CN116639650A - Method and system for decomposing water by photocatalysis by utilizing nonlinear spectrum conversion - Google Patents
Method and system for decomposing water by photocatalysis by utilizing nonlinear spectrum conversion Download PDFInfo
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- CN116639650A CN116639650A CN202310613978.4A CN202310613978A CN116639650A CN 116639650 A CN116639650 A CN 116639650A CN 202310613978 A CN202310613978 A CN 202310613978A CN 116639650 A CN116639650 A CN 116639650A
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- Prior art keywords
- reaction tank
- photocatalytic
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- water splitting
- reaction
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 164
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 131
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 65
- 238000000034 method Methods 0.000 title claims abstract description 50
- 238000001228 spectrum Methods 0.000 title claims abstract description 26
- 238000007146 photocatalysis Methods 0.000 title abstract description 10
- 239000011941 photocatalyst Substances 0.000 claims abstract description 28
- 230000003595 spectral effect Effects 0.000 claims abstract description 19
- 239000000498 cooling water Substances 0.000 claims abstract description 18
- 239000002904 solvent Substances 0.000 claims abstract description 11
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 129
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 78
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 63
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 44
- 238000003756 stirring Methods 0.000 claims description 43
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 42
- -1 oxynitrides Chemical class 0.000 claims description 10
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
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- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 claims description 2
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- 238000004519 manufacturing process Methods 0.000 abstract description 18
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- 239000001257 hydrogen Substances 0.000 abstract description 15
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 15
- 230000007062 hydrolysis Effects 0.000 abstract description 2
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 113
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- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 24
- 150000003839 salts Chemical class 0.000 description 24
- 239000005457 ice water Substances 0.000 description 22
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- 239000011734 sodium Substances 0.000 description 15
- 229910052724 xenon Inorganic materials 0.000 description 15
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 14
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 14
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 14
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- 229910052761 rare earth metal Inorganic materials 0.000 description 14
- 238000001816 cooling Methods 0.000 description 13
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- 238000013032 photocatalytic reaction Methods 0.000 description 13
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- 238000009210 therapy by ultrasound Methods 0.000 description 13
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- 238000010438 heat treatment Methods 0.000 description 9
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- 239000002994 raw material Substances 0.000 description 8
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 8
- OJPDDQSCZGTACX-UHFFFAOYSA-N 2-[n-(2-hydroxyethyl)anilino]ethanol Chemical compound OCCN(CCO)C1=CC=CC=C1 OJPDDQSCZGTACX-UHFFFAOYSA-N 0.000 description 7
- KCKZIWSINLBROE-UHFFFAOYSA-N 3,4-dihydro-1h-naphthalen-2-one Chemical compound C1=CC=C2CC(=O)CCC2=C1 KCKZIWSINLBROE-UHFFFAOYSA-N 0.000 description 7
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 7
- 239000005695 Ammonium acetate Substances 0.000 description 7
- 229960000583 acetic acid Drugs 0.000 description 7
- 229940043376 ammonium acetate Drugs 0.000 description 7
- 235000019257 ammonium acetate Nutrition 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 239000000706 filtrate Substances 0.000 description 7
- 239000012362 glacial acetic acid Substances 0.000 description 7
- 239000010410 layer Substances 0.000 description 7
- 239000012044 organic layer Substances 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 6
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- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 5
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- CNUDBTRUORMMPA-UHFFFAOYSA-N formylthiophene Chemical compound O=CC1=CC=CS1 CNUDBTRUORMMPA-UHFFFAOYSA-N 0.000 description 5
- 229910052740 iodine Inorganic materials 0.000 description 5
- 239000011630 iodine Substances 0.000 description 5
- 238000004020 luminiscence type Methods 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
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- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 5
- 230000001376 precipitating effect Effects 0.000 description 5
- 229910000033 sodium borohydride Inorganic materials 0.000 description 5
- 239000012279 sodium borohydride Substances 0.000 description 5
- 238000010025 steaming Methods 0.000 description 5
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 5
- 238000003828 vacuum filtration Methods 0.000 description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
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- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
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- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
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- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 238000006303 photolysis reaction Methods 0.000 description 2
- 230000015843 photosynthesis, light reaction Effects 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
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- 229910052793 cadmium Inorganic materials 0.000 description 1
- 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 1
- AUIZLSZEDUYGDE-UHFFFAOYSA-L cadmium(2+);diacetate;dihydrate Chemical compound O.O.[Cd+2].CC([O-])=O.CC([O-])=O AUIZLSZEDUYGDE-UHFFFAOYSA-L 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
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- 239000004065 semiconductor Substances 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
- 241000894007 species Species 0.000 description 1
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Classifications
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- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F33/00—Other mixers; Mixing plants; Combinations of mixers
- B01F33/45—Magnetic mixers; Mixers with magnetically driven stirrers
-
- 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
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0053—Details of the reactor
-
- 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
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J19/12—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electromagnetic waves
- B01J19/122—Incoherent waves
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D221/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00
- C07D221/02—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00 condensed with carbocyclic rings or ring systems
- C07D221/04—Ortho- or peri-condensed ring systems
- C07D221/18—Ring systems of four or more rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
- C07D333/14—Radicals substituted by singly bound hetero atoms other than halogen
- C07D333/20—Radicals substituted by singly bound hetero atoms other than halogen by nitrogen atoms
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1014—Carbocyclic compounds bridged by heteroatoms, e.g. N, P, Si or B
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
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Abstract
The invention discloses a method and a system for decomposing water by photocatalysis by utilizing nonlinear spectrum conversion. The photocatalytic water splitting method comprises the following steps: in the photocatalytic water splitting reaction, firstly, a photocatalyst is utilized to absorb a light source spectrum, then a fluorescent solution is utilized to secondarily absorb an unabsorbed light source spectrum, and low-energy photons are converted into high-energy photons for the photocatalyst to absorb again; the fluorescent solution is obtained by dissolving a solute having nonlinear spectral conversion characteristics in a solvent. The system comprises a reaction tank, a jacket, a light source, a magnetic stirrer, a cooling water inlet, a cooling water outlet, an air inlet and an air outlet; the reaction tank is sleeved with a jacket; a light source is arranged above the reaction tank; the magnetic stirrer is positioned at the bottom of the jacket; a cooling water inlet and a cooling water outlet are formed in the jacket; the reaction tank is provided with an air inlet and an air outlet. The method and the system can improve the hydrogen production performance of the photocatalytic hydrolysis, and have the advantages of simple method, unique conception and convenient operation of the system.
Description
Technical Field
The invention belongs to the technical field of photocatalysis, and particularly relates to a method and a system for decomposing water by utilizing nonlinear spectrum conversion.
Background
Since the beginning of the industrial revolution, coal, oil, and natural gas have been three major sources of energy commonly used by humans. However, with the continuous development of human society, the demand for renewable energy is also increasing, and the technology of decomposing water by solar energy, which is rising from the inspired photosynthesis of plants, is widely focused on obtaining renewable hydrogen energy with high heat value and no pollution. The first discovery of TiO from Fujishima 2 Since the performance of decomposing water under visible light, the field of photocatalytic water decomposition has opened a new gate, and through continuous research for decades, the photocatalytic technology has become a research hotspot in the scientific field.
Photocatalysts are the heart of research in the field of photocatalysis. The conventional photocatalyst can be divided into a wide-bandgap catalyst and a narrow-bandgap catalyst according to the division of the forbidden bandwidth. Most of the wide band gap catalysts can only absorb ultraviolet light which only accounts for 5% of solar energy, so that the wide band gap catalysts are greatly limited in the application process, the narrow band gap catalysts can only absorb ultraviolet light and part of visible light, infrared light which accounts for more than 50% of solar spectrum energy cannot be utilized, and the too narrow band gap can cause the problems that the catalyst has insufficient driving force of oxidation-reduction potential and further has reduced oxidation-reduction capability and the like. In response to these problems, the related art has also studied various methods for modifying the catalyst. Such as morphology control, metal doping, promoter loading, construction of heterojunction, external field coordination, etc. Although the methods can improve the performance of the catalyst to a certain extent, the absorption of the modified catalyst to the solar spectrum is still very limited, and compared with the method for realizing the aim that the industrial application can be carried out only when the STH value reaches 10 percent, the method has a great gap.
Rare earth doped up-conversion luminescence is based on the process of continuously absorbing two or more photons with longer wavelength and lower energy, reaching a final luminescence energy level through non-radiative relaxation, and finally transitioning from the luminescence energy level to a ground state energy level, and emitting a photon with shorter wavelength and higher energy. The process can solve the problem that the photocatalyst has too low utilization of solar spectrum energy to a great extent, thereby improving the water decomposition performance of the photocatalyst.
