CN111517276B - Method for preparing hydrogen and hydrogen peroxide by photocatalytic water decomposition - Google Patents
Method for preparing hydrogen and hydrogen peroxide by photocatalytic water decomposition Download PDFInfo
- Publication number
- CN111517276B CN111517276B CN201910106984.4A CN201910106984A CN111517276B CN 111517276 B CN111517276 B CN 111517276B CN 201910106984 A CN201910106984 A CN 201910106984A CN 111517276 B CN111517276 B CN 111517276B
- Authority
- CN
- China
- Prior art keywords
- hydrogen
- photocatalyst
- titanium dioxide
- hydrogen peroxide
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 title claims abstract description 112
- 238000000034 method Methods 0.000 title claims abstract description 85
- 239000001257 hydrogen Substances 0.000 title claims abstract description 74
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 74
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 72
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 32
- 238000000354 decomposition reaction Methods 0.000 title claims abstract description 20
- 239000011941 photocatalyst Substances 0.000 claims abstract description 59
- 238000002360 preparation method Methods 0.000 claims abstract description 27
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 19
- 230000001678 irradiating effect Effects 0.000 claims abstract description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 114
- 239000004408 titanium dioxide Substances 0.000 claims description 49
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 46
- 239000004065 semiconductor Substances 0.000 claims description 38
- 239000002105 nanoparticle Substances 0.000 claims description 30
- 229910052697 platinum Inorganic materials 0.000 claims description 23
- 239000000243 solution Substances 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 16
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 11
- 238000007540 photo-reduction reaction Methods 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 239000011261 inert gas Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 238000007872 degassing Methods 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 8
- 229910052753 mercury Inorganic materials 0.000 claims description 8
- 229910052763 palladium Inorganic materials 0.000 claims description 7
- 238000007789 sealing Methods 0.000 claims description 7
- 229910003074 TiCl4 Inorganic materials 0.000 claims description 6
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052737 gold Inorganic materials 0.000 claims description 6
- 239000010931 gold Substances 0.000 claims description 6
- 230000009467 reduction Effects 0.000 claims description 6
- 238000006722 reduction reaction Methods 0.000 claims description 6
- 239000008156 Ringer's lactate solution Substances 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000011068 loading method Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 17
- 239000001301 oxygen Substances 0.000 abstract description 17
- 229910052760 oxygen Inorganic materials 0.000 abstract description 17
- 238000000926 separation method Methods 0.000 abstract description 8
- 230000000052 comparative effect Effects 0.000 description 12
- 238000007254 oxidation reaction Methods 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 9
- 238000007146 photocatalysis Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920000767 polyaniline Polymers 0.000 description 3
- 238000000634 powder X-ray diffraction Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- CYDQOEWLBCCFJZ-UHFFFAOYSA-N 4-(4-fluorophenyl)oxane-4-carboxylic acid Chemical compound C=1C=C(F)C=CC=1C1(C(=O)O)CCOCC1 CYDQOEWLBCCFJZ-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000013064 chemical raw material Substances 0.000 description 2
- 239000003426 co-catalyst Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- RNVCVTLRINQCPJ-UHFFFAOYSA-N o-toluidine Chemical compound CC1=CC=CC=C1N RNVCVTLRINQCPJ-UHFFFAOYSA-N 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000000053 physical method Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229940005581 sodium lactate Drugs 0.000 description 2
- 239000001540 sodium lactate Substances 0.000 description 2
- 235000011088 sodium lactate Nutrition 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910002621 H2PtCl6 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010812 external standard method Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- BBKFSSMUWOMYPI-UHFFFAOYSA-N gold palladium Chemical compound [Pd].[Au] BBKFSSMUWOMYPI-UHFFFAOYSA-N 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical group [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- -1 on the other hand Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 238000002211 ultraviolet spectrum Methods 0.000 description 1
Images
Classifications
-
- 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
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/52—Gold
-
- 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
- C01B15/00—Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
- C01B15/01—Hydrogen peroxide
- C01B15/027—Preparation from water
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a method for preparing hydrogen and hydrogen peroxide by photocatalytic water splitting, which comprises the steps of adding a photocatalyst into water to obtain a mixed reaction liquid, irradiating the mixed reaction liquid by light to generate hydrogen and hydrogen peroxide, realizing the simultaneous preparation of hydrogen and hydrogen peroxide by photocatalytic water splitting, avoiding the generation of oxygen in the preparation process and avoiding the difficulty brought by the separation of hydrogen and oxygen; in the process of simultaneously preparing hydrogen and hydrogen peroxide, the highest output efficiency of the hydrogen can reach 8.5 mu mol/mg/h, the highest output efficiency of the hydrogen peroxide can reach 7.0 mu mol/mg/h, and the output efficiency of the method is still 90-95% of the highest output efficiency after continuous photocatalytic decomposition is carried out for 10 days.
