CN110227500A - A kind of Cd1-xZnxS-Ni/MoS2Composite photo-catalyst and preparation method thereof, application - Google Patents

A kind of Cd1-xZnxS-Ni/MoS2Composite photo-catalyst and preparation method thereof, application Download PDF

Info

Publication number
CN110227500A
CN110227500A CN201910516149.8A CN201910516149A CN110227500A CN 110227500 A CN110227500 A CN 110227500A CN 201910516149 A CN201910516149 A CN 201910516149A CN 110227500 A CN110227500 A CN 110227500A
Authority
CN
China
Prior art keywords
mos
catalyst
nanosphere
composite photo
preparation
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.)
Withdrawn
Application number
CN201910516149.8A
Other languages
Chinese (zh)
Inventor
王磊
林海峰
黎艳艳
马晓伟
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Qingdao University of Science and Technology
Original Assignee
Qingdao University of Science and Technology
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Qingdao University of Science and Technology filed Critical Qingdao University of Science and Technology
Priority to CN201910516149.8A priority Critical patent/CN110227500A/en
Publication of CN110227500A publication Critical patent/CN110227500A/en
Withdrawn legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/04—Sulfides
    • B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
    • B01J27/051—Molybdenum
    • B01J27/0515—Molybdenum with iron group metals or platinum group metals
    • B01J35/23—
    • B01J35/33—
    • B01J35/39—
    • B01J35/61—
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/10—Heat treatment in the presence of water, e.g. steam
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/50—Processes
    • C25B1/55—Photoelectrolysis
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/0004—Gaseous mixtures, e.g. polluted air
    • G01N33/0009—General constructional details of gas analysers, e.g. portable test equipment
    • G01N33/0027—General constructional details of gas analysers, e.g. portable test equipment concerning the detector
    • G01N33/0036—Specially adapted to detect a particular component
    • G01N33/005—Specially adapted to detect a particular component for H2
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
    • C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1047—Group VIII metal catalysts
    • C01B2203/1052—Nickel or cobalt catalysts
    • C01B2203/1058—Nickel catalysts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Abstract

The present invention relates to a kind of Cd1‑xZnxS‑Ni/MoS2Composite photo-catalyst and preparation method thereof, application.Belong to field of inorganic nano material.MoS in composite material2The crystallinity of nanometer sheet is very low, can expose a large amount of production hydrogen activity site.The redox ability of the photogenerated charge of CdS is significantly improved by the doping of Zn and Ni and promotes the separation of photogenerated charge.The assemble nanometer ball of size uniformity has good anti-light corrosion and anti-ability of aggregation.Ultrasonic water bath method combination Electrostatic Absorption assembling process used by synthetic material is simply controllable, and the composite material that is prepared of the method is not necessarily to carried noble metal under visible light and the purpose of efficient photocatalysis Decomposition aquatic products hydrogen can be realized, energy consumption and cost are greatly reduced, the composite material catalysis hydrogen-producing speed being prepared is up to 112mmolh‑1·g‑1。