Although the rare earth doped up-conversion material can improve the performance of photocatalytic water splitting to a certain extent, the method still has some problems:
first, in order to realize efficient excited state absorption process, rare earth ions as luminescence centers must have a large absorption cross section, a ladder-like distributed energy level structure, a relatively stable intermediate energy level of active ions, and sufficient electron population. Only a few rare earth ions such as Er 3+ 、Ho 3+ ,Tm 3+ And Nd 3+ Such an energy level structure is provided.
Secondly, in order to make the catalyst have photon up-conversion property, rare earth ions must be compounded with the catalyst by doping, and due to the existence of interfaces between the up-conversion material and the semiconductor material, improper interface defects in the compounding process can cause quenching of up-conversion luminescence or become a compound center of photo-generated carriers, which greatly reduces the catalytic activity of the up-conversion photocatalytic material, and meanwhile, the doping process also has the condition that the structure and active sites of the catalyst are influenced due to energy level mismatch, so that the photocatalytic performance is reduced.
Third, for rare earth doped up-conversion materials, lasers such as 1500mw, 980mw, 808mw are commonly used as light sources to irradiate rare earth ions, because the up-conversion material can only convert photons at a single wavelength into photons within the absorption edge range of the catalyst, and the converted spectrum is very narrow and cannot fully utilize photons in the near infrared region, so that the absorption efficiency of the rare earth doped catalyst for the whole spectrum is still low.
Fourth, rare earth doped up-conversion materials have harsh preparation conditions, not only the catalyst has a proper band gap to capture the high-energy light emitted by up-conversion, but also the sensitizer and the activator are needed to assist in spectral conversion, so that not all catalysts can utilize the up-conversion effect to convert low-energy photons in a rare earth doping manner. For the above reasons, almost no full water splitting of rare earth doped catalysts under full spectrum is currently reported.
In view of this, the present invention has been proposed.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide a photocatalysis water decomposing method and system by utilizing nonlinear spectrum conversion, which solve the problem that the prior rare earth metal doped up-conversion material is applied to photocatalysis water decomposing, and the performance of the photocatalysis water decomposing is obviously improved.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a method of photocatalytic water splitting using nonlinear spectral conversion, comprising: in the photocatalytic water splitting reaction, firstly, a photocatalyst is utilized to absorb a light source spectrum, then a fluorescent solution is utilized to secondarily absorb an unabsorbed light source spectrum, and low-energy photons are converted into high-energy photons for the photocatalyst to absorb again;
wherein the fluorescent solution is obtained by dissolving a solute with nonlinear spectral conversion characteristics in a solvent.
As a preferred embodiment of the present invention, the photocatalytic water splitting method includes:
s1, dissolving a solute with nonlinear spectrum conversion characteristics in a solvent to obtain a fluorescent solution;
s2, placing the photocatalyst in a reaction tank;
s3, adding the fluorescent solution obtained in the step S1 into a jacket outside the reaction tank;
s4, controlling the temperature of the reaction tank, and carrying out photocatalytic water splitting reaction by using a light source under the stirring condition.
Preferably, the photocatalyst is selected from one or more of composite oxides, sulfides, oxysulfides, nitrides, oxynitrides, halides and oxyhalides. Such as the usual CdS, etc., can be selected by those skilled in the art.
As a preferred aspect of the present invention, the solute having nonlinear spectral conversion characteristics is selected from one or two of dscs and X2;
wherein, the structural formula of DSc is as follows:
wherein, the structural formula of X2 is as follows:
as the preferable selection of the technical scheme of the invention, the preparation method of the DSc is as follows: 81.60g (0.45 mol) of dihydroxyethylaniline was dissolved in 108mL of pyridine, 127.50mL (1.35 mol) of acetic anhydride was added thereto, and the mixture was heated under reflux at 110℃for 6 hours; cooling, pouring into ice water, washing with water for more than 10 times until the color of the upper layer solution turns light grey, extracting with dichloromethane, evaporating to dryness, concentrating, and purifying with petroleum ether and ethyl acetate by 20:1 column chromatography to obtain white solid; under ice bath conditions, 23.70g (0.15 mol) of phosphorus oxychloride is weighed and dripped into 5.60g (0.07 mol) of dimethylformamide to form frozen salt, 50mL of chloroform solution dissolved with 8.00g (0.03 mol) of raw material is added into the frozen salt, the temperature is slowly raised to 65 ℃, and the mixture is refluxed for 6 hours; pouring the product into crushed ice, regulating the pH value to be slightly alkaline by using a sodium hydroxide solution, extracting by using dichloromethane, taking a lower organic layer, evaporating to dryness to obtain the product, dispersing by using ethanol to obtain a white solid, and naming the white solid as M;
3.85g (50 mmol) of ammonium acetate, 1.47g (5 mmol) of M, 1.49g (10 mmol) of 2-tetralone and 30mL of glacial acetic acid are added into a round bottom flask in sequence, and stirring is carried out for 24h at normal temperature; filtering to obtain solid, pouring the filtrate into a large amount of water to obtain milky solid, filtering, drying, purifying with petroleum ether and ethyl acetate by 5:1 column chromatography to obtain milky solid (marked as intermediate a); 0.50g (0.90 mmol) of intermediate a is added into a round-bottom flask, 100mL of ethanol is used for dissolution, 10% sodium hydroxide aqueous solution with the mass of the solution is added, stirring is carried out for 24 hours at normal temperature, the pH is regulated to be neutral by dilute hydrochloric acid solution, solid is obtained by suction filtration, a large amount of water is used for washing, dichloromethane extraction is carried out, and fluorescent solute DSc is obtained by evaporation.
As the preferable technical scheme of the invention, the preparation method of X2 is as follows: dimethylformamide (7.3 g,0.1 mol) was added to a 150mL round bottom flask, placed in an ice bath, and phosphorus oxychloride (60 g,0.4 mol) was slowly dropped into the flask with stirring using a constant pressure dropping funnel until the dropping was completed in the form of a white frozen salt; weighing triphenylamine (12 g,0.05 mol), adding into the frozen salt, transferring into an oil bath, heating to 65 ℃ after melting, cooling to room temperature after reaction for 3 hours, pouring into ice water, regulating the pH to about neutral by using sodium hydroxide solution, precipitating a large amount of light yellow solid, filtering, and drying; separating by column chromatography (silica gel column, developing agent-petroleum ether: ethyl acetate-30:1) to obtain white crystal; into a 250mL round bottom flask was added 100mL of the above white crystals (5.00 g,0.02 mol), sodium borohydride (2 g,0.05 mol) was added in portions with stirring, and the mixture was refluxed for 2h, cooled to room temperature, poured into ice water, extracted with dichloromethane, dried over anhydrous sodium sulfate, filtered, and the dichloromethane was evaporated to give a colorless liquid; adding the liquid (3.00 g, 0.0111 mmol) into a 150mL round bottom flask, placing the flask in ice water, respectively adding 50mL of methanol, 10mL of triethyl phosphite and iodine (2.81 g, 0.0111 mol), reacting for 12h under the protection of nitrogen, performing vacuum filtration after the reaction is finished, removing excessive triethyl phosphite, and separating by column chromatography to obtain light blue solid;
Under the irradiation of an infrared lamp at a drying position, adding the obtained solid (5.510 g, 0.010mol) and potassium tert-butoxide (4.490 g,0.040 mol) into an agate mortar respectively, rapidly grinding for 10 minutes, gradually changing the white solid in the mortar into an oil state, then adding thiophenecarboxaldehyde (1.122 g, 0.010mol), and continuously grinding for 10 minutes; pouring into water, stirring for 1h, extracting the liquid with dichloromethane, drying with anhydrous sodium sulfate, filtering, steaming out dichloromethane, and separating by column chromatography (silica gel column, developing agent-petroleum ether: ethyl acetate=10:1) to obtain light blue solid X2.
It should be emphasized that the principle of selection of the solute species is: the spectrum wavelength emitted after the fluorescence solution absorbs the spectrum is matched with the optimal excitation wavelength of the photocatalyst; for the solute, photoluminescence spectrum test can be performed, and then the photoluminescence spectrum test is matched with the excitation characteristics of the corresponding photocatalyst. As shown in FIG. 1, the photoluminescence spectrum of DSc is shown, and the wavelength emitted after absorption is matched with CdS.
Preferably, the solvent is selected from one or more of dimethylformamide, dimethyl sulfoxide, acetonitrile, tetrahydrofuran, dichloromethane, benzene, ethanol and ethyl acetate.
It is emphasized that the solvent and solute provided by the present invention are compatible, i.e. the solvent can dissolve the solute.
As a preferred embodiment of the present invention, the concentration of the solute in the solvent is 10 -4 ~10 -1 mol/L。
As a preferable mode of the technical scheme of the invention, in the step S4, the temperature of the reaction tank is 10-20 ℃.