Description
Technical Field
The invention relates to the technical field of photocatalysis, in particular to a method for preparing hydrogen and hydrogen peroxide by photocatalytic water decomposition.
Background
The method for preparing hydrogen by photocatalytic water decomposition by using solar energy is an effective way for solving the problems of energy shortage and environmental pollution at present. The water decomposition process involves both reduction and oxidation processes of water. The oxidation process of water is the key to limiting its decomposition rate. In order to increase the reaction rate, most of the existing photocatalytic water splitting systems introduce a sacrificial agent to participate in the oxidation reaction, but the sacrificial agent is only used for the oxidation reaction, and is not a true water oxidation reaction. The main direction of research at present is to realize the preparation of hydrogen and oxygen by fully decomposing water. However, the oxygen generated has the following disadvantages: (1) the reverse reaction is easy to occur with hydrogen, and the reaction rate is reduced; (2) the generated hydrogen and oxygen are both gases, so that the cost of later separation is increased; (3) the generated oxygen relates to a four-electron transfer process, the reaction difficulty is high, and the reaction efficiency is low; in addition, hydrogen peroxide is an important chemical raw material and is widely applied to the textile, pharmaceutical and paper-making industries. At present, the oxidation method of anthraquinone is mainly used for industrially producing hydrogen peroxide, and the method has high cost, generates a large amount of industrial wastewater and causes environmental pollution.
CN102381684A discloses a method for preparing hydrogen by decomposing water using sunlight photocatalysis, wherein the method uses oxalic acid as a sacrificial agent; according to the scheme, oxalic acid is added as a sacrificial agent in the preparation process, the prepared product comprises hydrogen and carbon dioxide, a large amount of acetic acid is consumed in the preparation process, and the preparation cost is high.
CN101629300A discloses a method for directly separating and producing hydrogen by decomposing water by adopting the photocatalytic fuel cell technology of the hydrogen fuel cell reverse principle; the proposal adopts the reverse principle of a hydrogen fuel cell, a photo-anode takes a photocatalyst as a raw material, and a cathode is a platinum or nickel or carbon electrode; proton or hydroxyl ion is transferred between the two electrodes by adopting an ionic membrane, and the photoanode and the cathode are connected by a lead to form a circuit; the sunlight or the simulated sunlight is used as a light source, and the light directly irradiates the photo-anode; hydrogen is generated at the cathode, and oxidation reaction is generated at the anode, so that the aim of separating and producing hydrogen by photolysis water is fulfilled; the products of the photocatalytic water decomposition of the scheme are hydrogen and oxygen, and although the scheme can realize the separation of the hydrogen and the oxygen, the problems of complicated separation equipment and high cost still exist.
CN102730634A discloses a method for preparing hydrogen by sunlight catalytic decomposition of water, which uses polyaniline as a catalyst, and irradiates water mixed in polyaniline with sunlight, so that the water is decomposed into hydrogen and oxygen under the combined action of the sunlight and polyaniline.
The above documents disclose some methods for preparing hydrogen and oxygen by photocatalytic water splitting, but still have the problem that the prepared hydrogen and oxygen are difficult to separate, while hydrogen peroxide is an important industrial raw material, so that the development of a method for preparing hydrogen and hydrogen peroxide by photocatalytic water splitting is still of great significance.
Disclosure of Invention
The invention aims to provide a method for preparing hydrogen and hydrogen peroxide by photocatalytic water decomposition, which comprises the steps of adding a photocatalyst into water to obtain a mixed reaction liquid, irradiating the mixed reaction liquid with light to generate hydrogen and hydrogen peroxide, realizing the simultaneous preparation of hydrogen and hydrogen peroxide by photocatalytic water decomposition, avoiding the generation of oxygen in the preparation process and avoiding the difficulty brought by the separation of hydrogen and oxygen; in the process of simultaneously preparing hydrogen and hydrogen peroxide, the highest output efficiency of the hydrogen can reach 8.5 mu mol/mg/h, the highest output efficiency of the hydrogen peroxide can reach 7.0 mu mol/mg/h, and the output efficiency of the method can still be kept to be 90-95 percent of the highest output efficiency after continuous photocatalytic decomposition is carried out for 10 days, such as 90 percent, 91 percent, 92 percent, 93 percent, 94 percent or 95 percent and the like.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a method for preparing hydrogen and hydrogen peroxide by photocatalytic water decomposition, which comprises the following steps:
(1) adding a photocatalyst into water to obtain a mixed reaction solution;
(2) and (2) irradiating the mixed reaction liquid obtained in the step (1) with light to generate hydrogen and hydrogen peroxide.
The method comprises the steps of adding a photocatalyst into water to obtain a mixed reaction liquid, and irradiating the mixed reaction liquid with light to generate hydrogen and hydrogen peroxide.
