CN110064426A - A kind of LixMoS2/CdS/g-C3N4The preparation and its decomposition aquatic products hydrogen application of composite photo-catalyst - Google Patents
A kind of LixMoS2/CdS/g-C3N4The preparation and its decomposition aquatic products hydrogen application of composite photo-catalyst Download PDFInfo
- Publication number
- CN110064426A CN110064426A CN201910371311.1A CN201910371311A CN110064426A CN 110064426 A CN110064426 A CN 110064426A CN 201910371311 A CN201910371311 A CN 201910371311A CN 110064426 A CN110064426 A CN 110064426A
- Authority
- CN
- China
- Prior art keywords
- cds
- mos
- preparation
- catalyst
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 239000001257 hydrogen Substances 0.000 title claims abstract description 32
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 32
- 239000002131 composite material Substances 0.000 title claims abstract description 23
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 23
- 229910016043 LixMoS2 Inorganic materials 0.000 title claims abstract description 9
- 238000000354 decomposition reaction Methods 0.000 title abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000003054 catalyst Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 10
- 230000008569 process Effects 0.000 claims abstract description 4
- 229910052961 molybdenite Inorganic materials 0.000 claims description 49
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims description 49
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 37
- 239000000243 solution Substances 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 19
- 239000000843 powder Substances 0.000 claims description 19
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 18
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 17
- 238000009210 therapy by ultrasound Methods 0.000 claims description 17
- 238000001354 calcination Methods 0.000 claims description 16
- 238000004519 manufacturing process Methods 0.000 claims description 15
- 239000002244 precipitate Substances 0.000 claims description 15
- 238000001291 vacuum drying Methods 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- -1 transition metal sulfide Chemical class 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 11
- 238000000227 grinding Methods 0.000 claims description 10
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 10
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- 229910052723 transition metal Inorganic materials 0.000 claims description 8
- 238000006303 photolysis reaction Methods 0.000 claims description 7
- 230000015843 photosynthesis, light reaction Effects 0.000 claims description 7
- 239000004202 carbamide Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- LHQLJMJLROMYRN-UHFFFAOYSA-L cadmium acetate Chemical compound [Cd+2].CC([O-])=O.CC([O-])=O LHQLJMJLROMYRN-UHFFFAOYSA-L 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 235000015393 sodium molybdate Nutrition 0.000 claims description 5
- 239000011684 sodium molybdate Substances 0.000 claims description 5
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 5
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 230000000877 morphologic effect Effects 0.000 claims description 4
- 229910052724 xenon Inorganic materials 0.000 claims description 4
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 4
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- 229910017464 nitrogen compound Inorganic materials 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 3
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 8
- 238000007146 photocatalysis Methods 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 229910052976 metal sulfide Inorganic materials 0.000 abstract description 3
- 239000011206 ternary composite Substances 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 230000001052 transient effect Effects 0.000 abstract 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000012986 modification Methods 0.000 abstract 1
- 230000004048 modification Effects 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 230000008901 benefit Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- VDQVEACBQKUUSU-UHFFFAOYSA-M disodium;sulfanide Chemical compound [Na+].[Na+].[SH-] VDQVEACBQKUUSU-UHFFFAOYSA-M 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000004083 survival effect Effects 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229940101006 anhydrous sodium sulfite Drugs 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229940048181 sodium sulfide nonahydrate Drugs 0.000 description 1
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 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
- 238000001179 sorption measurement Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
- C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a kind of LixMoS2/CdS/g‑C3N4The preparation and its decomposition aquatic products hydrogen application of composite photo-catalyst.The catalyst the preparation method comprises the following steps: preparing CdS/g-C first3N4Heterojunction structure, then transient metal sulfide is carried on hetero-junctions by ultrasonic disperse, the modification of transient metal sulfide, synthesis of ternary composite photo-catalyst are finally completed using metal-doped method.The catalyst can be applied to photocatalysis Decomposition aquatic products hydrogen process, show excellent H2-producing capacity.Catalyst structure prepared by the present invention is novel, has good stability, and can effectively improve visible light-responded range, increases and produces hydrogen activity site, promotes electronics fast transfer, inhibits the compound of electronics and hole, efficiently converts water to clean energy resource hydrogen.