As a preferable mode of the technical scheme of the invention, in the step S4, the stirring speed is 400 r/min-600 r/min.
As a preferred embodiment of the present invention, the volume of the fluorescent solution in the jacket is preferably 15 to 20mL.
As a preferred embodiment of the present invention, the mass of the photocatalyst in the reaction tank is preferably 50 to 500mg.
As the preferable technical scheme of the invention, the volume of deionized water in the reaction tank is preferably 30-80 mL.
As a preferable mode of the technical scheme of the invention, the materials of the reaction tank and the jacket are preferably Pyrex glass with light transmittance of more than 90 percent.
As the optimization of the technical scheme of the invention, the stirring in the step S4 can be realized by selecting conventional stirring modes such as mechanical stirring, magnetic stirring and the like; preferably, magnetic stirring is selected.
Meanwhile, the invention also provides a system for implementing the photocatalytic water splitting method, which comprises a reaction tank, a jacket, a light source, a magnetic stirrer, a cooling water inlet, a cooling water outlet, an air inlet and an air outlet;
The reaction tank is sleeved with a jacket, and the jacket and the reaction tank form a cavity structure; the light source is arranged above the reaction tank; the magnetic stirrer is positioned at the bottom of the jacket; the jacket is provided with a cooling water inlet and a cooling water outlet; the reaction tank is provided with an air inlet and an air outlet.
Obviously, the cavity structure is used for containing fluorescent solution, and deionized water and photocatalyst are added into the reaction tank; the light source may be a common xenon lamp or the like.
Compared with the prior art, the invention has the following beneficial effects:
the invention firstly makes the catalyst absorb the light source by using the fluorescent solution with spectrum conversion, and makes the fluorescent solution absorb the light source spectrum which can not be absorbed by the catalyst for the second time, and converts the low-energy photons in the wide wavelength range which can be utilized by the fluorescent solution into the high-energy photons which can be absorbed by the catalyst by a nonlinear conversion mode, and the high-energy photons fed back by the fluorescent solution are absorbed by the catalyst again, so that the catalyst indirectly has spectrum conversion performance, and the water decomposition performance is obviously improved.
The invention is different from the rare earth metal doped up-conversion form in the prior art by using the fluorescent solution with spectrum conversion, does not need to consider whether the energy level of the catalyst is matched with that of the rare earth metal, has a proper sensitizer and activator, and needs to use a laser with specific wavelength for excitation, and can greatly improve the water decomposition performance of the catalyst by only selecting the fluorescent solution with proper emission wavelength according to the optimal excitation wavelength of the catalyst. No corresponding system is reported in the prior study, so if the system is combined with a series of modified photocatalysts with high full water splitting performance, the water splitting performance of the photocatalysts is greatly improved, and the aim of over 10% of STH value is fulfilled.
In a word, the method and the system of the invention can realize the improvement of the hydrogen production performance of the photocatalytic hydrolysis, and have the advantages of simple method, unique conception and convenient operation of the system.
Drawings
FIG. 1 shows photoluminescence spectra of DSc intermediates;
FIG. 2 is a schematic diagram of a system according to the present invention;
FIG. 3 is a graph showing the hydrogen production performance of CdS before and after adding the fluorescent solution in example 2 and comparative example 1;
FIG. 4 is an infrared plot of DSc synthesized in example 2;
FIG. 5 is a mass spectrum of DSc synthesized in example 2;
FIG. 6 is a hydrogen spectrum of DSc synthesized in example 2.
Wherein, 1, a reaction tank; 2. a jacket; 3. a light source; 4. a magnetic stirrer; 5. a cooling water inlet; 6. a cooling water outlet; 7. an air inlet; 8. and an air outlet.
Detailed Description
The following description of the embodiments of the present invention will clearly and fully describe the technical aspects of the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, are intended to fall within the scope of the present invention.
All commercial products or reagents of the invention are purchased through market channels unless otherwise specified.
Example 1
A system for a photocatalytic water splitting method comprises a reaction tank 1, a jacket 2, a light source 3, a magnetic stirrer 4, a cooling water inlet 5, a cooling water outlet 6, an air inlet 7 and an air outlet 8;
the reaction tank 1 is sleeved with a jacket 2, and the jacket 2 and the reaction tank form a cavity structure; the light source 3 is arranged above the reaction tank 1; the magnetic stirrer 4 is positioned at the bottom of the jacket 2; the jacket 2 is provided with a cooling water inlet 5 and a cooling water outlet 6; an air inlet 7 and an air outlet 8 are formed in the reaction tank 1.
Wherein, the material of the reaction tank and the jacket is preferably Pyrex glass with more than 90 percent of light transmittance.
Wherein the light source 3 is a 300W xenon lamp (MC-PF 300C).
Example 2
Based on the system provided in example 1, there is provided a photocatalytic water splitting method using nonlinear spectral conversion, comprising:
preparation of S1 and CdS
2.67g of Cd (CH) were weighed out 3 COO) 2 ·2H 2 O (10 mmol) and 2.29g of thiourea (30 mmol) were added to 60mL of ethylenediamine and stirred with a magnetic stirrer for 45min to complete dissolution, and then the above solution was transferred to a 100mL reaction vessel and kept at 160℃for 18h; after the reaction kettle is cooled to room temperature, collecting precipitates, washing the precipitates with ethanol and deionized water for 3 times respectively, and finally drying the precipitates in a vacuum drying oven to obtain CdS yellow powder;
S2: preparation of fluorescent solute DSc
81.60g (0.45 mol) of dihydroxyethylaniline was dissolved in 108mL of pyridine, 127.50mL (1.35 mol) of acetic anhydride was added thereto, and the mixture was heated under reflux at 110℃for 6 hours; cooling, pouring into ice water, washing with water for more than 10 times until the color of the upper layer solution turns light grey, extracting with dichloromethane, evaporating to dryness, concentrating, and purifying with petroleum ether and ethyl acetate by 20:1 column chromatography to obtain white solid; under ice bath conditions, 23.70g (0.15 mol) of phosphorus oxychloride is weighed and dripped into 5.60g (0.07 mol) of dimethylformamide to form frozen salt, 50mL of chloroform solution dissolved with 8.00g (0.03 mol) of raw material is added into the frozen salt, the temperature is slowly raised to 65 ℃, and the mixture is refluxed for 6 hours; pouring the product into crushed ice, regulating the pH value to be slightly alkaline by using a sodium hydroxide solution, extracting by using dichloromethane, taking a lower organic layer, evaporating to dryness to obtain the product, dispersing by using ethanol to obtain a white solid, and naming the white solid as M;
3.85g (50 mmol) of ammonium acetate, 1.47g (5 mmol) of M, 1.49g (10 mmol) of 2-tetralone and 30mL of glacial acetic acid are added into a round bottom flask in sequence, and stirring is carried out for 24h at normal temperature; filtering to obtain solid, pouring the filtrate into a large amount of water to obtain milky solid, filtering, drying, purifying with petroleum ether and ethyl acetate by 5:1 column chromatography to obtain milky solid (marked as intermediate a); adding 0.50g (0.90 mmol) of intermediate a into a round-bottom flask, dissolving with 100mL of ethanol, adding 10% sodium hydroxide aqueous solution by mass, stirring at normal temperature for 24h, adjusting pH to neutrality with diluted hydrochloric acid solution, filtering to obtain solid, washing with a large amount of water, extracting with dichloromethane, and evaporating to obtain fluorescent solute DSc; infrared, mass spectrum and hydrogen spectrograms of the DSc are shown in fig. 4, 5 and 6;
S3, preparing fluorescent solution
Weighing 0.0092g of fluorescent solute, and dissolving in 19mL of dimethyl sulfoxide (DMSO) to obtain a concentration of 10 -3 A mol/L fluorescent solution;
s4, weighing 0.1g of CdS powder obtained in the step S1, dissolving in 50mL of deionized water, and then adding 0.35M Na respectively 2 S and 0.35M Na 2 SO 3 As a sacrificial agent, after ultrasonic treatment for 15min, the catalyst solution is moved into a Pyrex reaction tank;
s5, adding the fluorescent solution obtained in the step S3 into a cavity structure formed between the reaction tank 1 and the jacket 2;
s6, vacuumizing the system to remove air in the system before the photocatalytic reaction; then the reaction tank is controlled to 15 ℃, a magnetic stirrer is turned on, and a 300W xenon lamp is used for testing the photocatalytic hydrogen production reaction performance.