In the process of decomposing water by photocatalysis, on one hand, water is reduced into hydrogen, on the other hand, water is oxidized into hydrogen peroxide, and in the process of oxidizing water into hydrogen peroxide, a two-electron transfer process can occur, so that compared with a four-electron transfer process for oxidizing water into oxygen, more energy is saved, and the efficiency of decomposing water by photocatalysis is increased.
Preferably, the photocatalyst of step (1) comprises a semiconducting titanium dioxide and a promoter.
The method selects semiconductor titanium dioxide and a cocatalyst to combine to form the photocatalyst, the photocatalyst is used in the process of generating hydrogen peroxide and hydrogen by photocatalytic water decomposition, the type of the generated water oxidation intermediate is hydroxyl radical, and the product of further oxidation is hydrogen peroxide.
Preferably, the photocatalyst is a composite of a semiconducting titanium dioxide and a promoter.
Preferably, the semiconducting titanium dioxide is brookite.
Preferably, the semiconductive titanium dioxide has a particle size of ≦ 300nm, such as 100nm, 150nm, 200nm, 250nm, 300nm, or the like, preferably ≦ 200 nm.
The method controls the granularity of the semiconductor titanium dioxide to be less than or equal to 300nm, and is beneficial to the uniformity of the dispersion of the cocatalyst on the semiconductor titanium dioxide, thereby ensuring the output efficiency of hydrogen and hydrogen peroxide.
Preferably, the promoter comprises any one or a mixture of two of platinum, gold or palladium nanoparticles, preferably platinum nanoparticles; here, the two mixtures refer to bimetallic nanoparticles or a mixture of any two nanoparticles formed between any two of platinum, gold or palladium; the bimetallic nanoparticles comprise platinum bimetallic nanoparticles, platinum palladium bimetallic nanoparticles or gold palladium bimetallic nanoparticles; the mixture of any two nanoparticles comprises a mixture of platinum nanoparticles and gold nanoparticles, a mixture of platinum nanoparticles and palladium nanoparticles, or a mixture of gold nanoparticles and palladium nanoparticles.
According to the method, when the platinum nanoparticles are used as the cocatalyst, the hydrogen output efficiency and the hydrogen peroxide output efficiency are high, wherein the hydrogen output efficiency can reach 8.5 mu mol/mg/h at most, the hydrogen peroxide output efficiency can reach 7.0 mu mol/mg/h at most, and the hydrogen output efficiency can still be 90-95% of the maximum hydrogen output efficiency after continuous photocatalytic decomposition is carried out for 10 days.
Preferably, the co-catalyst has a particle size of ≦ 5nm, such as 1nm, 2nm, 3nm, 4nm, or 5nm, and the like.
Preferably, the preparation method of the semiconductive titanium dioxide comprises the following steps: adding urea and sodium lactate solution to TiCl4Stirring the solution at room temperature, then carrying out hydrothermal reaction, filtering and washing to obtain the semiconductor titanium dioxide.
Preferably, the sodium lactate solution has a sodium lactate mass fraction of 30-70 wt%, such as 30 wt%, 40 wt%, 50 wt%, 60 wt% or 70 wt%, etc., preferably 60 wt%.
Preferably, the TiCl4The concentration of the solution is 0.2-0.35M, such as 0.2M, 0.25M, 0.3M, or 0.35M, etc.
Preferably, the urea is reacted with TiCl4The molar ratio of (2) to (3) is (6-20):1, for example 6:1, 7:1, 9:1, 11:1, 13:1, 15:1, 18:1 or 20:1, preferably (15-18): 1.
Preferably, the volume of the sodium lactate solution is in proportion to TiCl4The volume ratio of the solution is 1 (10-30), for example, 1:10, 1:15, 1:20, 1:25 or 1:30, preferably 1 (10-15).
Preferably, the stirring time is 20-120min, such as 20min, 30min, 40min, 50min, 60min, 70min, 80min, 90min, 100min, 110min or 120min, etc., preferably 30 min.
Preferably, the temperature of the hydrothermal reaction is 180-220 ℃, such as 180 ℃, 190 ℃, 200 ℃, 210 ℃ or 220 ℃, preferably 200 ℃.
Preferably, the hydrothermal reaction time is 10-24h, such as 10h, 12h, 14h, 16h, 18h, 20h or 24h, etc.
The semiconductor titanium dioxide prepared by the method is brookite, more than 90% (exemplary including 90%, 93%, 95% or 98% and the like) of the prepared semiconductor titanium dioxide is in a short rod-shaped structure, the particle size of the semiconductor titanium dioxide is less than or equal to 200nm, more active crystal faces are exposed, and the semiconductor titanium dioxide has better hydrophilicity, so that the prepared photocatalyst has better hydrophilicity, and the photocatalyst obtained by taking the semiconductor titanium dioxide as a carrier loaded cocatalyst has higher efficiency of decomposing catalytic water to produce hydrogen and hydrogen peroxide, when the loaded platinum nanoparticles are taken as the photocatalyst, the highest hydrogen production efficiency can reach 8.5 mu mol/mg/h, and the highest hydrogen peroxide production efficiency can reach 7.0 mu mol/mg/h.