Description
Technical Field
The invention relates to a process for catalyzing hydrogen production under the condition of visible light, in particular to a novel ternary composite catalyst LixMoS2/CdS/g-C3N4The preparation method and the application thereof.
Background
Energy is the basis of human survival development, all economic activities and survival of human depend on the supply of energy, and exploitation and utilization of other resources also depend on energy. The long-term use of fossil fuels such as coal, oil and natural gas leads to the increasing exhaustion of fossil energy, and at the same time, the fossil fuels generate a large amount of harmful gases such as SO during the combustion process2、NO、CO2Etc., causing environmental pollution problems. Therefore, there is an increasing interest in developing clean renewable energy sources. Hydrogen energy is an ideal pollution-free green energy source in the new century, and hydrogen does not exist in the atmosphere, but exists in various water in large quantity. Hydrogen can be obtained from water by electrolysis or the like, but requires a large energy supply and is extremely expensive. The hydrogen is prepared by a convenient and cheap method, and the method becomes the desire of workers in energy and environmental sciences to dreams. Because sunlight belongs to inexhaustible renewable energy in nature, the photocatalysis technology is a green technology, if the photocatalysis technology can be utilized, huge economic benefits and ecological benefits can be generated for social development, and a great step is taken in the process of new energy technology. The catalytic decomposition of water by sunlight to produce hydrogen is one of the most excellent ways to solve energy and environmental problems. The exploration of efficient, stable and economic visible light catalytic materials is the key point for the practicability of the photocatalytic hydrogen production technology.
Metal sulfides are considered to be the most promising photocatalysts due to their good band gap and photocatalytic properties. CdS has gained wide attention from scientists due to its excellent performanceBut the larger band gap width limits its development. CdS/g-C3N4、CdS/TiO2The heterogeneous structure can effectively improve the hydrogen production rate, and a certain amount of cocatalyst is loaded to show more excellent catalytic performance. MoS2As a non-noble metal catalyst, it has advantages such as large specific surface area, strong adsorption capacity, and high reactivity, and has been widely studied in recent years.
Aiming at the problems, the invention constructs a lithium battery made of LixMoS2CdS and g-C3N4The three-element composite photocatalyst is formed. The novel catalyst is efficient, stable, environment-friendly, low in cost and long in service life, and has a good application prospect in the field of photocatalytic hydrogen production.
Disclosure of Invention
The technical problem is as follows: the invention aims to provide a new way for efficiently decomposing hydrogen produced by water by photocatalysis, in particular to a ternary composite catalyst LixMoS2/CdS/g-C3N4Preparation and application of the compound in decomposing water to produce hydrogen. The invention researches the hydrogen production by photolysis of water, water exists in the nature in large quantity, hydrogen is a novel energy structure which can be used as a substitute at present, the research of the hydrogen production by photolysis of water meets the requirements of reasonable utilization of resources, alleviation of energy crisis and reduction of excessive dependence on traditional energy, and has great significance for the healthy development of ecological environment.
The technical scheme is as follows: one kind of Li of the present inventionxMoS2/CdS/g-C3N4The preparation method of the composite photocatalyst comprises the steps of firstly preparing CdS and g-C3N4The heterojunction structure of the composite material is loaded with transition metal sulfide, and finally the morphological structure of the surface transition metal sulfide is changed to form the composite material; the specific operation steps are as follows:
step 1: g-C3N4The preparation of (1): grinding urea, calcining in muffle furnace at 400-700 deg.C for 3-7 hr, and calcining at 300-600 deg.C0.5-5h to obtain g-C3N4；
Step 2: heterojunction CdS/g-C3N4The preparation of (1): dissolving cadmium acetate and thioacetamide into ethanol according to the mol ratio of 1:10-1:5, and adding g-C according to the stoichiometric ratio3N4Stirring the solution at 60-100 deg.C for 3-8h, performing ultrasonic treatment for 3-8h to obtain uniform aqueous solution, centrifuging, and vacuum drying at 60-100 deg.C to obtain CdS/g-C3N4Powder;
and step 3: MoS2The preparation of (1): dissolving sodium molybdate nonahydrate and thiourea in a mixed solution of deionized water and ethanol according to a molar ratio of 1:7-1:2, carrying out ultrasonic treatment for 30-60min, and stirring for 2-5h until the solution is clear and transparent; putting the uniformly mixed deionized water and ethanol mixed solution into a hydrothermal kettle, reacting for 15-30h at 200-500 ℃, washing with water and ethanol for 3-6 times, taking the lower layer precipitate, and drying in vacuum at 60-100 ℃ to obtain MoS2Powder;
and 4, step 4: high dispersion MoS2/CdS/g-C3N4The preparation of (1): mixing MoS2With the prepared CdS/g-C3N4Dissolving the powder in deionized water according to the mass ratio of 1:500-1:1000, ultrasonically treating the solution for 3-8h, stirring at 50-100 ℃ for 8-12h to form uniform aqueous solution, centrifuging to take lower-layer precipitate, and vacuum drying at 60-100 ℃ to obtain MoS2/CdS/g-C3N4Powder;
and 5: lixMoS2/CdS/g-C3N4The preparation of (1): mixing Li2CO3And MoS2/CdS/g-C3N4Dispersing in deionized water for 1-3h, centrifuging to remove the lower precipitate, vacuum drying at 60-100 deg.C to obtain sample, grinding for 1-3h, and calcining at 400-700 deg.C under Ar protection for 2-5h to obtain the desired photocatalyst.