Example 3
In comparison with example 2, the difference is that S6 is the same as the rest, specifically, based on the system provided in example 1, there is provided a photocatalytic water splitting method using nonlinear spectral conversion, including:
preparation of S1 and CdS
2.67g of Cd (CH) were weighed out 3 COO) 2 ·2H 2 O(10mmol) and 2.29g of thiourea (30 mmol) were added to 60mL of ethylenediamine and stirred with a magnetic stirrer for 45min until complete dissolution, then the above solution was transferred to a 100mL reaction kettle and kept at 160℃for 18h; after the reaction kettle is cooled to room temperature, collecting precipitates, washing the precipitates with ethanol and deionized water for 3 times respectively, and finally drying the precipitates in a vacuum drying oven to obtain CdS yellow powder;
S2: preparation of fluorescent solutes
81.60g (0.45 mol) of dihydroxyethylaniline was dissolved in 108mL of pyridine, 127.50mL (1.35 mol) of acetic anhydride was added thereto, and the mixture was heated under reflux at 110℃for 6 hours; cooling, pouring into ice water, washing with water for more than 10 times until the color of the upper layer solution turns light grey, extracting with dichloromethane, evaporating to dryness, concentrating, and purifying with petroleum ether and ethyl acetate by 20:1 column chromatography to obtain white solid; under ice bath conditions, 23.70g (0.15 mol) of phosphorus oxychloride is weighed and dripped into 5.60g (0.07 mol) of dimethylformamide to form frozen salt, 50mL of chloroform solution dissolved with 8.00g (0.03 mol) of raw material is added into the frozen salt, the temperature is slowly raised to 65 ℃, and the mixture is refluxed for 6 hours; pouring the product into crushed ice, regulating the pH value to be slightly alkaline by using a sodium hydroxide solution, extracting by using dichloromethane, taking a lower organic layer, evaporating to dryness to obtain the product, dispersing by using ethanol to obtain a white solid, and naming the white solid as M;
3.85g (50 mmol) of ammonium acetate, 1.47g (5 mmol) of M, 1.49g (10 mmol) of 2-tetralone and 30mL of glacial acetic acid are added into a round bottom flask in sequence, and stirring is carried out for 24h at normal temperature; filtering to obtain solid, pouring the filtrate into a large amount of water to obtain milky solid, filtering, drying, purifying with petroleum ether and ethyl acetate by 5:1 column chromatography to obtain milky solid (marked as intermediate a); adding 0.50g (0.90 mmol) of intermediate a into a round-bottom flask, dissolving with 100mL of ethanol, adding 10% sodium hydroxide aqueous solution by mass, stirring at normal temperature for 24h, adjusting pH to neutrality with diluted hydrochloric acid solution, filtering to obtain solid, washing with a large amount of water, extracting with dichloromethane, and evaporating to obtain fluorescent solute DSc;
S3, preparing fluorescent solution
Weighing 0.0092g of fluorescent solute, and dissolving in 19mL of dimethyl sulfoxide (DMSO) to obtain a concentration of 10 -3 A mol/L fluorescent solution;
s4, weighing 0.1gThe CdS powder obtained in S1 was dissolved in 50mL deionized water, and 0.35M Na was added respectively 2 S and 0.35M Na 2 SO 3 As a sacrificial agent, after ultrasonic treatment for 15min, the catalyst solution is moved into a Pyrex reaction tank;
s5, adding the fluorescent solution obtained in the step S3 into a cavity structure formed between the reaction tank 1 and the jacket 2;
s6, vacuumizing the system to remove air in the system before the photocatalytic reaction; and then controlling the reaction tank to 5 ℃ to enable the fluorescent solution to be in a frozen state, turning on a magnetic stirrer, and testing the photocatalytic hydrogen production reaction performance by using a 300W xenon lamp.
Example 4
In comparison with example 2, the only difference is that S2 fluorescent solutes are the same, specifically, based on the system provided in example 1, a method for photocatalytic water splitting using nonlinear spectral conversion is provided, comprising:
preparation of S1 and CdS
2.67g of Cd (CH) were weighed out 3 COO) 2 ·2H 2 O (10 mmol) and 2.29g of thiourea (30 mmol) were added to 60mL of ethylenediamine and stirred with a magnetic stirrer for 45min to complete dissolution, and then the above solution was transferred to a 100mL reaction vessel and kept at 160℃for 18h; after the reaction kettle is cooled to room temperature, collecting precipitates, washing the precipitates with ethanol and deionized water for 3 times respectively, and finally drying the precipitates in a vacuum drying oven to obtain CdS yellow powder;
S2: preparation of fluorescent solutes
Dimethylformamide (7.3 g,0.1 mol) was added to a 150mL round bottom flask, placed in an ice bath, and phosphorus oxychloride (60 g,0.4 mol) was slowly dropped into the flask with stirring using a constant pressure dropping funnel until the dropping was completed in the form of a white frozen salt; weighing triphenylamine (12 g,0.05 mol), adding into the frozen salt, transferring into an oil bath, heating to 65 ℃ after melting, cooling to room temperature after reaction for 3 hours, pouring into ice water, regulating the pH to about neutral by using sodium hydroxide solution, precipitating a large amount of light yellow solid, filtering, and drying; separating by column chromatography (silica gel column, developing agent-petroleum ether: ethyl acetate-30:1) to obtain white crystal; into a 250mL round bottom flask was added 100mL of the above white crystals (5.00 g,0.02 mol), sodium borohydride (2 g,0.05 mol) was added in portions with stirring, and the mixture was refluxed for 2h, cooled to room temperature, poured into ice water, extracted with dichloromethane, dried over anhydrous sodium sulfate, filtered, and the dichloromethane was evaporated to give a colorless liquid; adding the liquid (3.00 g, 0.0111 mmol) into a 150mL round bottom flask, placing the flask in ice water, respectively adding 50mL of methanol, 10mL of triethyl phosphite and iodine (2.81 g, 0.0111 mol), reacting for 12h under the protection of nitrogen, performing vacuum filtration after the reaction is finished, removing excessive triethyl phosphite, and separating by column chromatography to obtain light blue solid;
Under the irradiation of an infrared lamp at a drying position, adding the obtained solid (5.510 g, 0.010mol) and potassium tert-butoxide (4.490 g,0.040 mol) into an agate mortar respectively, rapidly grinding for 10min, gradually changing the white solid in the mortar into an oil state, then adding thiophenecarboxaldehyde (1.122 g, 0.010mol), and continuously grinding for 10min; pouring into water, stirring for 1h, extracting the liquid with dichloromethane, drying with anhydrous sodium sulfate, filtering, steaming out dichloromethane, separating by column chromatography (silica gel column, developing agent-petroleum ether: ethyl acetate=10:1), and obtaining light blue solid X2 to obtain fluorescent solute;
s3, preparing fluorescent solution
Weighing 0.0092g of fluorescent solute, and dissolving in 19mL of dimethyl sulfoxide (DMSO) to obtain a concentration of 10 -3 A mol/L fluorescent solution;
s4, weighing 0.1g of the CdS solid powder obtained in the step S1, dissolving in 50mL of deionized water, and respectively adding 0.35MNA 2 S and 0.35M Na 2 SO 3 As a sacrificial agent, after ultrasonic treatment for 15min, the catalyst solution is moved into a Pyrex reaction tank;
s5, adding the fluorescent solution obtained in the step S3 into a cavity structure formed between the reaction tank 1 and the jacket 2;
s6, vacuumizing the system to remove air in the system before the photocatalytic reaction; then the reaction tank is controlled to 15 ℃, a magnetic stirrer is turned on, and a 300W xenon lamp is used for testing the photocatalytic hydrogen production reaction performance.