Preferably, the preparation method of the photocatalyst comprises the step of mixing the semiconductor titanium dioxide and the cocatalyst by in-situ photoreduction or a physical method.
Preferably, the preparation method of the photocatalyst comprises supporting the promoter on the semiconducting titanium dioxide by a photo-reduction method.
Preferably, the reduction time of the photo-reduction method is 10-120min, such as 10min, 20min, 30min, 40min, 50min, 60min, 70min, 80min, 90min, 100min, 110min or 120min, etc., preferably 30-90min, and more preferably 60 min.
Preferably, the physical method comprises ultrasonic immersion or grinding.
Preferably, the mass percentage of the promoter in the photocatalyst is 0.1-5 wt% (the mass of the promoter is calculated by the reduced metal of the promoter), such as 0.1 wt%, 1 wt%, 2 wt%, 3 wt%, 4 wt% or 5 wt%.
The mass percentage of the cocatalyst on the photocatalyst is required to be controlled to be 0.1-5 wt%, so that the process of photocatalytic water decomposition of the invention is ensured to keep higher output efficiency of hydrogen and hydrogen peroxide; when the mass percentage of the cocatalyst in the photocatalyst is less than 0.1 wt% or more than 5 wt%, the efficiency of the preparation process is reduced.
Preferably, in step (1), the solid-to-liquid ratio of the photocatalyst to water is (0.01-100) mg/mL, for example, 0.01mg/mL, 0.1mg/mL, 1mg/mL, 5mg/mL, 10mg/mL, 20mg/mL, 30mg/mL, 40mg/mL, 50mg/mL, 60mg/mL, 70mg/mL, 80mg/mL, 90mg/mL, or 100 mg/mL.
The method needs to control the solid-liquid ratio of the photocatalyst to water to be (0.01-100) mg/mL, which is beneficial to ensuring the stable operation of the preparation process, when the solid-liquid ratio is less than 0.01mg/mL, the efficiency of the preparation process is too low, when the solid-liquid ratio is more than 100mg/mL, the preparation efficiency is reduced to some extent, and the preparation process is difficult to be stably operated due to the excessive addition of the photocatalyst.
Preferably, the water in step (1) is deionized water.
The method adopts deionized water as a solvent for photocatalytic water decomposition without adding other reagents such as a sacrificial agent and the like, so that the preparation process has the advantages of low cost, no need of complex equipment, contribution to practical application and good industrial prospect.
Preferably, the light source irradiated by the light in the step (2) comprises any one of ultraviolet light, sunlight, full-band xenon lamp or mercury lamp or the combination of at least two of the above, wherein the combination comprises the combination of ultraviolet light and sunlight, the combination of sunlight and mercury lamp or the combination of ultraviolet light and full-band xenon lamp, and the like, and is preferably mercury lamp.
Preferably, the wavelength of the light irradiation in step (2) is 50-420nm, such as 50nm, 70nm, 100nm, 120nm, 150nm, 170nm, 200nm, 250nm, 300nm, 350nm, 400nm or 420nm, etc., preferably 300-420 nm.
Preferably, the light source for the light irradiation in step (2) is selected from mercury lamps with the light emission wavelength of 300-420 nm.
Preferably, the mixed reaction solution of step (1) is subjected to degassing and sealing treatment before the light irradiation of step (2).
Before the method of the invention is used for preparing hydrogen and hydrogen peroxide by light irradiation, degassing and sealing treatment are carried out on the mixed reaction liquid; the degassing process removes air dissolved in the mixed reaction liquid, thereby avoiding the influence of the air on the preparation process; the sealing treatment can avoid the influence of air entering the mixed reaction liquid on the preparation process; by the treatment mode before illumination, the method provided by the invention achieves higher output efficiency of hydrogen and hydrogen peroxide and higher stability of the preparation process.
Preferably, the degassing method comprises introducing an inert gas into the mixed reaction liquid.
Preferably, the inert gas comprises argon and/or nitrogen.
As a preferred technical scheme of the invention, the method comprises the following steps:
(1) adding a photocatalyst into water to obtain a mixed reaction solution, wherein the photocatalyst is a compound of semiconductor titanium dioxide and a cocatalyst; the mass percentage of the cocatalyst in the photocatalyst is 0.1-5 wt%; the solid-liquid ratio of the photocatalyst to water is (0.01-100) mg/mL, the semiconductor titanium dioxide is brookite, the particle size of the semiconductor titanium dioxide is less than or equal to 200nm, and the cocatalyst is platinum nanoparticles;
(2) and (2) introducing inert gas into the mixed reaction liquid for degassing, sealing, and irradiating the mixed reaction liquid obtained in the step (1) by using a mercury lamp with the light-emitting wavelength of 300-420nm as a light source to generate hydrogen and hydrogen peroxide, wherein the inert gas comprises argon and/or nitrogen.