Wherein,
the carbon-nitrogen compound g-C in the heterojunction structure3N4The thickness is 0.1-10 nm.
The CdS and g-C3N4The mass ratio of the particles is 1:1-5:1, a heterojunction structure can be formed under the ultrasonic condition of 40-60kHz, and the prepared particles are fully subjected to ultrasonic treatment and are uniformly mixed.
The MoS2With heterojunction CdS/g-C3N4The mass ratio of the particles is 1:500-1:1000, and the prepared particles are fully stirred and uniformly dispersed.
The Li2CO3And MoS2/CdS/g-C3N4The mass ratio of (1: 1000) - (1: 100), and modifying MoS by using lithium carbonate2Make MoS2Has metal phase structure and increased surface active sites.
The application of the composite photocatalyst prepared by the method is as follows: the catalyst is applied to the hydrogen production reaction by photolysis, the reaction is carried out in a normal pressure reactor, the mass ratio of the catalyst to water in the reaction raw materials is 1:1000-1:1500, and a sacrificial agent Na2S、Na2SO3The concentration of (A) is 0.35M, 0.25M, respectively, at 84mW/cm3The reaction was carried out under irradiation of a xenon lamp.
Has the advantages that: compared with the prior art, the invention has the following advantages:
1. the invention researches the hydrogen production by photolysis of water, water exists in the nature in large quantity, hydrogen is a novel energy structure which can be used as a substitute at present, the research of the hydrogen production by photolysis of water meets the requirements of reasonable utilization of resources, alleviation of energy crisis and reduction of excessive dependence on traditional energy, and has great significance for the healthy development of ecological environment.
2. MoS in the catalyst prepared by the invention2CdS and g-C3N4The complex photocatalyst is formed by compounding, which is beneficial to widening the visible light response range, improving the transfer rate of electrons and inhibiting the combination of photo-generated electrons and holes, thereby improving the photocatalytic efficiency and accelerating the generation of hydrogen.
3. The catalyst prepared by the method is beneficial to increasing the hydrogen production active sites of the catalyst and improving the hydrogen production efficiency by doping the metal Li with the modified catalyst promoter.