Example 5
In comparison with example 2, the differences are only that S1 and S4 are the same, specifically, based on the system provided in example 1, a method for decomposing water by photocatalysis using nonlinear spectral conversion is provided, which comprises:
s1, preparation of photocatalyst
1.1547g of Na 2 WO 4 ·2H 2 O was added to 35mL of distilled water and allowed to dissolve completely after vigorous stirring for 10 min. Then, 35mL of HCl (wt 35%) is dropwise added into the solution to gradually form light yellow precipitate, and after intense stirring is carried out for 30min, the obtained mixture is transferred into a 100mL reaction kettle to be subjected to hydrothermal treatment, the reaction kettle is kept at 160 ℃ for 12h, after being cooled to room temperature, the precipitate is collected and respectively washed with ethanol and deionized water for 3 times to be neutral; finally, drying the product to constant weight at 60 ℃, grinding and sieving, annealing at 500 ℃ for 1h, and storing for later use;
s2: preparation of fluorescent solutes
81.60g (0.45 mol) of dihydroxyethylaniline was dissolved in 108mL of pyridine, 127.50mL (1.35 mol) of acetic anhydride was added thereto, and the mixture was heated under reflux at 110℃for 6 hours; cooling, pouring into ice water, washing with water for more than 10 times until the color of the upper layer solution turns light grey, extracting with dichloromethane, evaporating to dryness, concentrating, and purifying with petroleum ether and ethyl acetate by 20:1 column chromatography to obtain white solid; under ice bath conditions, 23.70g (0.15 mol) of phosphorus oxychloride is weighed and dripped into 5.60g (0.07 mol) of dimethylformamide to form frozen salt, 50mL of chloroform solution dissolved with 8.00g (0.03 mol) of raw material is added into the frozen salt, the temperature is slowly raised to 65 ℃, and the mixture is refluxed for 6 hours; pouring the product into crushed ice, regulating the pH value to be slightly alkaline by using a sodium hydroxide solution, extracting by using dichloromethane, taking a lower organic layer, evaporating to dryness to obtain the product, dispersing by using ethanol to obtain a white solid, and naming the white solid as M;
3.85g (50 mmol) of ammonium acetate, 1.47g (5 mmol) of M, 1.49g (10 mmol) of 2-tetralone and 30mL of glacial acetic acid are added into a round bottom flask in sequence, and stirring is carried out for 24h at normal temperature; filtering to obtain solid, pouring the filtrate into a large amount of water to obtain milky solid, filtering, drying, purifying with petroleum ether and ethyl acetate by 5:1 column chromatography to obtain milky solid (marked as intermediate a); adding 0.50g (0.90 mmol) of intermediate a into a round-bottom flask, dissolving with 100mL of ethanol, adding 10% sodium hydroxide aqueous solution by mass, stirring at normal temperature for 24h, adjusting pH to neutrality with diluted hydrochloric acid solution, filtering to obtain solid, washing with a large amount of water, extracting with dichloromethane, and evaporating to obtain fluorescent solute DSc;
s3, preparing fluorescent solution
Weighing 0.0092g of fluorescent solute, and dissolving in 19mL of dimethyl sulfoxide (DMSO) to obtain a concentration of 10 -3 A mol/L fluorescent solution;
s4, weighing 0.1g of the substance obtained in the step S1, dissolving in 50mL of deionized water, and then adding 0.35M FeCl 3 As a sacrificial agent, after ultrasonic treatment for 15min, the catalyst solution is moved into a Pyrex reaction tank;
s5, adding the fluorescent solution obtained in the step S3 into a cavity structure formed between the reaction tank 1 and the jacket 2;
s6, vacuumizing the system to remove air in the system before the photocatalytic reaction; then the reaction tank is controlled to 15 ℃, a magnetic stirrer is turned on, and a 300W xenon lamp is used for testing the photocatalytic oxygen production reaction performance.
Example 6
In comparison with example 5, the difference is that S1 is the same as the rest, specifically, based on the system provided in example 1, there is provided a photocatalytic water splitting method using nonlinear spectral conversion, comprising:
s1, preparing a photocatalyst: znO nano rod synthesized by hydrothermal method
First, 1.1g of Zn (CH 3 COO) 2· 2H 2 O was dispersed in 50mL of absolute ethanol (0.1M concentration), while 2g of sodium hydroxide (NaOH) was dissolved in 100mL of absolute ethanol (0.5M concentration); next, an alcoholic solution of NaOH was dropwise added to Zn (CH) 3 COO) 2· 2H 2 In an alcoholic solution of O, during this process Zn (CH 3 COO) 2· 2H 2 The alcohol solution of O is always stirred, and the stirring is continued for 30min after the dripping is finished to form white emulsion; then transferring the white emulsion into a 200mL polytetrafluoroethylene lining, sealing the reaction kettle, and placing the reaction kettle in an electrothermal blowing drying oven at 150 ℃ for reaction for 24 hours; finally, after the reaction kettle is naturally cooled to room temperature, collecting a sample, centrifugally cleaning the sample for 3 times by using absolute ethyl alcohol and deionized water respectively, and then drying and carrying outGrinding into powder for later use;
s2: preparation of fluorescent solutes
81.60g (0.45 mol) of dihydroxyethylaniline was dissolved in 108mL of pyridine, 127.50mL (1.35 mol) of acetic anhydride was added thereto, and the mixture was heated under reflux at 110℃for 6 hours; cooling, pouring into ice water, washing with water for more than 10 times until the color of the upper layer solution turns light grey, extracting with dichloromethane, evaporating to dryness, concentrating, and purifying with petroleum ether and ethyl acetate by 20:1 column chromatography to obtain white solid; under ice bath conditions, 23.70g (0.15 mol) of phosphorus oxychloride is weighed and dripped into 5.60g (0.07 mol) of dimethylformamide to form frozen salt, 50mL of chloroform solution dissolved with 8.00g (0.03 mol) of raw material is added into the frozen salt, the temperature is slowly raised to 65 ℃, and the mixture is refluxed for 6 hours; pouring the product into crushed ice, regulating the pH value to be slightly alkaline by using a sodium hydroxide solution, extracting by using dichloromethane, taking a lower organic layer, evaporating to dryness to obtain the product, dispersing by using ethanol to obtain a white solid, and naming the white solid as M;
3.85g (50 mmol) of ammonium acetate, 1.47g (5 mmol) of M, 1.49g (10 mmol) of 2-tetralone and 30mL of glacial acetic acid are added into a round bottom flask in sequence, and stirring is carried out for 24h at normal temperature; filtering to obtain solid, pouring the filtrate into a large amount of water to obtain milky solid, filtering, drying, purifying with petroleum ether and ethyl acetate by 5:1 column chromatography to obtain milky solid (marked as intermediate a); adding 0.50g (0.90 mmol) of intermediate a into a round-bottom flask, dissolving with 100mL of ethanol, adding 10% sodium hydroxide aqueous solution by mass, stirring at normal temperature for 24h, adjusting pH to neutrality with diluted hydrochloric acid solution, filtering to obtain solid, washing with a large amount of water, extracting with dichloromethane, and evaporating to obtain fluorescent solute DSc;
s3, preparing fluorescent solution
Weighing 0.0092g of fluorescent solute, and dissolving in 19mL of dimethyl sulfoxide (DMSO) to obtain a concentration of 10 -3 A mol/L fluorescent solution;
s4, weighing 0.1g of the substance obtained in the step S1, dissolving in 50mL of deionized water, and adding 0.35M FeCl 3 As a sacrificial agent, after ultrasonic treatment for 15min, the catalyst solution is moved into a Pyrex reaction tank;
s5, adding the fluorescent solution obtained in the step S3 into a cavity structure formed between the reaction tank 1 and the jacket 2;
s6, vacuumizing the system to remove air in the system before the photocatalytic reaction; then the reaction tank is controlled to 15 ℃, a magnetic stirrer is turned on, and a 300W xenon lamp is used for testing the photocatalytic oxygen production reaction performance.
Example 7
In comparison with example 2, the difference is that S1 is the same as the rest, specifically, based on the system provided in example 1, there is provided a photocatalytic water splitting method using nonlinear spectral conversion, including:
s1, preparation of photocatalyst
0.36g of zinc nitrate hexahydrate (Zn (NO) 3 ) 2· 6H 2 O) and 0.48g of cadmium nitrate tetrahydrate (Cd (NO) 3 ) 3· 4H 2 O) dissolve in 20mL deionized water; next, 0.71g of sodium sulfide nonahydrate (Na 2 S·9H 2 O) in 80mL of ethylenediamine (C 2 H 8 N 2 ) And 50mL of deionized water. Then, na is added 2 S·9H 2 Dropwise adding O solution to Zn (NO) 3 ) 2· 6H 2 O and Cd (NO) 3 ) 3· 4H 2 O in water solution, transferring the mixed solution into 200mL polytetrafluoroethylene lining, sealing the reaction kettle, placing the reaction kettle in an electrothermal blowing drying oven at 200 ℃ for reaction for 24 hours, collecting a sample after natural cooling to room temperature, centrifugally cleaning the sample with absolute ethyl alcohol and deionized water for 3 times respectively, and then drying and grinding to obtain Zn x Cd 1-x S powder;
s2: preparation of fluorescent solutes
81.60g (0.45 mol) of dihydroxyethylaniline was dissolved in 108mL of pyridine, 127.50mL (1.35 mol) of acetic anhydride was added thereto, and the mixture was heated under reflux at 110℃for 6 hours; cooling, pouring into ice water, washing with water for more than 10 times until the color of the upper layer solution turns light grey, extracting with dichloromethane, evaporating to dryness, concentrating, and purifying with petroleum ether and ethyl acetate by 20:1 column chromatography to obtain white solid; under ice bath conditions, 23.70g (0.15 mol) of phosphorus oxychloride is weighed and dripped into 5.60g (0.07 mol) of dimethylformamide to form frozen salt, 50mL of chloroform solution dissolved with 8.00g (0.03 mol) of raw material is added into the frozen salt, the temperature is slowly raised to 65 ℃, and the mixture is refluxed for 6 hours; pouring the product into crushed ice, regulating the pH value to be slightly alkaline by using a sodium hydroxide solution, extracting by using dichloromethane, taking a lower organic layer, evaporating to dryness to obtain the product, dispersing by using ethanol to obtain a white solid, and naming the white solid as M;
3.85g (50 mmol) of ammonium acetate, 1.47g (5 mmol) of M, 1.49g (10 mmol) of 2-tetralone and 30mL of glacial acetic acid are added into a round bottom flask in sequence, and stirring is carried out for 24h at normal temperature; filtering to obtain solid, pouring the filtrate into a large amount of water to obtain milky solid, filtering, drying, purifying with petroleum ether and ethyl acetate by 5:1 column chromatography to obtain milky solid (marked as intermediate a); adding 0.50g (0.90 mmol) of intermediate a into a round-bottom flask, dissolving with 100mL of ethanol, adding 10% sodium hydroxide aqueous solution by mass, stirring at normal temperature for 24h, adjusting pH to neutrality with diluted hydrochloric acid solution, filtering to obtain solid, washing with a large amount of water, extracting with dichloromethane, and evaporating to obtain fluorescent solute DSc;
s3, preparing fluorescent solution
Weighing 0.0092g of fluorescent solute, and dissolving in 19mL of dimethyl sulfoxide (DMSO) to obtain a concentration of 10 -3 A mol/L fluorescent solution;
s4, weighing 0.1g of Zn obtained in the step S1 x Cd 1-x S powder, dissolving in 50mL deionized water, and adding 0.35MNA respectively 2 S and 0.35M Na 2 SO 3 As a sacrificial agent, after ultrasonic treatment for 15min, the catalyst solution is moved into a Pyrex reaction tank;
s5, adding the fluorescent solution obtained in the step S3 into a cavity structure formed between the reaction tank 1 and the jacket 2;
s6, vacuumizing the system to remove air in the system before the photocatalytic reaction; then the reaction tank is controlled to 15 ℃, a magnetic stirrer is turned on, and a 300W xenon lamp is used for testing the photocatalytic hydrogen production reaction performance.
Example 8
In comparison with example 7, the differences are only that S1 and S3 are the same, specifically, based on the system provided in example 1, a method for decomposing water by photocatalysis using nonlinear spectral conversion is provided, which comprises:
s1, preparation of photocatalyst
0.93g of oxygen was weighed outZinc oxide (ZnO) nanorods and 1.07g of commercial gallium oxide (Ga) 2 O 3 ) (the atomic ratio of Zn to Ga is 1: 1) Grinding in a mortar until the mixture is uniform. Then, the mixture was spread in a quartz boat, and the quartz boat was placed in a tube furnace, purged with ammonia gas for 10 minutes, and then heated to 850 ℃ at a heating rate of 10 ℃/min, and nitrided for 15 hours. Finally, after the tube furnace is naturally cooled to room temperature, the sample is taken out and ground into powder for standby. Then, the (Ga is deposited by means of light 1- x Zn x )(N 1-x O x ) Solid solution Rh 3+ 、Cr 3+ Is filtered and dried for standby;
s2: preparation of fluorescent solutes
81.60g (0.45 mol) of dihydroxyethylaniline was dissolved in 108mL of pyridine, 127.50mL (1.35 mol) of acetic anhydride was added thereto, and the mixture was heated under reflux at 110℃for 6 hours; cooling, pouring into ice water, washing with water for more than 10 times until the color of the upper layer solution turns light grey, extracting with dichloromethane, evaporating to dryness, concentrating, and purifying with petroleum ether and ethyl acetate by 20:1 column chromatography to obtain white solid; under ice bath conditions, 23.70g (0.15 mol) of phosphorus oxychloride is weighed and dripped into 5.60g (0.07 mol) of dimethylformamide to form frozen salt, 50mL of chloroform solution dissolved with 8.00g (0.03 mol) of raw material is added into the frozen salt, the temperature is slowly raised to 65 ℃, and the mixture is refluxed for 6 hours; pouring the product into crushed ice, regulating the pH value to be slightly alkaline by using a sodium hydroxide solution, extracting by using dichloromethane, taking a lower organic layer, evaporating to dryness to obtain the product, dispersing by using ethanol to obtain a white solid, and naming the white solid as M;
3.85g (50 mmol) of ammonium acetate, 1.47g (5 mmol) of M, 1.49g (10 mmol) of 2-tetralone and 30mL of glacial acetic acid are added into a round bottom flask in sequence, and stirring is carried out for 24h at normal temperature; filtering to obtain solid, pouring the filtrate into a large amount of water to obtain milky solid, filtering, drying, purifying with petroleum ether and ethyl acetate by 5:1 column chromatography to obtain milky solid (marked as intermediate a); adding 0.50g (0.90 mmol) of intermediate a into a round-bottom flask, dissolving with 100mL of ethanol, adding 10% sodium hydroxide aqueous solution by mass, stirring at normal temperature for 24h, adjusting pH to neutrality with diluted hydrochloric acid solution, filtering to obtain solid, washing with a large amount of water, extracting with dichloromethane, and evaporating to obtain fluorescent solute DSc;
s3, preparing fluorescent solution
Weighing 0.0092g of fluorescent solute, and dissolving in 19mL of dimethyl sulfoxide (DMSO) to obtain a concentration of 10 -3 A mol/L fluorescent solution;
s4, 0.1g of the material obtained in step S1 was weighed out, and dissolved in 50mL of deionized water (since (Ga 1-x Zn x )(N 1-x O x ) The catalyst has full water-dissolving performance, so that a sacrificial agent is not needed to be added), and after ultrasonic treatment is carried out for 15min, the catalyst solution is moved into a Pyrex reaction tank;
s5, adding the fluorescent solution obtained in the step S3 into a cavity structure formed between the reaction tank 1 and the jacket 2;
s6, vacuumizing the system to remove air in the system before the photocatalytic reaction; then the reaction tank is controlled to 15 ℃, a magnetic stirrer is turned on, and a 300W xenon lamp is used for testing the photocatalytic hydrogen production reaction performance.
Example 9
Compared with example 4, the difference is only that S1 is different and the rest is the same, and S1 is identical with S1 of example 5; specifically, based on the system provided in example 1, there is provided a photocatalytic water splitting method using nonlinear spectral conversion, comprising:
s1, preparation of photocatalyst
1.1547g of Na 2 WO 4 ·2H 2 O was added to 35mL of distilled water and allowed to dissolve completely after vigorous stirring for 10 min. Then, 35mL of HCl (wt 35%) is dropwise added into the solution to gradually form light yellow precipitate, and after intense stirring is carried out for 30min, the obtained mixture is transferred into a 100mL reaction kettle to be subjected to hydrothermal treatment, the reaction kettle is kept at 160 ℃ for 12h, after being cooled to room temperature, the precipitate is collected and respectively washed with ethanol and deionized water for 3 times to be neutral; finally, drying the product to constant weight at 60 ℃, grinding and sieving, annealing at 500 ℃ for 1h, and storing for later use;
s2: preparation of fluorescent solutes
Dimethylformamide (7.3 g,0.1 mol) was added to a 150mL round bottom flask, placed in an ice bath, and phosphorus oxychloride (60 g,0.4 mol) was slowly dropped into the flask with stirring using a constant pressure dropping funnel until the dropping was completed in the form of a white frozen salt; weighing triphenylamine (12 g,0.05 mol), adding into the frozen salt, transferring into an oil bath, heating to 65 ℃ after melting, cooling to room temperature after reaction for 3 hours, pouring into ice water, regulating the pH to about neutral by using sodium hydroxide solution, precipitating a large amount of light yellow solid, carrying out suction filtration, and drying. Separating by column chromatography (silica gel column, developing agent-petroleum ether: ethyl acetate-30:1) to obtain white crystal. Into a 250mL round bottom flask was added 100mL of the above white crystals (5.00 g,0.02 mol), sodium borohydride (2 g,0.05 mol) was added in portions with stirring, and the mixture was refluxed for 2h, cooled to room temperature, poured into ice water, extracted with dichloromethane, dried over anhydrous sodium sulfate, filtered, and the dichloromethane was evaporated to give a colorless liquid; adding the liquid (3.00 g, 0.0111 mmol) into a 150mL round bottom flask, placing the flask in ice water, respectively adding 50mL of methanol, 10mL of triethyl phosphite and iodine (2.81 g, 0.0111 mol), reacting for 12h under the protection of nitrogen, performing vacuum filtration after the reaction is finished, removing excessive triethyl phosphite, and separating by column chromatography to obtain light blue solid;
Under the irradiation of an infrared lamp at a drying position, adding the obtained solid (5.510 g, 0.010mol) and potassium tert-butoxide (4.490 g,0.040 mol) into an agate mortar respectively, rapidly grinding for 10min, gradually changing the white solid in the mortar into an oil state, then adding thiophenecarboxaldehyde (1.122 g, 0.010mol), and continuously grinding for 10min; pouring into water, stirring for 1h, extracting the liquid with dichloromethane, drying with anhydrous sodium sulfate, filtering, steaming out dichloromethane, separating by column chromatography (silica gel column, developing agent-petroleum ether: ethyl acetate=10:1), and obtaining light blue solid X2 to obtain fluorescent solute;
s3, preparing fluorescent solution
Weighing 0.0092g of fluorescent solute, and dissolving in 19mL of dimethyl sulfoxide (DMSO) to obtain a concentration of 10 -3 A mol/L fluorescent solution;
s4, weighing 0.1g of the material obtained in the step S1, dissolving in 50mL of deionized water, and respectively adding 0.35M Na 2 S and 0.35M Na 2 SO 3 As a sacrificial agent, after ultrasonic treatment for 15min, the catalyst solution is moved into a Pyrex reaction tank;
s5, adding the fluorescent solution obtained in the step S3 into a cavity structure formed between the reaction tank 1 and the jacket 2;
s6, vacuumizing the system to remove air in the system before the photocatalytic reaction; then the reaction tank is controlled to 15 ℃, a magnetic stirrer is turned on, and a 300W xenon lamp is used for testing the photocatalytic oxygen production reaction performance.