The method of the invention generates hydrogen and hydrogen peroxide by decomposing water through photocatalysis, avoids the phenomenon of difficult separation of products, and compared with the traditional process of generating hydrogen and oxygen, the preparation process of the invention has obviously improved efficiency, and the generated hydrogen peroxide is an important chemical raw material; the method of the invention also obtains higher efficiency of photocatalytic water decomposition by controlling the types of the photocatalyst, especially the types of the semiconductor titanium dioxide and the cocatalyst, when the semiconductor titanium dioxide is selected as the carrier and the platinum is selected as the cocatalyst, the highest hydrogen output efficiency can reach 8.5 mu mol/mg/h, and the highest hydrogen peroxide output efficiency can reach 7.0 mu mol/mg/h.
Compared with the prior art, the invention has the following beneficial effects:
(1) the method realizes the simultaneous preparation of hydrogen and hydrogen peroxide by photocatalytic water decomposition, simultaneously avoids the generation of oxygen in the preparation process, and avoids the difficulty brought by the separation of the hydrogen and the oxygen;
(2) in the process of simultaneously preparing hydrogen and hydrogen peroxide, the highest output efficiency of the hydrogen can reach 8.5 mu mol/mg/h, and the highest output efficiency of the hydrogen peroxide can reach 7.0 mu mol/mg/h;
(3) after the continuous photocatalytic decomposition is carried out for 10 days, the output efficiency of the method is still kept to be 90-95% of the highest output efficiency;
(4) the method has the advantages of short process flow, low preparation cost, no need of complex reaction equipment, more contribution to practical application and good industrialization prospect.
Drawings
FIG. 1 is a morphology of a semiconductor titanium dioxide prepared in example 1 of the present invention under a transmission electron microscope;
FIG. 2 is an X-ray powder diffraction pattern of the semiconductive titanium dioxide prepared in example 1 of the present invention;
FIG. 3 is a diagram of the morphology of the photocatalyst prepared in example 1 under a transmission electron microscope;
FIG. 4 is an X-ray powder diffraction pattern of the photocatalyst prepared in example 1 of the present invention;
FIG. 5 is a bar graph of the production of hydrogen and hydrogen peroxide over time as produced in example 1 of the present invention.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The method for preparing hydrogen and hydrogen peroxide by photocatalysis comprises the following steps:
(1) adding 1mg of photocatalyst into 10mL of deionized water, and transferring the mixture into a 50mL quartz tube to obtain a mixed reaction solution, wherein the photocatalyst is a compound of semiconductor titanium dioxide and a cocatalyst; the mass percentage of the cocatalyst in the photocatalyst is 1 wt%; the semiconductor titanium dioxide is brookite, the cocatalyst is platinum nanoparticles, the photocatalyst is prepared by adopting a photoreduction method, and the reduction time is 60 min;
(2) introducing inert gas into the mixed reaction liquid for degassing treatment to remove air dissolved in the mixed reaction liquid, sealing by using a rubber plug, irradiating the mixed reaction liquid obtained in the step (1) by using a mercury lamp with the light-emitting wavelength of 300-420nm as a light source to generate hydrogen and hydrogen peroxide, wherein the inert gas is argon, and the power density of the light irradiation is 500mW/cm2。
The preparation method of the semiconductive titanium dioxide of the present example is as follows: mixing 15g of urea and 5mL of sodium lactate solution (mass concentration of sodium lactate)60% by weight) is added to TiCl4Stirring the solution (0.25M,60mL) at room temperature for 30min, transferring the solution into a reaction kettle, heating the solution at 200 ℃ for 12h, and then washing and drying the solution to obtain the semiconductor titanium dioxide.
The steps of the photoreduction method described in this example include formulating H2PtCl6Adding a methanol aqueous solution (the mass fraction of methanol is 20 wt%) into semiconductor titanium dioxide, mixing, performing ultrasonic dispersion, performing ultraviolet irradiation for 60min, and performing centrifugal separation to obtain the photocatalyst.