Description

A kind of Cd1-xZnxS-Ni/MoS2Composite photo-catalyst and preparation method thereof, application
Technical field
The present invention relates to field of inorganic nano material, and in particular to a kind of efficient Cd1-xZnxS-Ni/MoS2Complex light is urged Agent and preparation method thereof.
Background technique
Disclosing the information of the background technology part, it is only intended to increase understanding of the overall background of the invention, without certainty It is considered as recognizing or implying in any form that information composition has become existing skill well known to persons skilled in the art Art.
Energy shortage and environmental pollution are two main bugbears for restricting world today's development.In order to realize human society Sustainable development, the demand produced about the depollution of environment and clean energy resource are more more and more urgent.Not with social energy-output ratio Disconnected to increase, the demand of fossil fuel also further increases therewith, however, it is non-renewable due to fossil fuel, if things go on like this Fossil energy will be reduced rapidly until disappearing totally.In addition, greenhouse effects caused by combustion of fossil fuel and environmental pollution Problem is increasingly serious, and therefore, the exploitation of novel sustainable energy is imperative.The hydrogen energy carrier emerging as one kind, it It is the ideal substitute of fossil energy with the advantages such as energy density height and combustion product be pollution-free.There are many approach of hydrogen manufacturing, Current most widely used method is hydrogen to be extracted from fossil fuel, however can generate the CO for leading to environmental problem in this way2、CO Equal by-products.Solar energy is inexhaustible, and photocatalytic hydrogen production by water decomposition technology is because it can directly be utilized and be converted too Sun can receive the extensive concern of people, show wide application prospect.
Cadmium sulfide (CdS) is a kind of typical II-VI race's semiconductor material, belongs to direct band-gap semicondictor compound.CdS Edge energy be about 2.4eV, corresponding ABSORPTION EDGE is located in the visible-range of solar radiation, moreover, CdS have it is suitable Band structure can effectively excite photodissociation aquatic products hydrogen to react.Therefore, CdS is a kind of excellent visible photocatalysis aquatic products hydrogen catalysis Agent.Nevertheless, the photogenerated charge recombination rate that individually CdS particle shows in light-catalyzed reaction is high, photoetch with And clustering phenomena etc., seriously reduce the efficiency of its light-catalyzed reaction.In order to promote photogenerated charge to separate, partly with other by CdS It is a kind of effective strategy that conductor, which carries out compound hetero-junctions of constructing,.Recent research indicate that the transient metal sulfide of layer structure Such as MoS2, WS2Deng showing very excellent production in photocatalysis and electrocatalytic reaction as catalyst or co-catalyst Hydrogen activity has been even more than noble metal decorated catalyst.Therefore, the transient metal sulfide of layer structure is loaded into CdS On be expected to realize efficient visible photocatalysis aquatic products hydrogen reaction.Meanwhile the study found that it can be made to the CdS doping for carrying out Zn Conduction band potential becomes more negative, and the light absorpting ability of CdS not only can be improved in the doping of Ni but also can enhance it to photoproduction electricity Therefore the separating capacity of lotus facilitates the activity for being obviously improved its photodissociation aquatic products hydrogen to the CdS doping for carrying out Zn and Ni.In addition, In order to improve the anticorrosive and dispersibility of CdS nano particle, by the way that CdS nano-particles self assemble is formed answering for size uniformity Closing nanosphere is a kind of effective method.However, being doped the hydrothermal/solvent heat for usually requiring high temperature and pressure to CdS Reaction condition, and inventor has found: and up to the present, size uniformity is assembled by Zn, the CdS particle of Ni codope Nanosphere is also difficult to be produced to obtain.
Summary of the invention
In view of the deficiencies of the prior art, the present invention is intended to provide a kind of efficient Cd1-xZnxS-Ni/MoS2Composite photocatalyst The preparation method of agent is synthesized first by ultrasonic water bath method by Zn, the Cd of Ni codope1-xZnxThe nanometer of S-Ni assembling Then ball further loads upper MoS by the method for Electrostatic Absorption2, obtain Cd1-xZnxS-Ni/MoS2Compound assemble nanometer ball. The material has large specific surface area, and active site is more, it is seen that it is excellent that light absorpting ability is strong and photogenerated charge recombination rate is low etc. Gesture presents excellent photocatalysis Decomposition aquatic products hydrogen activity.
To realize the above-mentioned technical purpose, The technical solution adopted by the invention is as follows:
A kind of Cd1-xZnxS-Ni/MoS2Composite photo-catalyst, comprising:
Cd1-xZnxS-Ni nanosphere；
It is supported on the Cd1-xZnxMoS on S-Ni nanosphere2Nanometer sheet；
Wherein, 0≤x≤0.9.
For current hydrothermal/solvent thermal method be difficult to prepare size uniformity, by Zn, the CdS particle group of Ni codope Nanosphere made of dress, Cd1-xZnxThe bad problem of the anti-light corrosivity and dispersibility of S-Ni solid solution composite material, the application It has been prepared by ultrasonic water bath method combination Electrostatic Absorption process evenly dispersed by Cd1-xZnxS-Ni is nanocrystalline and MoS2Nanometer The Cd that piece is combined1-xZnxS-Ni/MoS2Assemble nanometer ball, this novel photocatalyst show efficient visible light point Solve water H2-producing capacity.
Research is found: with the increase of Ni doping, Cd1-xZnxS-Ni/MoS2The photocatalysis liberation of hydrogen of compound assemble nanometer ball Performance improves, but after the molar ratio of Ni doping reaches 10%, the additive amount for continuing to improve Ni will lead to compound assemble nanometer The photocatalysis liberation of hydrogen efficiency of ball declines, therefore, in some embodiments, the molar ratio of CdS, Zn, Ni be 1:0~0.9:0~ 0.1。
Research is found: with MoS2The increase of nanometer sheet adsorbance, Cd1-xZnxS-Ni/MoS2The light of compound assemble nanometer ball Catalytic hydrogen evolution performance improves, if but MoS2The large amount of adsorption of nanometer sheet will lead to Cd in 20%1-xZnxS-Ni/MoS2Compound assembling The anti-light corrosivity and dispersibility decline of nanosphere, therefore, in some embodiments, the Cd1-xZnxS-Ni nanosphere and MoS2 The mass ratio of nanometer sheet is 1:0.05~0.2.
An aspect of of the present present invention additionally provides a kind of Cd1-xZnxS-Ni/MoS2The preparation method of composite photo-catalyst, packet It includes:
Cd is prepared using ultrasonic water bath method1-xZnxS-Ni nanosphere；