Detailed Description
The invention discloses LixMoS2/CdS/g-C3N4The preparation method of the composite photocatalyst comprises the steps of firstly preparing CdS and g-C3N4The heterojunction structure of the composite material is loaded with transition metal sulfide, and finally the morphological structure of the surface transition metal sulfide is changed to form the composite material; the specific operation steps are as follows:
step 1: g-C3N4The preparation of (1): grinding 100-200g of urea, calcining in a muffle furnace at the temperature of 400-700 ℃ for 3-7h, and calcining at the temperature of 300-600 ℃ for 0.5-5h to obtain g-C3N4；
Step 2: heterojunction CdS/g-C3N4The preparation of (1): dissolving cadmium acetate and thioacetamide in a molar ratio of 1:10-1:5 in 100mL of ethanol, and adding g-C according to a stoichiometric ratio3N4Stirring the solution at 60-100 deg.C for 3-8h, performing ultrasonic treatment for 3-8h to obtain uniform aqueous solution, centrifuging, and vacuum drying at 60-100 deg.C to obtain CdS/g-C3N4Powder;
and step 3: MoS2The preparation of (1): dissolving sodium molybdate nonahydrate and thiourea in a mixed solution of deionized water and ethanol according to a molar ratio of 1:7-1:2, carrying out ultrasonic treatment for 30-60min, and stirring for 2-5h until the solution is clear and transparent; putting the uniformly mixed deionized water and ethanol mixed solution into a hydrothermal kettle, reacting for 15-30h at 200-500 ℃, washing with water and ethanol for 3-6 times, taking the lower layer precipitate, and drying in vacuum at 60-100 ℃ to obtain MoS2Powder;
and 4, step 4: high dispersion MoS2/CdS/g-C3N4The preparation of (1): mixing MoS2With the prepared CdS/g-C3N4Dissolving the powder in deionized water according to the mass ratio of 1:500-1:1000, and performing ultrasonic treatment on the solution for 3-8h, stirring for 8-12h at 50-100 ℃ to form a uniform aqueous solution, centrifuging to take the lower layer precipitate, and vacuum drying at 60-100 ℃ to obtain MoS2/CdS/g-C3N4Powder;
and 5: lixMoS2/CdS/g-C3N4The preparation of (1): mixing Li2CO3And MoS2/CdS/g-C3N4Dispersing in deionized water for 1-3h, centrifuging to remove the lower precipitate, vacuum drying at 60-100 deg.C to obtain sample, grinding for 1-3h, and calcining at 400-700 deg.C under Ar protection for 2-5h to obtain the desired photocatalyst.
Wherein:
the carbon-nitrogen compound g-C in the heterojunction structure3N4The thickness is 0.1-10 nm.
The CdS and g-C3N4The mass ratio of the particles is 1:1-5:1, a heterojunction structure can be formed under the ultrasonic condition of 40-60kHz, and the prepared particles are fully subjected to ultrasonic treatment and are uniformly mixed.
The MoS2With heterojunction CdS/g-C3N4The mass ratio of the particles is 1:500-1:1000, and the prepared particles are fully stirred and uniformly dispersed.
The Li2CO3And MoS2/CdS/g-C3N4The mass ratio of (1: 1000) - (1: 100), and modifying MoS by using lithium carbonate2Make MoS2Has metal phase structure and increased surface active sites.
The application of the composite photocatalyst prepared by the method of the invention is as follows: the catalyst is applied to the reaction of photolysis of water to produce hydrogen,
the reaction is carried out in a normal pressure reactor, the mass ratio of the catalyst to the water in the reaction raw materials is 1:1000-1:1500, and the sacrificial agent Na2S、Na2SO3The concentration of (A) is 0.35M, 0.25M, respectively, at 84mW/cm3The reaction was carried out under irradiation of a xenon lamp. The technical solution of the present invention is further illustrated by the following examplesAnd (6) detailed description.
The preparation method firstly prepares CdS and g-C3N4The heterojunction structure of the composite material is loaded with transition metal sulfide, and finally the morphological structure of the surface transition metal sulfide is changed to form the composite material; the specific operation steps are as follows:
step 1: g-C3N4The preparation of (1): grinding urea, calcining in a muffle furnace at the temperature of 400-700 ℃ for 3-7h, and calcining at the temperature of 300-600 ℃ for 0.5-5h to obtain g-C3N4；
Step 2: heterojunction CdS/g-C3N4The preparation of (1): dissolving cadmium acetate and thioacetamide into ethanol according to the mol ratio of 1:10-1:5, and adding g-C according to the stoichiometric ratio3N4Stirring the solution at 60-100 deg.C for 3-8h, performing ultrasonic treatment for 3-8h to obtain uniform aqueous solution, centrifuging, and vacuum drying at 60-100 deg.C to obtain CdS/g-C3N4Powder;
and step 3: MoS2The preparation of (1): dissolving sodium molybdate nonahydrate and thiourea in a mixed solution of deionized water and ethanol according to a molar ratio of 1:7-1:2, carrying out ultrasonic treatment for 30-60min, and stirring for 2-5h until the solution is clear and transparent; putting the uniformly mixed deionized water and ethanol mixed solution into a hydrothermal kettle, reacting for 15-30h at 200-500 ℃, washing with water and ethanol for 3-6 times, taking the lower layer precipitate, and drying in vacuum at 60-100 ℃ to obtain MoS2Powder;
and 4, step 4: high dispersion MoS2/CdS/g-C3N4The preparation of (1): mixing MoS2With the prepared CdS/g-C3N4Dissolving the powder in deionized water according to the mass ratio of 1:500-1:1000, ultrasonically treating the solution for 3-8h, stirring at 50-100 ℃ for 8-12h to form uniform aqueous solution, centrifuging to take lower-layer precipitate, and vacuum drying at 60-100 ℃ to obtain MoS2/CdS/g-C3N4Powder;
and 5: lixMoS2/CdS/g-C3N4The preparation of (1): mixing Li2CO3And MoS2/CdS/g-C3N4Dispersing in deionized water for 1-3h, centrifuging to remove the lower precipitate, vacuum drying at 60-100 deg.C to obtain sample, grinding for 1-3h, and calcining at 400-700 deg.C under Ar protection for 2-5h to obtain the desired photocatalyst.