Example 10
Compared with example 9, the difference is that S1 is different and the rest is the same, and S1 is identical with S1 of example 6; specifically, based on the system provided in example 1, there is provided a photocatalytic water splitting method using nonlinear spectral conversion, comprising:
s1, preparing a photocatalyst: znO nano rod synthesized by hydrothermal method
First, 1.1g of Zn (CH 3 COO) 2· 2H 2 O was dispersed in 50mL of absolute ethanol (0.1M concentration), while 2g of sodium hydroxide (NaOH) was dissolved in 100mL of absolute ethanol (0.5M concentration); next, an alcoholic solution of NaOH was dropwise added to Zn (CH) 3 COO) 2· 2H 2 In an alcoholic solution of O, during this process Zn (CH 3 COO) 2· 2H 2 The alcohol solution of O is always stirred, and the stirring is continued for 30min after the dripping is finished to form white emulsion; then transferring the white emulsion into a 200mL polytetrafluoroethylene lining, sealing the reaction kettle, and placing the reaction kettle in an electrothermal blowing drying oven at 150 ℃ for reaction for 24 hours; finally, after the reaction kettle is naturally cooled to room temperature, collecting a sample, centrifugally cleaning the sample for 3 times by using absolute ethyl alcohol and deionized water respectively, and then drying and grinding the sample into powder for later use;
s2: preparation of fluorescent solutes
Dimethylformamide (7.3 g,0.1 mol) was added to a 150mL round bottom flask, placed in an ice bath, and phosphorus oxychloride (60 g,0.4 mol) was slowly dropped into the flask with stirring using a constant pressure dropping funnel until the dropping was completed in the form of a white frozen salt; weighing triphenylamine (12 g,0.05 mol), adding into the frozen salt, transferring into an oil bath, heating to 65 ℃ after melting, cooling to room temperature after reaction for 3 hours, pouring into ice water, regulating the pH to about neutral by using sodium hydroxide solution, precipitating a large amount of light yellow solid, carrying out suction filtration, and drying. Separating by column chromatography (silica gel column, developing agent-petroleum ether: ethyl acetate-30:1) to obtain white crystal. Into a 250mL round bottom flask was added 100mL of the above white crystals (5.00 g,0.02 mol), sodium borohydride (2 g,0.05 mol) was added in portions with stirring, and the mixture was refluxed for 2h, cooled to room temperature, poured into ice water, extracted with dichloromethane, dried over anhydrous sodium sulfate, filtered, and the dichloromethane was evaporated to give a colorless liquid; adding the liquid (3.00 g, 0.0111 mmol) into a 150mL round bottom flask, placing the flask in ice water, respectively adding 50mL of methanol, 10mL of triethyl phosphite and iodine (2.81 g, 0.0111 mol), reacting for 12h under the protection of nitrogen, performing vacuum filtration after the reaction is finished, removing excessive triethyl phosphite, and separating by column chromatography to obtain light blue solid;
Under the irradiation of an infrared lamp at a drying position, adding the obtained solid (5.510 g, 0.010mol) and potassium tert-butoxide (4.490 g,0.040 mol) into an agate mortar respectively, rapidly grinding for 10min, gradually changing the white solid in the mortar into an oil state, then adding thiophenecarboxaldehyde (1.122 g, 0.010mol), and continuously grinding for 10min; pouring into water, stirring for 1h, extracting the liquid with dichloromethane, drying with anhydrous sodium sulfate, filtering, steaming out dichloromethane, separating by column chromatography (silica gel column, developing agent-petroleum ether: ethyl acetate=10:1), and obtaining light blue solid X2 to obtain fluorescent solute;
s3, preparing fluorescent solution
Weighing 0.0092g of fluorescent solute, and dissolving in 19mL of dimethyl sulfoxide (DMSO) to obtain a concentration of 10 -3 A mol/L fluorescent solution;
s4, weighing 0.1g of the material obtained in the step S1, dissolving in 50mL of deionized water, and respectively adding 0.35M Na 2 S and 0.35M Na 2 SO 3 As a sacrificial agent, after ultrasonic treatment for 15min, the catalyst solution is moved into a Pyrex reaction tank;
s5, adding the fluorescent solution obtained in the step S3 into a cavity structure formed between the reaction tank 1 and the jacket 2;
s6, vacuumizing the system to remove air in the system before the photocatalytic reaction; then the reaction tank is controlled to 15 ℃, a magnetic stirrer is turned on, and a 300W xenon lamp is used for testing the photocatalytic oxygen production reaction performance.
Example 11
The difference from example 10 is that S1 and S3 to S6 are the same, and S1, S3 to S6 are identical to S1 and S3 of example 8; specifically, based on the system provided in example 1, there is provided a photocatalytic water splitting method using nonlinear spectral conversion, comprising:
s1, preparation of photocatalyst
0.93g of zinc oxide (ZnO) nanorods and 1.07g of commercial gallium oxide (Ga) were weighed out 2 O 3 ) (the atomic ratio of Zn to Ga is 1: 1) Grinding in a mortar until the mixture is uniform. Then, the mixture was spread in a quartz boat, and the quartz boat was placed in a tube furnace, purged with ammonia gas for 10 minutes, and then heated to 850 ℃ at a heating rate of 10 ℃/min, and nitrided for 15 hours. Finally, after the tube furnace is naturally cooled to room temperature, the sample is taken out and ground into powder for standby. Then, the (Ga is deposited by means of light 1- x Zn x )(N 1-x O x ) Solid solution Rh 3+ 、Cr 3+ Is filtered and dried for standby;
s2: preparation of fluorescent solutes
Dimethylformamide (7.3 g,0.1 mol) was added to a 150mL round bottom flask, placed in an ice bath, and phosphorus oxychloride (60 g,0.4 mol) was slowly dropped into the flask with stirring using a constant pressure dropping funnel until the dropping was completed in the form of a white frozen salt; weighing triphenylamine (12 g,0.05 mol), adding into the frozen salt, transferring into an oil bath, heating to 65 ℃ after melting, cooling to room temperature after reaction for 3 hours, pouring into ice water, regulating the pH to about neutral by using sodium hydroxide solution, precipitating a large amount of light yellow solid, carrying out suction filtration, and drying. Separating by column chromatography (silica gel column, developing agent-petroleum ether: ethyl acetate-30:1) to obtain white crystal. Into a 250mL round bottom flask was added 100mL of the above white crystals (5.00 g,0.02 mol), sodium borohydride (2 g,0.05 mol) was added in portions with stirring, and the mixture was refluxed for 2h, cooled to room temperature, poured into ice water, extracted with dichloromethane, dried over anhydrous sodium sulfate, filtered, and the dichloromethane was evaporated to give a colorless liquid; adding the liquid (3.00 g, 0.0111 mmol) into a 150mL round bottom flask, placing the flask in ice water, respectively adding 50mL of methanol, 10mL of triethyl phosphite and iodine (2.81 g, 0.0111 mol), reacting for 12h under the protection of nitrogen, performing vacuum filtration after the reaction is finished, removing excessive triethyl phosphite, and separating by column chromatography to obtain light blue solid;
Under the irradiation of an infrared lamp at a drying position, adding the obtained solid (5.510 g, 0.010mol) and potassium tert-butoxide (4.490 g,0.040 mol) into an agate mortar respectively, rapidly grinding for 10min, gradually changing the white solid in the mortar into an oil state, then adding thiophenecarboxaldehyde (1.122 g, 0.010mol), and continuously grinding for 10min; pouring into water, stirring for 1h, extracting the liquid with dichloromethane, drying with anhydrous sodium sulfate, filtering, steaming out dichloromethane, separating by column chromatography (silica gel column, developing agent-petroleum ether: ethyl acetate=10:1), and obtaining light blue solid X2 to obtain fluorescent solute;
s3, preparing fluorescent solution
Weighing 0.0092g of fluorescent solute, and dissolving in 19mL of dimethyl sulfoxide (DMSO) to obtain a concentration of 10 -3 A mol/L fluorescent solution;
s4, 0.1g of the material obtained in step S1 was weighed out, and dissolved in 50mL of deionized water (since (Ga 1-x Zn x )(N 1-x O x ) The catalyst has full water-dissolving performance, so that a sacrificial agent is not needed to be added), and after ultrasonic treatment is carried out for 15min, the catalyst solution is moved into a Pyrex reaction tank;
s5, adding the fluorescent solution obtained in the step S3 into a cavity structure formed between the reaction tank 1 and the jacket 2;
s6, vacuumizing the system to remove air in the system before the photocatalytic reaction; then the reaction tank is controlled to 15 ℃, a magnetic stirrer is turned on, and a 300W xenon lamp is used for testing the photocatalytic oxygen production reaction performance.