By Cd1-xZnxS-Ni nanosphere and MoS2Dispersion liquid is uniformly mixed, and Electrostatic Absorption assembling forms Cd1-xZnxS-Ni/ MoS2Compound assemble nanometer ball.
The application research discovery: since reaction temperature is relatively uniform under condition of water bath heating for ultrasonic water bath method, while Under the concussion effect of ultrasonic wave, rapidly, and ultrasonic wave also has very for transfer in solution between reactant molecule and diffusion Big energy can be with induced product Cd1-xZnxThe nucleation and further growth of S-Ni.Therefore, enable reaction process equably It carries out, to obtain the Cd of single-size1-xZnxS-Ni nanosphere, effectively increases Cd1-xZnxS-Ni/MoS2Nanosphere can Decompose in light water H2-producing capacity.
In some embodiments, the Electrostatic Absorption assembling carries out under agitation.
In some embodiments, the MoS2Dispersion liquid is prepared using solvent supersonic stripping method.
In some embodiments, the specific steps of the ultrasonic water bath method are as follows:
S1, caddy, zinc chloride, nickel chloride and thiocarbamide are dissolved in water, ammonium hydroxide is then added, it is molten to be configured to presoma Liquid；
S2, the precursor solution of step S1 is carried out to ultrasonic water bath reaction, cooling, separation, washing, drying are to get Cd1- xZnxS-Ni nanosphere.
Research is found: the Cd of ultrasonic water bath method preparation0.5Zn0.5S/MoS2Composite Nano ball (undoped with Ni) is sacrificial in lactic acid Hydrogen-producing speed is up to 80mmolh under conditions of domestic animal agent-1·g-1, and the Cd of existing solvent-thermal method preparation0.85Zn0.15S/ MoS2Nanometer rods hydrogen-producing speed under conditions of lactic acid is sacrifice agent is up to 54mmolh-1·g-1, it follows that ultrasonic water Bath method helps to promote Cd1-xZnxS-Ni/MoS2The catalytic hydrogen evolution performance of composite photo-catalyst.
In some embodiments, the Cd1-xZnxS-Ni nanosphere and MoS2Dispersion liquid mixing method is ultrasonic mixing.
The present invention also provides the Cd of any above-mentioned method preparation1-xZnxS-Ni/MoS2Composite photo-catalyst.
The present invention also provides any above-mentioned Cd1-xZnxS-Ni/MoS2Composite photo-catalyst is preparing hydrogen-precipitating electrode or analysis Application in hydrogen sensor.
The beneficial effects of the present invention are:
(1) the present invention provides it is a kind of completely new prepare size uniformity contain MoS2And Cd1-xZnxS-Ni solid solution is answered It closes nanometer and assembles ball (Cd1-xZnxS-Ni/MoS2) and its preparation method and application, the composite wood being prepared using the method Material has the lesser Cd of size1-xZnxS-Ni is nanocrystalline and MoS compared with low-crystallinity2Clad can increase active site Quantity, to promote the raising of photocatalytic activity.The preparation method is simply controllable, and the composite wood that the method is prepared The purpose of photocatalysis Decomposition aquatic products hydrogen can be realized without carried noble metal under visible light in material, greatly reduce energy consumption and at This, the composite material catalytic activity being prepared is up to 112mmolh-1·g-1。
(2) the photodissociation aquatic products hydrogen catalyst that synthesizes of the present invention by be doped into CdS lattice Zn and Ni in combination with MoS2As co-catalyst, significantly reduces the recombination rate of photogenerated charge and introduce a large amount of production hydrogen activity site, and The assembling spherical structure of its size uniformity improves the anticorrosive and dispersibility of catalyst, to obtain excellent photocatalysis point Solve water efficiency.Therefore it is a meaningful hair that the composite material, which has the industrial applicability of the production novel environment friendly energy, Bright creation.
(3) operating method of the application it is simple, it is at low cost, have universality, be easy to large-scale production.
Detailed description of the invention
The accompanying drawings constituting a part of this application is used to provide further understanding of the present application, and the application's shows Meaning property embodiment and its explanation are not constituted an undue limitation on the present application for explaining the application.
Fig. 1 is the powder x-ray diffraction map of the various catalyst of 1-4 of embodiment of the present invention preparation.
Fig. 2 is Cd prepared by the embodiment of the present invention 60.5Zn0.5The scanning electron microscope (SEM) photograph of S-Ni assemble nanometer ball.
Fig. 3 is Cd prepared by the embodiment of the present invention 60.5Zn0.5The transmission electron microscope picture of S-Ni assemble nanometer ball.
Fig. 4 is the photodissociation aquatic products hydrogen curve graph of the various catalyst of 1-6 of embodiment of the present invention preparation.
Specific embodiment
It is noted that following detailed description is all illustrative, it is intended to provide further instruction to the application.Unless another It indicates, all technical and scientific terms used in this application have logical with the application person of an ordinary skill in the technical field The identical meanings understood.
It should be noted that term used herein above is merely to describe specific embodiment, and be not intended to restricted root According to the illustrative embodiments of the application.As used herein, unless the context clearly indicates otherwise, otherwise singular Also it is intended to include plural form, additionally, it should be understood that, when in the present specification using term "comprising" and/or " packet Include " when, indicate existing characteristics, step, operation, device, component and/or their combination.
In the examples where no specific technique or condition is specified, according to the literature in the art described technology or conditions or Person carries out according to product description.Reagents or instruments used without specified manufacturer, being can be by the normal of commercially available acquisition Advise product.
As background technique is introduced, for some problems of CdS semiconductor in the presence of light-catalyzed reaction, this hair The bright one kind that proposes is by MoS2Nanometer sheet and Zn, the Cd of Ni codope1-xZnxThe composite Nano ball that S-Ni particle assembles, note For Cd1-xZnxS-Ni/MoS2.There is the composite material uniform size to be distributed, Cd1-xZnxIt is coated on S-Ni nano particle MoS2Nanometer sheet.
Wherein, Cd1-xZnxThe smaller specific surface area for helping to improve composite Nano ball of the size of S-Ni nano particle, and And MoS in composite Nano ball2The crystallinity of nanometer sheet very low energy is enough exposed than usual high-crystallinity MoS2Nanometer sheet more produces Hydrogen activity site.