Example 1
g-C3N4The preparation of (1): grinding 150g of urea, transferring the ground urea into a crucible, sealing the crucible, putting the crucible into a muffle furnace for calcination, raising the temperature to 500 ℃ by a program of 5 ℃/min, calcining for 5h, reducing the temperature to 400 ℃ by 5 ℃/min, calcining for 2h, and finally reducing the temperature to 20 ℃ by 5 ℃/min to obtain the g-C3N4。
Example 2
CdS/g-C3N4The preparation of (1): respectively dissolving 7.977g of cadmium acetate, 13.173g of thioacetamide and 3g of graphite-phase carbon nitride in 100mL of ethanol, stirring the solution at 70 ℃ for 8h, performing ultrasonic treatment at 40kHz for 5h to form a uniform solution, centrifuging the uniform solution to remove the lower layer precipitate, and performing vacuum drying at 70 ℃ for 10h to obtain CdS/g-C3N4And (3) powder.
Example 3
MoS2The preparation of (1): 2.419g of sodium molybdate nonahydrate and 3.806g of thiourea are dissolved in 35mL of deionized water and 35mL of ethanol solution, and the solution is stirred for 2h after ultrasonic treatment for 15min until the solution is clear and transparent. Putting the uniformly mixed solution into a hydrothermal kettle, reacting for 20h at 200 ℃, washing for 3 times with water, washing for 3 times with alcohol, taking the lower layer for precipitation, and drying for 10h at 70 ℃ in vacuum to obtain MoS2And (3) powder.
Example 4
0.01g of MoS was added to each deionized water25g CdS/g-C3N4Performing ultrasonic treatment on the solution for 3h, stirring at 90 ℃ for 12h to form a uniform aqueous solution, centrifuging to remove the lower layer precipitate, and vacuum drying at 70 ℃ for 10h to obtain MoS2/CdS/g-C3N4And (3) powder.
Other conditions were unchanged, MoS was changed2In different proportions, to prepare MoS2/CdS/g-C3N4。
Example 5
2g of prepared 0.5% by weight MoS are taken2/CdS/g-C3N4With 0.01g Li2CO3Dissolving in 30mL water, performing ultrasonic treatment for 2h, centrifuging to obtain the precipitate, vacuum drying at 70 deg.C for 10h to obtain sample, grinding for 1h, calcining at 500 deg.C for 3h under the protection of argon gas to obtain LixMoS2/CdS/g-C3N4A catalyst.
Other conditions were not changed, changing Li2CO3To prepare Li with different Li contentsxMoS2/CdS/g-C3N4。
Example 6
Adding 0.5g of catalyst into a mixed solution of 50.408g of sodium sulfide nonahydrate, 18.906g of anhydrous sodium sulfite and 600mL of deionized water, performing ultrasonic treatment for 30min until the mixture is uniformly mixed, placing the mixed solution in a reactor, discharging the air in the reactor by using a vacuum pump and argon, and controlling the concentration of the air in the reactor to be 84mW/cm3The reaction was carried out under xenon lamp irradiation, and the hydrogen yield was measured by gas chromatography.
The catalytic performance of several photocatalysts is shown in table 1.
TABLE 1 comparison of hydrogen production Performance of different catalysts
It can be seen from the table that when MoS2Is added in an amount of 0.5 wt%, Li2CO3When the addition amount of (B) is 1.5 wt%, the hydrogen production performance is best, and the catalyst effect is best.