Comparative example 1
In contrast to example 2, the use of a fluorescent solution was excluded; specifically, a photocatalytic water splitting method includes:
s1, 2.67g of cadmium acetate dihydrate (Cd (CH) 3 COO) 2 ·2H 2 O) (10 mmol) and 2.29g of thiourea (30 mmol) were added to 60mL of ethylenediamine and stirred with a magnetic stirrer for 45min to complete dissolution, and then the above solution was transferred to a 100mL reaction vessel and kept at 160℃for 18h; after the reaction kettle is cooled to room temperature, collecting the sedimentRespectively washing the starch with ethanol and deionized water for 3 times, and finally drying in a vacuum drying oven to obtain CdS yellow powder;
s2, weighing 0.1g of CdS solid powder, dissolving in 50mL of deionized water, and respectively adding 0.35M Na 2 S and 0.35MNA 2 SO 3 After ultrasonic treatment is carried out for 15min as a sacrificial agent, the catalyst solution is moved into a Pyrex reaction tank, a fluorescent solution is added into a fluorescent tank outside the reaction tank, the temperature is controlled to be 15 ℃, a photolysis water hydrogen production system (MC-SPB 10) is connected, a magnetic stirrer is turned on, the system is vacuumized to remove air in the system before photocatalytic reaction, and a 300W xenon lamp (MC-PF 300C) is used for carrying out photocatalytic hydrogen production reaction performance test.
Comparative example 2
In contrast to example 5, the use of a fluorescent solution was excluded; specifically, a photocatalytic water splitting method includes:
S1, mixing 1.1547g of Na 2 WO 4 ·2H 2 O was added to 35mL of distilled water and allowed to dissolve completely after vigorous stirring for 10 min. Then, 35mL of HCl (wt 35%) was added dropwise to the solution, a pale yellow precipitate was gradually formed, and after intense stirring for 30min, the resulting mixture was transferred to a 100mL reaction vessel for hydrothermal treatment, kept at 160 ℃ for 12 hours, after the reaction vessel was cooled to room temperature, the precipitate was collected and washed 3 times with ethanol and deionized water, respectively, to neutrality. Finally, the product is dried to constant weight at 60 ℃, ground and sieved, annealed at 500 ℃ for 1h and stored for later use.
S2, weighing 0.1g of WO 3 Solid powder, dissolved in 50mL deionized water, added FeCl 3 After ultrasonic treatment is carried out for 15min as a sacrificial agent, the catalyst solution is moved into a Pyrex reaction tank, a fluorescent solution is added into a fluorescent tank outside the reaction tank, the temperature is controlled to be 15 ℃, a photolysis water hydrogen production system (MC-SPB 10) is connected, a magnetic stirrer is turned on, the system is vacuumized to remove air in the system before photocatalytic reaction, and a 300W xenon lamp (MC-PF 300C) is used for carrying out photocatalytic oxygen production reaction performance test.
Comparative example 3
In contrast to example 8, the use of a fluorescent solution was excluded; specifically, a photocatalytic water splitting method includes:
S1, weighing 0.93g of ZnO nano rod and 1.07g of commercial gallium oxide (Ga 2 O 3 ) (the atomic ratio of Zn to Ga is 1: 1) Grinding in a mortar until the mixture is uniform. Then, spreading the mixture in a quartz boat, placing the quartz boat in a tube furnace, purging with ammonia gas for 10min to remove air, heating to 850 ℃ at a heating rate of 10 ℃/min, and nitriding for 15h; finally, after the tube furnace is naturally cooled to room temperature, the sample is taken out and ground into powder for standby. Then, the (Ga is deposited by means of light 1-x Zn x )(N 1-x O x ) Solid solution Rh 3+ 、Cr 3+ Is filtered and dried for standby;
s2, 0.1g (Ga 1-x Zn x )(N 1-x O x ) And (3) dissolving solid powder in 50mL of deionized water, performing ultrasonic treatment for 15min, transferring the catalyst solution into a Pyrex reaction tank, adding a fluorescent solution into a fluorescent tank outside the reaction tank, controlling the temperature to be 15 ℃, connecting a photocatalytic water splitting hydrogen production system (MC-SPB 10), opening a magnetic stirrer, vacuumizing the system to remove air in the system before photocatalytic reaction, and performing photocatalytic total water splitting reaction performance test by using a 300W xenon lamp (MC-PF 300C).
The results of the photocatalytic performance test of examples 2 to 11 and comparative examples 1 to 3 are shown in Table 1. It can be seen from the table that the efficiency of photocatalytic water splitting can be greatly improved based on the fluorescent solute provided by the invention.
TABLE 1 photocatalytic Performance test results
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The technical idea of the present invention is described by the above embodiments, but the present invention is not limited to the above embodiments, that is, it does not mean that the present invention must be implemented depending on the above embodiments. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of individual raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.
Claims (10)
1. A method for photocatalytic water splitting using nonlinear spectral conversion, comprising: in the photocatalytic water splitting reaction, firstly, a photocatalyst is utilized to absorb a light source spectrum, then a fluorescent solution is utilized to secondarily absorb an unabsorbed light source spectrum, and low-energy photons are converted into high-energy photons for the photocatalyst to absorb again;
wherein the fluorescent solution is obtained by dissolving a solute with nonlinear spectral conversion characteristics in a solvent.
2. A method of photocatalytic water splitting utilizing nonlinear spectral conversion as set forth in claim 1, comprising:
s1, dissolving a solute with nonlinear spectrum conversion characteristics in a solvent to obtain a fluorescent solution;
S2, placing the photocatalyst in a reaction tank;
s3, adding the fluorescent solution obtained in the step S1 into a jacket outside the reaction tank;
s4, controlling the temperature of the reaction tank, and carrying out photocatalytic water splitting reaction by using a light source under the stirring condition.
3. The photocatalytic water splitting method according to claim 1 or 2, wherein the photocatalyst is one or more selected from the group consisting of complex oxides, sulfides, oxysulfides, nitrides, oxynitrides, halides and oxyhalides.
4. The photocatalytic water splitting method according to claim 1 or 2, wherein the solute having a nonlinear spectral conversion characteristic is selected from one or both of DSc, X2;
wherein, the structural formula of DSc is as follows:
wherein, the structural formula of X2 is as follows:
5. the photocatalytic water splitting method according to claim 1 or 2, wherein the solvent is one or more selected from dimethylformamide, dimethylsulfoxide, acetonitrile, tetrahydrofuran, dichloromethane, benzene, ethanol, ethyl acetate.
6. The photocatalytic water splitting method according to claim 1 or 2, wherein the concentration of the solute in the solvent is 10 -4 ~10 -1 mol/L。
7. The photocatalytic water splitting method as set forth in claim 1 or 2, wherein the amount of the photocatalyst is 50 to 500mg.
8. The photocatalytic water splitting method according to claim 2, wherein in step S4, the reaction tank temperature is 10 to 20 ℃.
9. The photocatalytic water splitting method according to claim 2, wherein in step S4, the stirring speed is 400 to 600r/min.
10. A system for implementing the photocatalytic water splitting method according to any one of claims 1 to 9, characterized by comprising a reaction tank (1), a jacket (2), a light source (3), a magnetic stirrer (4), a cooling water inlet (5), a cooling water outlet (6), an air inlet (7), an air outlet (8);
the reaction tank (1) is sleeved with a jacket (2), and the jacket form a cavity structure; the light source (3) is arranged above the reaction tank (1); the magnetic stirrer (4) is positioned at the bottom of the jacket (2); a cooling water inlet (5) and a cooling water outlet (6) are formed in the jacket (2); an air inlet (7) and an air outlet (8) are formed in the reaction tank (1).
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