The morphology of the semiconductor titanium dioxide prepared in the embodiment under a transmission electron microscope is shown in fig. 1, and it can be seen from the graph that more than 90% of the semiconductor titanium dioxide is in a short rod-like structure, the particle size of the semiconductor titanium dioxide is less than or equal to 200nm, the X-ray diffraction pattern of the semiconductor titanium dioxide is shown in fig. 2, and it can be seen from the graph that the semiconductor titanium dioxide prepared in the embodiment is brookite-type titanium dioxide; the appearance of the photocatalyst prepared by the embodiment under a transmission electron microscope is shown in fig. 3, and it can be seen from the figure that the particle size of the platinum nanoparticles is less than or equal to 5nm, and the platinum nanoparticles are tightly combined with the semiconductor titanium dioxide; the X-ray powder diffraction pattern of the photocatalyst prepared in this example is shown in fig. 4, from which it can be seen that no diffraction peak of platinum is substantially observed, indicating that the platinum nanoparticles have good dispersibility on the surface of the semiconductor titanium dioxide; the histogram of the change of the yields of hydrogen and hydrogen peroxide over time obtained in this example is shown in fig. 5, and can be obtained by calculation from data in the graph, the reaction is performed for 5 hours, and the efficiencies of producing hydrogen and hydrogen peroxide are respectively 8.5 μmol/mg/h and 7.0 μmol/mg/h (i.e., the average hydrogen and hydrogen peroxide production rate within 5 hours, i.e., the average hydrogen and hydrogen peroxide production amount within 1g of photocatalyst per 1 hour).
Example 2
This example replaces the semiconductive titanium dioxide of example 1 with brookite or the like quality with anatase selected from shanghai aladine (hydrophilic type, 25nm particle size), all other conditions being exactly the same as in example 1.
Example 3
This example replaced the semiconductor titanium dioxide in example 1 from brookite or the like by a mixture of brookite and anatase in a mass ratio of 1:1 (the brookite used in this example was the same as in example 1, and anatase was the same as in example 2), and the other conditions were exactly the same as in example 1.
Example 4
In this example, the promoter in example 1 was replaced with palladium nanoparticles, and the other conditions were exactly the same as those in example 1.
Example 5
In this example, the promoter in example 1 was replaced by gold nanoparticles, and the other conditions were completely the same as those in example 1.
Example 6
This example replaces the photo-reduction method with the ultrasonic immersion method for preparing the photocatalyst in example 1, and the other conditions are exactly the same as those in example 1.
Example 7
The difference between the embodiment and the embodiment 1 is that the mass percentage content of the cocatalyst in the photocatalyst is changed from 1 wt% to 0.1 wt%, and other conditions are completely the same compared with the embodiment 1.
Example 8
The difference between the embodiment and the embodiment 1 is that the mass percentage content of the cocatalyst in the photocatalyst is changed from 1 wt% to 5 wt%, and other conditions are completely the same compared with the embodiment 1.
Example 9
The difference between the embodiment and the embodiment 1 is that the mass percentage content of the cocatalyst in the photocatalyst is changed from 1 wt% to 6 wt%, and other conditions are completely the same compared with the embodiment 1.
Example 10
The difference between the embodiment and the embodiment 1 is that the mass percentage content of the cocatalyst in the photocatalyst is changed from 1 wt% to 0.01 wt%, and other conditions are completely the same compared with the embodiment 1.
Example 11
This example is different from example 1 in that the amount of the photocatalyst added was replaced with 0.1mg, and other conditions were completely the same as those in example 1.
Example 12
This example is different from example 1 in that the amount of the photocatalyst added was replaced with 1000mg, and other conditions were completely the same as those in example 1.
Comparative example 1
The comparative example replaces the photocatalyst of the example 1 with brookite (same as the brookite used in the example 1, namely, the photocatalyst of the comparative example does not contain noble metal) in the same quality, and other conditions are completely the same as those of the example 1.
The performance test method comprises the following steps:
the hydrogen production test was performed for examples 1 to 12 and comparative example 1 by using a gas chromatograph of Tianmei 7900; the gas chromatography uses a 0.5nm molecular sieve column (3m multiplied by 2mm), a thermal conductivity cell detector (TCD), helium is used as carrier gas, and the generated hydrogen amount is calibrated by an external standard method.
The method for testing the hydrogen peroxide output of examples 1 to 12 and comparative example 1 is o-toluidine oxidation, and the absorption intensity is tested by using an ultraviolet spectrum.
The production efficiencies (i.e., average production efficiencies over 5 h) of hydrogen and hydrogen peroxide prepared in examples 1-12 and comparative example 1 are shown in table 1:
TABLE 1
As can be seen from the above table, in the process of simultaneously preparing hydrogen and hydrogen peroxide by the method, the highest output efficiency of the hydrogen can reach 8.5 mu mol/mg/h, and the highest output efficiency of the hydrogen peroxide can reach 7.0 mu mol/mg/h; has practical production significance.