Claims (6)
1. LixMoS2/CdS/g-C3N4The preparation method of the composite photocatalyst is characterized by comprising the following steps: the preparation method firstly prepares CdS and g-C3N4The heterojunction structure of the composite material is loaded with transition metal sulfide, and finally the morphological structure of the surface transition metal sulfide is changed to form the composite material; the specific operation steps are as follows:
step 1: g-C3N4The preparation of (1): grinding urea, calcining in muffle furnace at 400-700 deg.C for 3-7h, and calcining at 300-600 deg.C for 0.5-5h to obtain the final productTo obtain g-C3N4；
Step 2: heterojunction CdS/g-C3N4The preparation of (1): dissolving cadmium acetate and thioacetamide into ethanol according to the mol ratio of 1:10-1:5, and adding g-C according to the stoichiometric ratio3N4Stirring the solution at 60-100 deg.C for 3-8h, performing ultrasonic treatment for 3-8h to obtain uniform aqueous solution, centrifuging, and vacuum drying at 60-100 deg.C to obtain CdS/g-C3N4Powder;
and step 3: MoS2The preparation of (1): dissolving sodium molybdate nonahydrate and thiourea in a mixed solution of deionized water and ethanol according to a molar ratio of 1:7-1:2, carrying out ultrasonic treatment for 30-60min, and stirring for 2-5h until the solution is clear and transparent; putting the uniformly mixed deionized water and ethanol mixed solution into a hydrothermal kettle, reacting for 15-30h at 200-500 ℃, washing with water and ethanol for 3-6 times, taking the lower layer precipitate, and drying in vacuum at 60-100 ℃ to obtain MoS2Powder;
and 4, step 4: high dispersion MoS2/CdS/g-C3N4The preparation of (1): mixing MoS2With the prepared CdS/g-C3N4Dissolving the powder in deionized water according to the mass ratio of 1:500-1:1000, ultrasonically treating the solution for 3-8h, stirring at 50-100 ℃ for 8-12h to form uniform aqueous solution, centrifuging to take lower-layer precipitate, and vacuum drying at 60-100 ℃ to obtain MoS2/CdS/g-C3N4Powder;
and 5: lixMoS2/CdS/g-C3N4The preparation of (1): mixing Li2CO3And MoS2/CdS/g-C3N4Dispersing in deionized water for 1-3h, centrifuging to remove the lower precipitate, vacuum drying at 60-100 deg.C to obtain sample, grinding for 1-3h, and calcining at 400-700 deg.C under Ar protection for 2-5h to obtain the desired photocatalyst.
2. Li according to claim 1xMoS2/CdS/g-C3N4The preparation method of the composite photocatalyst is characterized by comprising the following steps: the carbon-nitrogen compound g-C in the heterojunction structure3N4The thickness is 0.1-10 nm.
3. Li according to claim 1xMoS2/CdS/g-C3N4The preparation method of the composite photocatalyst is characterized by comprising the following steps: the CdS and g-C3N4The mass ratio of the particles is 1:1-5:1, a heterojunction structure can be formed under the ultrasonic condition of 40-60kHz, and the prepared particles are fully subjected to ultrasonic treatment and are uniformly mixed.
4. Li according to claim 1xMoS2/CdS/g-C3N4The preparation method of the composite photocatalyst is characterized by comprising the following steps: the MoS2With heterojunction CdS/g-C3N4The mass ratio of the particles is 1:500-1:1000, and the prepared particles are fully stirred and uniformly dispersed.
5. Li according to claim 1xMoS2/CdS/g-C3N4The preparation method of the composite photocatalyst is characterized by comprising the following steps: the Li2CO3And MoS2/CdS/g-C3N4The mass ratio of (1: 1000) - (1: 100), and modifying MoS by using lithium carbonate2Make MoS2Has metal phase structure and increased surface active sites.
6. Use of a composite photocatalyst prepared by the process of claim 1, wherein: the catalyst is applied to the hydrogen production reaction by photolysis, the reaction is carried out in a normal pressure reactor, the mass ratio of the catalyst to water in the reaction raw materials is 1:1000-1:1500, and a sacrificial agent Na2S、Na2SO3The concentration of (A) is 0.35M, 0.25M, respectively, at 84mW/cm3The reaction was carried out under irradiation of a xenon lamp.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910371311.1A CN110064426A (en) | 2019-05-06 | 2019-05-06 | A kind of LixMoS2/CdS/g-C3N4The preparation and its decomposition aquatic products hydrogen application of composite photo-catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910371311.1A CN110064426A (en) | 2019-05-06 | 2019-05-06 | A kind of LixMoS2/CdS/g-C3N4The preparation and its decomposition aquatic products hydrogen application of composite photo-catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110064426A true CN110064426A (en) | 2019-07-30 |
Family
ID=67370112
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910371311.1A Pending CN110064426A (en) | 2019-05-06 | 2019-05-06 | A kind of LixMoS2/CdS/g-C3N4The preparation and its decomposition aquatic products hydrogen application of composite photo-catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110064426A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113058601A (en) * | 2021-03-26 | 2021-07-02 | 华东理工大学 | Preparation method and application of ternary composite catalyst for photocatalytic hydrogen production by water splitting |
| CN113117718A (en) * | 2021-03-29 | 2021-07-16 | 安徽建筑大学 | NiCoP-g-C3N4/CdS composite photocatalyst, preparation method and application thereof |
| CN113663713A (en) * | 2021-09-22 | 2021-11-19 | 海南聚能科技创新研究院有限公司 | Preparation method of modified g-C3N4/CdS and method for preparing hydrogen by photocatalysis |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102403499A (en) * | 2011-11-18 | 2012-04-04 | 合肥国轩高科动力能源有限公司 | Lithium ion battery cathode material LixMoS2Preparation method of (1) |
| CN103785434A (en) * | 2014-03-10 | 2014-05-14 | 福州大学 | g-C3N4 nanosheet/CdS composite visible-light-driven photocatalyst |
| CN105664977A (en) * | 2016-02-03 | 2016-06-15 | 中国科学院化学研究所 | Molybdenum disulfide-cadmium sulfide nanometer composite material and preparing method and application thereof |
| CN105688945A (en) * | 2016-03-22 | 2016-06-22 | 福州大学 | Composite photo-catalyst with molybdenum disulfide (MoS2) nanosheet/cadmium sulfide (CdS) nanowire core-shell structure |
| CN107570196A (en) * | 2017-09-20 | 2018-01-12 | 广东工业大学 | The graphite phase carbon nitride of a kind of modification/CdS composite photo-catalysts, its preparation method and hydrogen production process |
| CN108144635A (en) * | 2018-01-16 | 2018-06-12 | 开封大学 | A kind of preparation method of graphite phase carbon nitride-cadmium sulfide composite material |
-
2019
- 2019-05-06 CN CN201910371311.1A patent/CN110064426A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102403499A (en) * | 2011-11-18 | 2012-04-04 | 合肥国轩高科动力能源有限公司 | Lithium ion battery cathode material LixMoS2Preparation method of (1) |
| CN103785434A (en) * | 2014-03-10 | 2014-05-14 | 福州大学 | g-C3N4 nanosheet/CdS composite visible-light-driven photocatalyst |
| CN105664977A (en) * | 2016-02-03 | 2016-06-15 | 中国科学院化学研究所 | Molybdenum disulfide-cadmium sulfide nanometer composite material and preparing method and application thereof |
| CN105688945A (en) * | 2016-03-22 | 2016-06-22 | 福州大学 | Composite photo-catalyst with molybdenum disulfide (MoS2) nanosheet/cadmium sulfide (CdS) nanowire core-shell structure |
| CN107570196A (en) * | 2017-09-20 | 2018-01-12 | 广东工业大学 | The graphite phase carbon nitride of a kind of modification/CdS composite photo-catalysts, its preparation method and hydrogen production process |
| CN108144635A (en) * | 2018-01-16 | 2018-06-12 | 开封大学 | A kind of preparation method of graphite phase carbon nitride-cadmium sulfide composite material |
Non-Patent Citations (2)
| Title |
|---|
| DANTONG ZHANG ET AL.: "Facile band alignment of C3N4/CdS/MoS2 sandwich hybrid for efficient charge separation and high photochemical performance under visible-light", 《POWDER TECHNOLOGY》 * |
| JUNYING LIU ET AL.: "Metallic 1T-LixMoS2 co-catalyst enhanced photocatalytic hydrogen evolution over ZnIn2S4 floriated microspheres under visible light irradiation", 《CATALYSIS SCIENCE & TECHNOLOGY》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113058601A (en) * | 2021-03-26 | 2021-07-02 | 华东理工大学 | Preparation method and application of ternary composite catalyst for photocatalytic hydrogen production by water splitting |
| CN113058601B (en) * | 2021-03-26 | 2022-09-09 | 华东理工大学 | Preparation method and application of ternary composite catalyst for photocatalytic hydrogen production by water splitting |
| CN113117718A (en) * | 2021-03-29 | 2021-07-16 | 安徽建筑大学 | NiCoP-g-C3N4/CdS composite photocatalyst, preparation method and application thereof |
| CN113117718B (en) * | 2021-03-29 | 2023-03-14 | 安徽建筑大学 | NiCoP-g-C 3 N 4 CdS composite photocatalyst, preparation method and application thereof |
| CN113663713A (en) * | 2021-09-22 | 2021-11-19 | 海南聚能科技创新研究院有限公司 | Preparation method of modified g-C3N4/CdS and method for preparing hydrogen by photocatalysis |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Jin et al. | Ni, Co-based selenide anchored g-C3N4 for boosting photocatalytic hydrogen evolution | |
| CN111203231B (en) | Indium zinc sulfide/bismuth vanadate composite material and preparation method and application thereof | |
| CN110252346B (en) | MoS2/SnS2Preparation method and application of/r-GO composite photocatalyst | |
| CN106362774B (en) | A kind of 1D/2D vertical configuration CdS/MoS2Produce the preparation method of hydrogen catalyst | |
| CN107081166A (en) | A kind of g C3N4/TiO2Multilevel hierarchy and preparation method thereof | |
| CN107983371B (en) | Photocatalytic material Cu2-xS/Mn0.5Cd0.5S/MoS2And preparation method and application thereof | |
| CN110064426A (en) | A kind of LixMoS2/CdS/g-C3N4The preparation and its decomposition aquatic products hydrogen application of composite photo-catalyst | |
| CN107282075B (en) | Composite photocatalyst and preparation method thereof | |
| CN110721698B (en) | Bismuth vanadate/copper vanadate composite photocatalyst and preparation method and application thereof | |
| CN111644192A (en) | g-C3N4@CdxZn1-xSe composite photocatalyst and preparation method and application thereof | |
| CN113058617A (en) | Photocatalyst and preparation method and application thereof | |
| CN115007174A (en) | Two-dimensional CdIn 2 S 4 Nanosheet and preparation method and application thereof | |
| CN114534746A (en) | Photocatalytic hydrogen production system based on heterojunction photocatalyst and formaldehyde aqueous solution | |
| CN110368999A (en) | A kind of catalyst and its preparation method and application | |
| CN112547125B (en) | CdS/NiPc photocatalyst for water photolysis and preparation method thereof | |
| CN106964380B (en) | Three-dimensional cadmium sulfide/bismuth oxybromide heterojunction photocatalyst, and preparation method and application thereof | |
| CN110038641B (en) | Bismuth vanadate/chromium porphyrin/graphene quantum dot two-dimensional composite Z-type photocatalytic material, preparation method and application | |
| CN107952489A (en) | A kind of synthetic method of organic inorganic hybridization photochemical catalyst | |
| CN112023948A (en) | Photocatalyst for efficiently decomposing water to produce hydrogen by photocatalysis and preparation method thereof | |
| CN116173987A (en) | CdIn 2 S 4 /CeO 2 Heterojunction photocatalyst, preparation method and application thereof | |
| Hu et al. | High-performance photocatalytic hydrogen evolution in a Zn0. 5Cd0. 5S/MoS2 p–n heterojunction | |
| CN113101946B (en) | NiMoO4Base Z-type heterojunction photocatalyst and preparation and application thereof | |
| CN112226230B (en) | Hydrophilic solid up-conversion luminescent material, preparation method thereof and application thereof in photolysis water hydrogen production reaction | |
| CN103433064A (en) | Preparation method of nitrogen-doped zinc sulfide with visible-light catalytic activity and high stability and application thereof | |
| CN113441144A (en) | Photocatalytic hydrogen production cocatalyst, photocatalytic system and hydrogen production method |
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 | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190730 |