The study found that MoS2It is anti-applied to Photocatalyzed Hydrogen Production to can be used as a kind of excellent co-catalyst for substituting noble metal It answers.Meanwhile the redox ability of the photogenerated charge of CdS can be significantly improved by doping Zn and Ni and promote photogenerated charge Separation.Therefore, MoS is constructed2And Cd1-xZnxComposite material (the Cd of S-Ni solid solution1-xZnxS-Ni/MoS2) will be expected to realize height The photocatalysis Decomposition aquatic products hydrogen of effect reacts.
The invention proposes a kind of methods for preparing the composite material, prepare Zn, Ni by ultrasonic water bath method first The Cd of codope1-xZnxThen S-Ni assemble nanometer ball passes through electrostatic adsorption for MoS2Load to Cd1-xZnxS-Ni particle On obtain final goal product Cd1-xZnxS-Ni/MoS2Compound assemble nanometer ball.The preparation method is simply controllable, is prepared Composite material as visible photocatalysis aquatic products hydrogen catalyst there is the catalytic activity that significantly improves (catalytic activity be up to 112mmol·h-1·g-1)。
Wherein, the Cd1-xZnxThe diameter of S-Ni nano particle is about 80~100 nanometers.
Wherein, mole doping ratio x of the Zn is 0~90%, for example, 80%, also for example, 50%.
Wherein, mole doping percentage of the Ni is 0~10%, for example, 5%, also for example, 2%.
Wherein, the MoS2Mass percent be 5-20%, for example, 15%, also for example, 10%.
The ultrasonic power of the ultrasonic machine is 500 watts, and heating power is 1200 watts, temperature range: room temperature~80 degree Celsius, Power supply: 220 volts/50 hertz.
With reference to the accompanying drawing and specific embodiment the present invention is described further.
Instrument and equipment
Labsolar-6A photocatalytic water system for producing hydrogen and day the beauty spectrum produced using Beijing Bo Feilai Science and Technology Ltd. is had The photodissociation aquatic products hydrogen activity of the GC-7806 type gas chromatograph test catalyst of limit company production.
Embodiment 1
(1) CdS assemble nanometer ball is synthesized
100 milliliters of deionized water is being cleaned and poured into dry beaker (250 milliliters), is then sequentially adding 7 milliliters The sodium citrate aqueous solution of 0.1 mol/L, the caddy aqueous solution of 5 milliliter of 0.1 mol/L, the sulphur of 10 milliliter of 0.1 mol/L Urea aqueous solution, is finally added dropwise 2 milliliters of ammonium hydroxide, and stirring obtains clear transparent solutions in 5 minutes.Then by beaker preservative film It is put into after being sealed in ultrasonic machine (ultrasonic power is 500 watts), reacts 6 hours at 50 c.To natural after reaction It is cooled to room temperature, is centrifugated product, use ethyl alcohol and deionized water alternately washing 3 times.Product is finally put into vacuum drying Case, 70 degrees Celsius drying 6 hours, obtain CdS assemble nanometer ball.
The x-ray diffraction pattern for the CdS assemble nanometer ball that Fig. 1 is, it can be seen that the diffracted signal of product has simultaneously The feature of cubic phase and hexagonal phase CdS.
(2) the photocatalytic water H2-producing capacity test of Pt/CdS
Take the CdS ultrasonic disperse synthesized in 20 milligrams of steps (1) in 100 milliliters be 20% containing volume fraction lactic acid water In solution, the chloroplatinic acid aqueous solution that 7 microlitres of concentration are 0.077 mol/L is then added and is transferred to pool Fei Laike after mixing evenly The Labsolar-6A type that skill Co., Ltd provides is produced online in hydrogen and detection system.Suspension is deaerated to vacuum state, is made Illumination is carried out with 300 watts of the PLS-SXE 300D type xenon lamp equipped with 420 nanometers of edge filters, and with GC-7806 type gas phase The hydrogen that chromatograph detection generates, it is as a result shown in Figure 4.
Embodiment 2
(1)MoS2The preparation of nanometer sheet
By 1 mM of MoCl5Thioacetamide with 10.1 mMs is added sequentially to 35 milliliters of N, N- dimethyl methyl Ultrasonic dissolution is carried out in amide solvent, is then uniformly mixing to obtain precursor solution.Precursor solution is transferred to 50 milliliters In the autoclave of polytetrafluoroethyllining lining, it is placed in baking oven under 200 degrees celsius and reacts 24 hours.It is cooling to reaction kettle To room temperature, with after water and ethyl alcohol alternately washing 3 times after solid product is centrifuged in solution, dried in 70 degrees Celsius of vacuum It is 6 hours dry in case, obtain MoS2Nanometer sheet.
The MoS that Fig. 1 is2The x-ray diffraction pattern of nanometer sheet, it can be seen that the diffracted signal and MoS of product2Phase one It causes.
(2)MoS2The photodissociation aquatic products hydrogen activity of nanometer sheet is tested
Take the MoS synthesized in 20 milligrams of steps (1)2Nanometer sheet ultrasonic disperse is 20% containing volume fraction in 100 milliliters Lactic acid aqueous solution in, suspension is then transferred to the Labsolar-6A type photocatalysis that Bo Fei Lay Science and Technology Ltd. provides In reaction unit, then suspension is deaerated to vacuum state.It the use of 300 watts of PLS-SXE 300D type xenon lamps is light source, dress Upper 420 nanometers of edge filter is to export required visible light, and the hydrogen generated with the detection of GC-7806 type gas chromatograph Gas, it is as a result shown in Figure 4.
Embodiment 3
Step (1) is the same as (1) the step of embodiment 1
Step (2) is the same as (1) the step of embodiment 2
(3) CdS/MoS is synthesized2Nanosphere.By the MoS of 0.02 gram of step (2)2Nanometer sheet is added to 100 milliliters of N, N- diformazan Ultrasound removing 3 hours in base formamide, are then added the CdS nanosphere of 0.2 gram of step (1) preparation, ultrasonic mixing 1 hour it Afterwards, continue to stir 12 hours progress Electrostatic Absorption assembling process.The solid product in solution is centrifugated after the reaction was completed, is made It is 6 hours dry in 70 degrees Celsius of vacuum drying oven after water and ethyl alcohol alternately washing 3 times, obtain CdS/MoS2Composite Nano Ball.
(4)CdS/MoS2The photodissociation aquatic products hydrogen activity of composite Nano ball is tested
The CdS/MoS synthesized in 20 milligrams of steps (3) is taken first2Composite Nano ball ultrasonic disperse contains body in 100 milliliters In the lactic acid aqueous solution that fraction is 20%, suspension is then transferred to what Bo Fei Lay Science and Technology Ltd. provided In Labsolar-6A type photocatalytic reaction device, then suspension is deaerated to vacuum state.Use 300 watts of PLS-SXE 300D type xenon lamp is light source, loads onto 420 nanometers of edge filter to export required visible light.With GC-7806 type gas phase The hydrogen that chromatograph detection generates, it is as a result shown in Figure 4.
Embodiment 4
(1) Cd is synthesized0.5Zn0.5S nanosphere
100 milliliters of deionized water is being cleaned and poured into (250 milliliters) in dry beaker, 7 millis are then sequentially added The sodium citrate aqueous solution of 0.1 mol/L of liter, the caddy aqueous solution of 2.5 milliliter of 0.1 mol/L, 2.5 milliliters 0.1 mole/ 2 milliliters of ammonium hydroxide is finally added dropwise in the solder(ing)acid risen, the thiourea solution of 10 milliliter of 0.1 mol/L, stirs 5 points Clock obtains clear transparent solutions.Then it is put into after beaker being sealed with preservative film in ultrasonic machine (ultrasonic power is 500 watts), It is reacted 6 hours under 50 degrees Celsius.To cooled to room temperature after reaction, it is centrifugated product, uses ethyl alcohol and deionization Water alternately washing 3 times.Product is finally put into vacuum oven, 70 degrees Celsius drying 6 hours, obtain Cd0.5Zn0.5S group accommodates Rice ball.
The Cd that Fig. 1 is0.5Zn0.5The x-ray diffraction pattern of S assemble nanometer ball, it can be seen that all diffraction maximums Index turns to the hexagonal phase structure of CdS.
(2)Cd0.5Zn0.5The photodissociation aquatic products hydrogen activity of S assemble nanometer ball is tested
Take the Cd synthesized in 20 milligrams of steps (1)0.5Zn0.5S assemble nanometer ball ultrasonic disperse contains volume point in 100 milliliters In the lactic acid aqueous solution that number is 20%, suspension is then transferred to the Labsolar-6A that Bo Fei Lay Science and Technology Ltd. provides In type photocatalytic reaction device, then suspension is deaerated to vacuum state.It is using 300 watts of PLS-SXE 300D type xenon lamp Light source loads onto 420 nanometers of edge filter to export required visible light, and detected with GC-7806 type gas chromatograph The hydrogen of generation, it is as a result shown in Figure 4.
Embodiment 5
Step (1) is the same as (1) the step of embodiment 4
Step (2) is the same as (1) the step of embodiment 2
Step (3) synthesizes Cd0.5Zn0.5S/MoS2Composite Nano ball.By the MoS in 0.02 gram of step (2)2Nanometer sheet is added Ultrasound removing 3 hours into 100 milliliters of n,N-Dimethylformamide, are then added preparation in 0.2 gram of step (1) Cd0.5Zn0.5S assemble nanometer ball ultrasonic mixing 1 hour, continues to stir 12 hours progress Electrostatic Absorption assembling process, in solution It is 6 hours dry in 70 degrees Celsius of vacuum drying oven after solid product is alternately washed 3 times after being centrifuged with water and ethyl alcohol, Obtain Cd0.5Zn0.5S/MoS2Composite Nano ball.
(4)Cd0.5Zn0.5S/MoS2The photodissociation aquatic products hydrogen activity of composite Nano ball is tested
The Cd synthesized in 20 milligrams of steps (3) is taken first0.5Zn0.5S/MoS2Catalyst ultrasonic disperse contains in 100 milliliters In the lactic acid aqueous solution that volume fraction is 20%, suspension is then transferred to the Labsolar-6A type that Bo Fei Lay company provides In photocatalytic reaction device, then suspension is deaerated to vacuum state.It the use of 300 watts of PLS-SXE 300D type xenon lamps is light 420 nanometers of edge filter is loaded onto export required visible light in source.It is detected and is generated with GC-7806 type gas chromatograph Hydrogen, it is as a result shown in Figure 4.
Embodiment 6
(1) Cd is synthesized0.5Zn0.5S-Ni assemble nanometer ball
100 milliliters of deionized water is being cleaned and poured into (250 milliliters) in dry beaker, 7 millis are then sequentially added The sodium citrate aqueous solution of 0.1 mol/L of liter, the caddy aqueous solution of 2.5 milliliter of 0.1 mol/L, 2.5 milliliters 0.1 mole/ The thiourea solution and 5 milligrams of chlorination nickel by powder of the solder(ing)acid and 10 milliliter of 0.1 mol/L that rise, finally dropwise 2 milliliters of ammonium hydroxide are added, stirring obtains clear transparent solutions in 5 minutes.Then ultrasonic machine is put into after beaker being sealed with preservative film In (ultrasonic power 500W), react 6 hours at 50 c.To cooled to room temperature after reaction, centrifuge separation Product uses ethyl alcohol and deionized water alternately washing 3 times.Finally product is put into vacuum oven, 70 degrees Celsius of dryings 6 are small When, obtain Cd0.5Zn0.5S-Ni assemble nanometer ball.
The Cd that Fig. 2 is0.5Zn0.5The scanning electron microscope image of S-Ni nanosphere.As can be seen from Figure 2 the product is equal Even chondritic, diameter are 80-100 nanometers.
Fig. 3 is the images of transmissive electron microscope of the product.It can be seen that Cd0.5Zn0.5S-Ni nanosphere is by a large amount of small nanometer What crystalline substance assembled.
Step (2) is the same as the step of implementing 2 (1)
Step (3) synthesizes Cd0.5Zn0.5S-Ni/MoS2Composite Nano ball.By the MoS in 0.02 gram of step (2)2Nanometer sheet adds Enter into 100 milliliters of n,N-Dimethylformamide ultrasound removing 3 hours, preparation in 0.2 gram of step (1) is then added Cd0.5Zn0.5S-Ni assemble nanometer ball ultrasonic mixing 1 hour, continue to stir 12 hours progress Electrostatic Absorption assembling process, in solution Solid product be centrifuged after with after water and ethyl alcohol alternately washing 3 times, dry 6 is small in 70 degrees Celsius of vacuum drying oven When, obtain Cd0.5Zn0.5S-Ni/MoS2Composite Nano ball.
(4)Cd0.5Zn0.5S-Ni/MoS2The photodissociation aquatic products hydrogen activity of composite Nano ball is tested
Take the Cd synthesized in 20 milligrams of steps (3)0.5Zn0.5S-Ni/MoS2Composite Nano ball ultrasonic disperse contains in 100 milliliters Have in the lactic acid aqueous solution that volume fraction is 20%, suspension is then transferred to the Labsolar-6A that Bo Fei Lay company provides In type photocatalytic reaction device, then suspension is deaerated to vacuum state.It is using 300 watts of PLS-SXE 300D type xenon lamp Light source loads onto 420 nanometers of edge filter to export required visible light, and detected with GC-7806 type gas chromatograph The hydrogen of generation, it is as a result shown in Figure 4.
Figure 4, it is seen that Cd prepared by above-described embodiment 60.5Zn0.5S-Ni/MoS2Composite Nano ball is with lactic acid Rate for photocatalysis Decomposition aquatic products hydrogen under conditions of sacrifice agent is significantly better than Pt/CdS, CdS/MoS2And Cd0.5Zn0.5S/MoS2 Catalyst, wherein Cd0.5Zn0.5S-Ni/MoS2Hydrogen-producing speed be as many as 22 times of Pt/CdS.
Finally it should be noted that the foregoing is only a preferred embodiment of the present invention, it is not limited to this hair It is bright, although the present invention is described in detail referring to the foregoing embodiments, for those skilled in the art, still It can modify to technical solution documented by previous embodiment, or part is equivalently replaced.It is all in this hair Within bright spirit and principle, any modification, equivalent replacement, improvement and so on should be included in protection scope of the present invention Within.Above-mentioned, although the foregoing specific embodiments of the present invention is described with reference to the accompanying drawings, not to the scope of the present invention Limitation, those skilled in the art should understand that, based on the technical solutions of the present invention, those skilled in the art are not required to Make the creative labor the various modifications or changes that can be made still within protection scope of the present invention.

Claims (10)

1. a kind of Cd1-xZnxS-Ni/MoS2Composite photo-catalyst characterized by comprising
Cd1-xZnxS-Ni nanosphere；
It is supported on the Cd1-xZnxMoS on S-Ni nanosphere2Nanometer sheet；
Wherein, 0≤x≤0.9.
2. Cd as described in claim 11-xZnxS-Ni/MoS2Composite photo-catalyst, which is characterized in that mole of CdS, Zn, Ni Than for 1:0~0.9:0~0.1.
3. Cd as described in claim 11-xZnxS-Ni/MoS2Composite photo-catalyst, which is characterized in that the Cd1-xZnxS-Ni Nanosphere and MoS2The mass ratio of nanometer sheet is 1:0.05~0.2.
4. a kind of Cd1-xZnxS-Ni/MoS2The preparation method of composite photo-catalyst characterized by comprising
Cd is prepared using ultrasonic water bath method1-xZnxS-Ni nanosphere；
By Cd1-xZnxS-Ni nanosphere and MoS2Dispersion liquid is uniformly mixed, and Electrostatic Absorption assembling forms Cd1-xZnxS-Ni/MoS2It is multiple Close assemble nanometer ball.
5. Cd as claimed in claim 41-xZnxS-Ni/MoS2The preparation method of composite photo-catalyst, which is characterized in that described Electrostatic Absorption assembling carries out under agitation.
6. Cd as claimed in claim 41-xZnxS-Ni/MoS2The preparation method of composite photo-catalyst, which is characterized in that described MoS2Dispersion liquid is prepared using solvent supersonic stripping method.
7. Cd as claimed in claim 41-xZnxS-Ni/MoS2The preparation method of composite photo-catalyst, which is characterized in that described The specific steps of ultrasonic water bath method are as follows:
S1, caddy, zinc chloride, nickel chloride and thiocarbamide are dissolved in water, ammonium hydroxide is then added, is configured to precursor solution；
S2, the precursor solution of step S1 is carried out to ultrasonic water bath reaction, cooling, separation, washing, drying are to get Cd1-xZnxS- Ni nanosphere.
8. Cd as claimed in claim 41-xZnxS-Ni/MoS2The preparation method of composite photo-catalyst, which is characterized in that described Cd1-xZnxS-Ni nanosphere and MoS2Dispersion liquid mixing method is ultrasonic mixing.
9. the Cd of the described in any item method preparations of claim 4-81-xZnxS-Ni/MoS2Composite photo-catalyst.
10. claim 1-3,9 described in any item Cd1-xZnxS-Ni/MoS2Composite photo-catalyst is preparing hydrogen-precipitating electrode or analysis Application in hydrogen sensor.
CN201910516149.8A 2019-06-14 2019-06-14 A kind of Cd1-xZnxS-Ni/MoS2Composite photo-catalyst and preparation method thereof, application Withdrawn CN110227500A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910516149.8A CN110227500A (en) 2019-06-14 2019-06-14 A kind of Cd1-xZnxS-Ni/MoS2Composite photo-catalyst and preparation method thereof, application