It can be seen from comparative examples 1 to 3 that the semiconductor titanium dioxide of the photocatalyst is the most efficient in catalytically decomposing water when brookite is selected, and it can be seen from comparative examples 1, 4 and 5 that the co-catalyst of the photocatalyst is the most efficient in catalytically decomposing water when platinum nanoparticles are selected; it can be seen from comparative examples 1 and 6 that the activity of the catalyst prepared by the photo-reduction method is the highest in the process of preparing hydrogen peroxide and hydrogen by decomposing water by photocatalysis, and it can be seen from comparative examples 1 and 7 to 10 that the optimum platinum nanoparticles loading amount is 0.1 to 5%, and when the loading amount is less than 0.1% or more than 5%, the photocatalytic effect is reduced. It can be seen from comparative examples 11-12 that the yields of hydrogen and hydrogen peroxide in the process of the present invention are both high in the range where the solid-to-liquid ratio of photocatalyst to water is (0.01-100) mg/mL. As can be seen by comparing example 1 with comparative example 1, when the photocatalyst is pure brookite, the yield efficiency of the hydrogen obtained by the method is 0.4 mu mol/mg/h, the yield efficiency of the hydrogen peroxide is 0.35 mu mol/mg/h, and the effect is obviously inferior to that of the photocatalyst loaded with platinum nanoparticles.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (18)
1. A method for preparing hydrogen and hydrogen peroxide by photocatalytic water decomposition is characterized by comprising the following steps:
(1) adding a photocatalyst into water to obtain a mixed reaction solution;
(2) irradiating the mixed reaction liquid obtained in the step (1) with light to generate hydrogen and hydrogen peroxide;
the photocatalyst in the step (1) comprises semiconductor titanium dioxide and a cocatalyst, and the preparation method of the semiconductor titanium dioxide comprises the following steps: adding urea and sodium lactate solution to TiCl4Stirring the solution at room temperature, then carrying out hydrothermal reaction, filtering and washing to obtain the semiconductor titanium dioxide, wherein the photocatalyst is a compound of the semiconductor titanium dioxide and a cocatalyst, and the semiconductor IIThe preparation method of the photocatalyst comprises the step of loading a promoter on semiconductor titanium dioxide by a photoreduction method, wherein the promoter is any one or a mixture of two of platinum, gold or palladium nanoparticles.
2. The method of claim 1, wherein the semiconducting titanium dioxide has a particle size of less than or equal to 300 nm.
3. The method of claim 2, wherein the semiconducting titanium dioxide has a particle size of 200nm or less.
4. The method of claim 1, wherein the promoter is a platinum nanoparticle.
5. The method of claim 1, wherein the promoter has a particle size of 5nm or less.
6. The method of claim 1, wherein the reduction time of the photo-reduction method is 10-120 min.
7. The method of claim 6, wherein the reduction time of the photo-reduction method is 30-90 min.
8. The method of claim 7, wherein the reduction time of the photo-reduction method is 60 min.
9. The method of claim 1, wherein the cocatalyst is present in the photocatalyst in an amount of 0.1 to 5 wt%.
10. The method of claim 1, wherein the solid to liquid ratio of photocatalyst to water in step (1) is (0.01-100) mg/mL.
11. The method of claim 1, wherein the water of step (1) is deionized water.
12. The method according to claim 1, wherein the light irradiation in step (2) is performed by a light source selected from the group consisting of mercury lamps having an emission wavelength of 300 and 420 nm.
13. The method as claimed in claim 1, wherein the power density of the light irradiation in step (2) is 100-1000mW/cm2。
14. The method of claim 13, wherein the light irradiation of step (2) is performed at a power density of 500mW/cm2。
15. The method according to claim 1, wherein the mixed reaction solution of step (1) is subjected to degassing and sealing treatment before the light irradiation of step (2).
16. The method of claim 15, wherein the degassing comprises introducing an inert gas into the mixed reaction solution.
17. The method of claim 16, wherein the inert gas comprises argon and/or nitrogen.
18. The method of claim 1, wherein the method comprises the steps of:
(1) adding a photocatalyst into water to obtain a mixed reaction solution, wherein the photocatalyst is a compound of semiconductor titanium dioxide and a cocatalyst; the mass percentage of the cocatalyst in the photocatalyst is 0.1-5 wt%; the solid-liquid ratio of the photocatalyst to water is (0.01-100) mg/mL, the semiconductor titanium dioxide is brookite, the particle size of the semiconductor titanium dioxide is less than or equal to 200nm, and the cocatalyst is platinum nanoparticles;
(2) and (2) introducing inert gas into the mixed reaction liquid for degassing, sealing, and irradiating the mixed reaction liquid obtained in the step (1) by using a mercury lamp with the light-emitting wavelength of 300-420nm as a light source to generate hydrogen and hydrogen peroxide, wherein the inert gas comprises argon and/or nitrogen.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910106984.4A CN111517276B (en) | 2019-02-02 | 2019-02-02 | Method for preparing hydrogen and hydrogen peroxide by photocatalytic water decomposition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910106984.4A CN111517276B (en) | 2019-02-02 | 2019-02-02 | Method for preparing hydrogen and hydrogen peroxide by photocatalytic water decomposition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111517276A CN111517276A (en) | 2020-08-11 |
