru, Rh, Au and Ir, and the mass of the metal is 0.1-2% of that of the ion-exchange cadmium sulfide; the alcohol-containing liquid is a mixed system only containing one or more of methanol, ethanol and isopropanol, or one or more of methanol, ethanol and isopropanol and one or more of water, acetonitrile and tetrahydrofuran, and the volume content of one or more of water, acetonitrile and tetrahydrofuran in the mixed system is 1-99%.
8. The method of claim 7, wherein: the volume content of one or more of water, acetonitrile and tetrahydrofuran in the mixed system is 10-60%.
9. The production method according to claim 1 or 7, characterized in that: the metal subjected to in-situ light deposition is one or more of Pt, Pd and Ru, and the mass of the metal is 0.1-0.5% of that of the ion exchange cadmium sulfide.
10. A cadmium sulfide material prepared by the preparation method of any one of claims 1 to 9.
11. Use of the cadmium sulfide material of claim 10 to photocatalytically dehydrogenate an alcohol in the absence of oxygen.
12. Use according to claim 11, characterized in that: the alcohol is one or more of methanol, ethanol and isopropanol, or a mixed system of one or more of methanol, ethanol and isopropanol and one or more of water, acetonitrile and tetrahydrofuran, the volume content of one or more of water, acetonitrile and tetrahydrofuran in the mixed system is 1-99%, and the selected light wavelength is 300-700 nm.
13. Use according to claim 12, characterized in that: the alcohol is one or more of methanol, ethanol and isopropanol, or a mixed system of one or more of methanol, ethanol and isopropanol and one or more of water, acetonitrile and tetrahydrofuran, the volume content of one or more of water, acetonitrile and tetrahydrofuran in the mixed system is 10-60%, and the selected light wavelength is 400-550 nm.
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