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910516149.8A CN110227500A (en) 2019-06-14 2019-06-14 A kind of Cd1-xZnxS-Ni/MoS2Composite photo-catalyst and preparation method thereof, application

Publications (1)

Publication Number Publication Date
CN110227500A true CN110227500A (en) 2019-09-13

Family

ID=67859329

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910516149.8A Withdrawn CN110227500A (en) 2019-06-14 2019-06-14 A kind of Cd1-xZnxS-Ni/MoS2Composite photo-catalyst and preparation method thereof, application

Country Status (1)

Country Link
CN (1) CN110227500A (en)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110841660A (en) * 2019-11-26 2020-02-28 福建农林大学 Ternary bionic composite visible light catalyst and preparation method thereof
CN110902654A (en) * 2019-12-03 2020-03-24 曾功昶 Method for preparing deuterium gas by photocatalytic heavy water
CN111534834A (en) * 2020-03-19 2020-08-14 中国科学技术大学 Corrosion-resistant photo-anode composite material and preparation method thereof
CN112007658A (en) * 2020-08-07 2020-12-01 西安工程大学 Preparation method of cadmium zinc sulfide-titanic acid nanotube composite photocatalyst
CN112023948A (en) * 2020-08-21 2020-12-04 西安工程大学 Photocatalyst for efficiently decomposing water to produce hydrogen by photocatalysis and preparation method thereof
CN113617365A (en) * 2021-08-24 2021-11-09 青岛科技大学 Porous Cd with stacking faults1-xZnxS/GO composite material and preparation method thereof
CN114849737A (en) * 2022-05-19 2022-08-05 电子科技大学长三角研究院(湖州) Flower-like cadmium sulfide/silver sulfide quantum dot composite photocatalyst and application thereof
CN115178279A (en) * 2022-06-29 2022-10-14 华南理工大学 Synthetic metal R-doped MoS 2 Thin-layer nanosheet method and product thereof

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110841660A (en) * 2019-11-26 2020-02-28 福建农林大学 Ternary bionic composite visible light catalyst and preparation method thereof
CN110841660B (en) * 2019-11-26 2022-10-14 福建农林大学 Ternary bionic composite visible light catalyst and preparation method thereof
CN110902654A (en) * 2019-12-03 2020-03-24 曾功昶 Method for preparing deuterium gas by photocatalytic heavy water
CN111534834B (en) * 2020-03-19 2021-12-14 中国科学技术大学 Corrosion-resistant photo-anode composite material and preparation method thereof
CN111534834A (en) * 2020-03-19 2020-08-14 中国科学技术大学 Corrosion-resistant photo-anode composite material and preparation method thereof
CN112007658A (en) * 2020-08-07 2020-12-01 西安工程大学 Preparation method of cadmium zinc sulfide-titanic acid nanotube composite photocatalyst
CN112007658B (en) * 2020-08-07 2023-02-03 西安工程大学 Preparation method of cadmium zinc sulfide-titanic acid nanotube composite photocatalyst
CN112023948A (en) * 2020-08-21 2020-12-04 西安工程大学 Photocatalyst for efficiently decomposing water to produce hydrogen by photocatalysis and preparation method thereof
CN113617365A (en) * 2021-08-24 2021-11-09 青岛科技大学 Porous Cd with stacking faults1-xZnxS/GO composite material and preparation method thereof
CN113617365B (en) * 2021-08-24 2023-08-04 青岛科技大学 Porous Cd with stacking fault 1-x Zn x S/GO composite material and preparation method thereof
CN114849737A (en) * 2022-05-19 2022-08-05 电子科技大学长三角研究院(湖州) Flower-like cadmium sulfide/silver sulfide quantum dot composite photocatalyst and application thereof
CN115178279A (en) * 2022-06-29 2022-10-14 华南理工大学 Synthetic metal R-doped MoS 2 Thin-layer nanosheet method and product thereof
CN115178279B (en) * 2022-06-29 2023-05-23 华南理工大学 Synthetic metal R doped MoS 2 Method for thin-layer nanoplatelets and products thereof

Similar Documents

Publication Publication Date Title
CN110227500A (en) A kind of Cd1-xZnxS-Ni/MoS2Composite photo-catalyst and preparation method thereof, application
Li et al. Phosphorus modified Ni-MOF–74/BiVO4 S-scheme heterojunction for enhanced photocatalytic hydrogen evolution
US11345616B2 (en) Heterojunction composite material consisting of one-dimensional IN2O3 hollow nanotube and two-dimensional ZnFe2O4 nanosheet, and application thereof in water pollutant removal
Wang et al. Insight into charge carrier separation and solar-light utilization: rGO decorated 3D ZnO hollow microspheres for enhanced photocatalytic hydrogen evolution
CN110560105B (en) Preparation of nickel phosphide-loaded sulfur indium zinc nano microsphere composite material and application of composite material in photocatalytic hydrogen production
CN102631939B (en) Graphene/silver phosphate composite visible light photocatalyst and preparation method thereof
CN111389442B (en) P-N heterojunction composite material loaded on surface of foamed nickel and preparation method and application thereof
CN101811044B (en) Potassium niobate nanotube photocatalyst and preparation method and application thereof
CN108499585B (en) Phosphorus-containing compound and preparation and application thereof
CN104324733B (en) The preparation method of non precious metal high activity photolytic hydrogen production catalyst
CN106362774B (en) A kind of 1D/2D vertical configuration CdS/MoS2Produce the preparation method of hydrogen catalyst
CN106732668A (en) A kind of hydrothermal preparing process of flower-shaped molybdenum bisuphide/cupric oxide composite nano materials
CN108479810A (en) A kind of WS2/ZnIn2S4Composite visible light catalyst and preparation method thereof
CN106378160B (en) It is a kind of to prepare CdS/MoS2The method of composite hollow square photochemical catalyst
CN109847786A (en) A kind of preparation method and application of Z-type photochemical catalyst MgAlLDH/CN-H
CN112264049B (en) Mo or Fe doped Zn for synthesizing ammonia by photocatalysis nitrogen fixation 1-x In 2 S 4 Process for preparing catalyst
Huang et al. A S-scheme heterojunction of Co9S8 decorated TiO2 for enhanced photocatalytic H2 evolution
Yu et al. NiO nanoparticles dotted TiO2 nanosheets assembled nanotubes PN heterojunctions for efficient interface charge separation and photocatalytic hydrogen evolution
CN108927174A (en) A kind of ZnS/rGO/CuS nano-photocatalyst and preparation method thereof
CN110368955A (en) A kind of VS2The preparation method of/CdS composite photo-catalyst
CN114160164B (en) CeO 2-x S x Preparation method and application of/CdZnS/ZnO nano material
Zhu et al. Cu-MOF modified Cd0. 5Zn0. 5S nanoparticles to form S-scheme heterojunction for efficient photocatalytic H2 evolution
CN113769764B (en) CdS/Cu 7 S 4 /CdMoO 4 Preparation method and application of nano heterostructure
Zhang et al. Construction of graphdiyne (CnH2n-2) based Co-SP/CuI double S-scheme heterojunctions proved with in situ XPS characterization for efficient photocatalytic hydrogen production
CN109046391A (en) A kind of composite material and preparation method and the application in visible photocatalysis aquatic products hydrogen

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
WW01 Invention patent application withdrawn after publication

Application publication date: 20190913

WW01 Invention patent application withdrawn after publication