| CN111517276B true CN111517276B (en) | 2021-12-24 |
Family
ID=71900476
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910106984.4A Active CN111517276B (en) | 2019-02-02 | 2019-02-02 | Method for preparing hydrogen and hydrogen peroxide by photocatalytic water decomposition |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111517276B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115073266A (en) * | 2022-07-20 | 2022-09-20 | 太原理工大学 | Device and process for preparing methanol based on coal |
| CN116065215B (en) * | 2023-03-07 | 2023-06-20 | 海南热带海洋学院 | Nanocomposite for preventing and treating artificial wetland matrix blockage and preparation method thereof |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1107680A (en) * | 1977-04-25 | 1981-08-25 | Sam L. Leach | Powerful energy transfer technique |
| JP2014114167A (en) * | 2011-03-30 | 2014-06-26 | Kyushu Univ | Method for direct production of hydrogen peroxide using brookite type titanium oxide |
| CN102718253A (en) * | 2012-06-20 | 2012-10-10 | 中国科学院福建物质结构研究所 | Brookite titanium dioxide nanocrystalline and preparation method and application thereof |
| CN104525168B (en) * | 2014-12-18 | 2017-02-22 | 黑龙江大学 | Method for synthesizing anatase/brookite nano composite material for photocatalytic decomposition of water into hydrogen through one-step hydrothermal method |
| CN106086922B (en) * | 2016-07-19 | 2018-02-02 | 李国岭 | It is a kind of to utilize solar energy low cost production hydrogen peroxide and the electrolytic method of hydrogen |
| CN108654648B (en) * | 2018-05-03 | 2020-04-24 | 东北林业大学 | Preparation method and application of photocatalyst for efficiently preparing hydrogen peroxide by photolyzing water |
-
2019
- 2019-02-02 CN CN201910106984.4A patent/CN111517276B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN111517276A (en) | 2020-08-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Andronic et al. | Black TiO2 synthesis by chemical reduction methods for photocatalysis applications | |
| CN111477889A (en) | Monoatomic iron-nitrogen co-doped carbon electrocatalyst and preparation method and application thereof | |
| Luo et al. | Noble-metal-free cobaloxime coupled with metal-organic frameworks NH2-MIL-125: A novel bifunctional photocatalyst for photocatalytic NO removal and H2 evolution under visible light irradiation | |
| US20210005902A1 (en) | Method of preparing catalyst containing platinum dispersed on graphene quantum dot containing carrier for direct alcohol fuel cell and catalyst obtained by this method | |
| Zhang et al. | Cu (OH) 2-modified TiO2 nanotube arrays for efficient photocatalytic hydrogen production | |
| CN108786787B (en) | Preparation method and application of copper-doped carbon quantum dot/bismuth tungstate composite photocatalyst | |
| Miao et al. | Photoelectrocatalysis for high-value-added chemicals production | |
| Wang et al. | Decoration of CdS nanowires with Ni3S4 nanoballs enhancing H2 and H2O2 production under visible light | |
| CN111517276B (en) | Method for preparing hydrogen and hydrogen peroxide by photocatalytic water decomposition | |
| CN103041865B (en) | Organic anthraquinone dye sensitized and precious metal supported inorganic semiconductor visible-light photocatalyst, and preparation method and application of photocatalyst | |
| CN107308967B (en) | Catalyst promoter for photocatalytic decomposition of formic acid to produce hydrogen, photocatalytic system and method for decomposing formic acid to produce hydrogen | |
| Parvizi et al. | High-efficient photocatalytic fuel cell integrated with periodate activation for electricity production by degradation of refractory organics | |
| Cao et al. | Promoting photocatalytic performance of TiO2 nanomaterials by structural and electronic modulation | |
| Chen et al. | The synergic generation of CO3− and O2− radicals in a novel photocatalytic fuel cell for efficient oxidation of carbonate-containing wastewater and simultaneous electricity production | |
| CN108043437B (en) | Preparation method of hollow SiC carrier type Ir-Ru catalyst | |
| CN113401876A (en) | Method for producing hydrogen peroxide through photocatalysis without sacrificial agent | |
| CN103331174A (en) | Palladium-loaded cadmium sulfide visible-light-induced photocatalyst and preparation method thereof | |
| Li et al. | Efficient electrochemical NO reduction to NH3 over metal-free g-C3N4 nanosheets and the role of interface microenvironment | |
| CN113422080B (en) | Preparation method and application of carbon-supported non-platinum palladium-ruthenium-tungsten alloy nanoparticle electrocatalyst for alkaline hydrogen oxidation | |
| CN112774694B (en) | Preparation method and application of functional carbon quantum dot modified Ag-In-Zn-S quantum dot | |
| Sun et al. | A Minireview: The Mechanism of H2O2 Photoproduction by Graphitic Carbon Nitride | |
| CN109553067B (en) | Method for decomposing formic acid by photocatalysis | |
| CN109037717A (en) | A kind of ferrum-based catalyst and preparation method of alkaline fuel cell | |
| CN115532298B (en) | Preparation method of diatomic cluster photocatalyst | |
| CN104810529A (en) | Surface cyaniding modified nano metal material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |