CN103934005B - A kind of zinc sulphide copper nano-wire visible light catalyst of cuprous ion doping and preparation established law and application - Google Patents
A kind of zinc sulphide copper nano-wire visible light catalyst of cuprous ion doping and preparation established law and application Download PDFInfo
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- CN103934005B CN103934005B CN201410181986.7A CN201410181986A CN103934005B CN 103934005 B CN103934005 B CN 103934005B CN 201410181986 A CN201410181986 A CN 201410181986A CN 103934005 B CN103934005 B CN 103934005B
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- 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
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
Abstract
The invention discloses a kind of quick synthetic method and application of zinc sulphide copper nano-wire visible light catalyst of cuprous ion doping, the present invention adopts pressure microwave to assist synthetic method, water is cooked solvent, divalent zinc salt is zinc source, copper nano-wire is substrate, through the sulfuration of over cure source, the clean zinc sulphide copper nano-wire visible light catalyst having compared with the cuprous ion doping of high visible activity that synthesized fast. Method for preparing catalyst of the present invention is simple, can not produce environmental pollution in preparation process. By the doping of cuprous ion, change zinc sulphide band structure, make catalyst photoresponse be extended to visible region; By the electronic conduction ability of copper nano-wire, strengthen electronics and hole to separative efficiency, there is no, under noble metal, greatly to improve the quantum efficiency of this type of material. Can be widely used in the fields such as photolysis water hydrogen, solar cell, antibacterial, photocatalysis treatment pollutant.
Description
Technical field
The present invention relates to photocatalyst technology field, be specifically related to a kind of zinc sulphide of cuprous ion dopingCopper nano-wire visible light catalyst and its preparation method and application.
Background technology
Environment and energy problem are one of significant challenge of facing of Present Global, address this problem meState's the Implement of sustainable development is built a harmonious society and is had great importance. Photocatalysis technology is the nearly more than ten yearsThe emerging technology growing up, its main application fields is degradable organic pollutant, preparation Hydrogen EnergyOxynitrides etc. in source, oxidation air. There is reaction condition gentleness, energy consumption is low, secondary pollution is fewEtc. advantage, aspect environment and the energy, there is very important application prospect. And at various photochemical catalystsIn, titanium dioxide research is the most extensive. Anatase phase titanium dioxide, its energy gap is 3.2eV, phaseThere is stronger redox ability and there is the spies such as high chemical stability for other photochemical catalystProperty. Zinc sulphide, as traditional fluorescent material, has also obtained research widely, and its energy gap is3.6eV, is widely used in the fields such as fluorescent material, sensor, photolysis water hydrogen, pollutant processing.But due to the restriction of titanium dioxide and zinc sulphide intrinsic energy gap, it can only be by ultraviolet excitation. CauseA kind of highly active visible light-responded property photochemical catalyst of this exploitation has great meaning. In this respect,Carry out cation doping by hydro-thermal reaction and can effectively change semiconductor energy band structure, thereby make purpleThe absorption band blue shift of outer photochemical catalyst, to visible region, is realized visible light catalytic reaction.
And utilize microwave chemical synthetic technology, and can reach and rapidly object be heated, make productReach better crystallinity degree, the advantages such as uniform doping. This patent, by pressure microwave-hydrothermal method, utilizes microwaveThe aqueous solution that contains He Liu source, zinc source is carried out to rapid and uniform heating, under relatively mild condition, exist fastOn copper nano-wire, wrap up zinc sulphide and be doped into cuprous ion, forming good visible-light response type light and urgeAgent.
Summary of the invention
The object of the invention is to for the existing defect of prior art and the market demand, provide a kind ofThe zinc sulphide copper nano-wire visible light catalyst of cuprous ion doping and simple, with low costPreparation method and application.
The concrete preparation side of the zinc sulphide copper nano-wire visible light catalyst of cuprous ion doping of the present inventionMethod, comprises the steps: wire copper nano-wire to be scattered in water, adds zinc source, stir,Add again sulphur source, after stirring, be placed in microwave reaction kettle, with the heating rate of 10～30 DEG C/minIntensification 5-10min, microwave power is 500-1200w, and initial pressure is 0-35bar, and reaction temperature is150-200 DEG C, the reaction time is 10-60min, is cooled to after room temperature, washing is to neutral, centrifugal and trueEmpty dry, obtain the zinc sulphide copper nano-wire visible light catalyst that cuprous ion adulterates.
The zinc sulphide copper nano-wire visible light catalyst of the cuprous ion doping that said method makes, its spyLevy and be, zinc sulphide is wrapped in the outside nucleocapsid structure that forms of copper nano-wire, and cuprous particle is at zinc sulphide tableFace doping.
In said method, the concrete steps of the preparation of wire copper nano-wire are: by cationic surface-activeAgent softex kw (CTAB) and organic amine solvent cetylamine (HDA) inUnder 150-200 DEG C of condition, dissolve completely, obtain solution A; Acetylacetone copper is dissolved in completely as copper sourceIn solution A, stir 3～5 minutes, the blackish green solution B obtaining, adds and is coated with your gold in solution BBelong to the silicon chip of platinum as catalyst, put into water heating kettle, under 140～200 DEG C of conditions, react 5～20Hour, be cooled to room temperature, clean 3～5 times, 50-80 DEG C of vacuum drying 2-8 hour of gained solid,Obtain wire copper nano-wire.
In the preparation method of the zinc sulphide copper nano-wire visible light catalyst of above-mentioned cuprous ion doping, lineRatio 1:0.5～the 1:10 of shape copper nano-wire and the amount of substance in zinc source, wherein optimum is 1:2.5.
In the preparation method of the zinc sulphide copper nano-wire visible light catalyst of above-mentioned cuprous ion doping, sulphurSource is 1:1～5:1 with the ratio of the total amount of substance of zinc-copper, and wherein optimum is 2:1.
In the preparation method of the zinc sulphide copper nano-wire visible light catalyst of above-mentioned cuprous ion doping, instituteThe zinc source of stating comprises zinc nitrate, zinc chloride, zinc sulfate, zinc acetate, zinc acetylacetonate, biphosphateZinc.
In the preparation method of the zinc sulphide copper nano-wire visible light catalyst of above-mentioned cuprous ion doping, instituteThe sulphur source of stating comprises vulcanized sodium, thiocarbamide, thioacetamide, cysteine, lauryl mercaptan.
The zinc sulphide copper nano-wire visible light catalyst of above-mentioned cuprous ion doping can be used for decomposing aquatic productsHydrogen.
Concrete steps are as follows:
The zinc sulphide copper nano-wire visible light catalyst of cuprous ion doping is scattered in to water and hole captureIn the mixed solution of agent, remove the air in reaction system, can under nitrogen or the protection of inert gas atmosphereSee irradiation 1-1.5h, the preferred 420nm of visible wavelength.
Described hole trapping agents comprise methyl alcohol, sodium oxalate, ammonium oxalate, disodium ethylene diamine tetraacetate,Tetrasodium ethylenediamine tetraacetate, vulcanized sodium, sodium sulphate, sodium sulfite, lactic acid and their mixture,Wherein optimum is the mixed solution of 0.35M vulcanized sodium and 0.25M sodium sulfite.
Product prepared by the present invention carries out structural characterization by following means: adopt at RigakuThe X-ray diffraction of measuring on RigakuD/Max-RB type X-ray diffractometer carries out the structure of sample and dividesAnalyse; Adopt the specific surface of the automatic physical adsorption appearance working sample of MicromeriticsTriStarII3020 typeAmass and pore structure; Adopt the ESEM that Japanese HitachiS-4800 type scanning electron Electronic Speculum obtains to shineSheet; The transmission electron microscope photo that adopts Japanese JEOLJEM-2100 type transmission electron microscope to obtain.
The present invention compared with prior art, has the following advantages and outstanding effect: used in the present inventionChemical reagent is common agents, cheap and easy to get. With at present need to be with various high-temperature roasting doping techniquesCompare, preparation technology is simple, easy to operate, and the pollution of generation is few, synthetic catalyst hydrogen outputGreatly, active high, cycle efficieny is good, and without carried noble metal co-catalyst, greatly reduces cost.The zinc sulphide copper nano-wire visible light catalyst non precious metal that the prepared cuprous ion of the present invention adulterates is negativeBe loaded in hydrogen generation efficiency under 420nm monochromatic light and reached 31.1%, be much higher than the zinc sulphide of pure phase and pureThe cuprous sulfide of phase.
Brief description of the drawings
Fig. 1 is the zinc sulphide copper nano-wire visible light catalyst of the obtained cuprous ion doping of embodiment 1XRD collection of illustrative plates (insertion figure is the XRD collection of illustrative plates that copper nano-wire vulcanizes sample under the same conditions),In XRD figure, each diffraction maximum is corresponding one by one with six side's phase zincblende zinc sulphide and elemental copper, shows sampleIn contain zincblende zinc sulphide and elemental copper, the peak of cuprous sulfide is not obvious, but comprises in insertion figureThe peak of cuprous sulfide and copper simple substance, also proves to contain in sample cuprous sulfide.
Fig. 2 is the prepared copper ion doped zinc sulphide copper nano-wire visible light catalyst of embodiment 1Nitrogen Adsorption and desorption isotherms, illustration is BJH graph of pore diameter distribution. The specific area of show sample in figureFor 8.183m2/g。
Fig. 3 is the prepared copper ion doped zinc sulphide copper nano-wire visible light catalyst of embodiment 1Field emission scanning electron microscope figure. Visible in figure, sample is wire, is divided into inside and outside double-decker.
Fig. 4 is the prepared copper ion doped zinc sulphide copper nano-wire visible light catalyst of embodiment 1Transmission electron microscope picture. Picture further proves the double wrapped nucleocapsid structure of sample, and its internal layer is that copper is receivedRice noodles one-dimentional structure, and outer wrap the zincblende zinc sulphide of the cuprous ion that adulterated.
Detailed description of the invention
That doing of how realizing is further detailed, clear, complete below in conjunction with specific embodiment to the present inventionIllustrate, listed embodiment is only further described the present invention wholely, does not therefore limit thisInvention:
Embodiment 1
By molten to cationic surface active agent softex kw (CTAB) and organic amineAgent cetylamine (HDA) dissolves completely under 180 DEG C of conditions, obtains solution A; Acetylacetone copper is doneFor copper source is dissolved in solution A completely, stir 3～5 minutes, the blackish green solution B obtaining, at solutionB adds the silicon chip that is coated with noble metal platinum as catalyst, puts into water heating kettle, anti-under 180 DEG C of conditionsAnswer 12 hours, be cooled to room temperature, clean 3～5 times, 80 DEG C of vacuum drying of gained solid 2 hours,Obtain wire copper nano-wire.
Get 2mmol copper nano-wire, 20mL water is in the beaker of 50mL, and ultrasonic dispersion, adds 5mmolZinc acetate and 14mmol thiocarbamide, after stirring. Proceed in microwave reaction kettle. Heating-up time is10min, microwave power is 1200w, and initial pressure is 35bar, and reaction temperature is 150 DEG C, when reactionBetween be 30min, to be cooled to room temperature. Wash neutrality with water, centrifugal and vacuum drying.
Fig. 1 is the zinc sulphide copper nano-wire visible light catalyst of the obtained cuprous ion doping of embodiment 1XRD collection of illustrative plates (insertion figure is the XRD collection of illustrative plates that copper nano-wire vulcanizes sample under the same conditions),In XRD figure, each diffraction maximum is corresponding one by one with six side's phase zincblende zinc sulphide and elemental copper, shows sampleIn contain zincblende zinc sulphide and elemental copper, the peak of cuprous sulfide is not obvious, but comprises in insertion figureThe peak of cuprous sulfide and copper simple substance, also proves to contain in sample cuprous sulfide.
Fig. 2 is the prepared copper ion doped zinc sulphide copper nano-wire visible light catalyst of embodiment 1Nitrogen Adsorption and desorption isotherms, illustration is BJH graph of pore diameter distribution. The specific area of show sample in figureFor 8.183m2/g。
Fig. 3 is the prepared copper ion doped zinc sulphide copper nano-wire visible light catalyst of embodiment 1Field emission scanning electron microscope figure. Visible in figure, sample is wire, is divided into inside and outside double-decker.
Fig. 4 is the prepared copper ion doped zinc sulphide copper nano-wire visible light catalyst of embodiment 1Transmission electron microscope picture. Picture further proves the double wrapped nucleocapsid structure of sample, and its internal layer is that copper is receivedRice noodles one-dimentional structure, and outer wrap the zincblende zinc sulphide of the cuprous ion that adulterated.
Embodiment 2,3,4
Difference from Example 1 is only copper nano-wire amount difference used, 2,3,4 points of embodimentWei 1mmol, 3mmol, 5mmol, the phase composition of products obtained therefrom thing is consistent, microscopic appearance is similar, thanSurface area has certain difference, wherein has the highest product hydrogen activity with 2mmol addition.
Embodiment 5,6,7,8,9
Difference from Example 1 is only zinc used source difference, 5,6,7,8,9 points of embodimentWei zinc nitrate, zinc chloride, zinc sulfate, zinc acetylacetonate, zinc dihydrogen phosphate, products therefrom thing phaseForm identical, in specific area, produce on hydrogen activity and all have any different, the wherein sample taking zinc acetate as zinc sourceProduct have the highest product hydrogen activity.
Embodiment 10,11,12,13,14
Difference from Example 1 is only sulphur used source difference, embodiment 10,11,12,13,14 are respectively vulcanized sodium, thiocarbamide, thioacetamide, cysteine, lauryl mercaptan, products therefrom thingPhase composition is identical, on specific area, product hydrogen activity, all has any different, and the wherein sample taking thiocarbamide as sulphur sourceProduct have the highest product hydrogen activity.
Embodiment 15,16,17,18,19,20
Difference from Example 1 is only microwave reaction temperature difference, embodiment 15,16,17,18,19,20 be respectively 140 DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 190 DEG C, 200 DEG C, gained producesThe phase composition of product thing is consistent, and microscopic appearance is similar, and specific area has certain difference, wherein anti-with 150 DEG CAnswer temperature to there is the highest product hydrogen activity.
Take sample 500mg that embodiment 1 makes in 100mL three-necked bottle, add 80mL's0.35M vulcanized sodium, 0.25M sodium sulfite mixed solution, ultrasonic being uniformly dispersed. In magnetic agitationIn situation, logical whole reactor nitrogen 10min is removed to the air in reaction system and reactor, juxtapositionIllumination 1h under 420nm monochromatic visible light lamp. With gas sample collector by sealing sillicon rubber blocking measureGas in 0.5mL reactor, then utilizes gas chromatograph to detect H2Amount.
Result shows that the zinc sulphide copper nano-wire visible ray of the prepared cuprous ion of the present embodiment doping urgesAgent non precious metal loads on hydrogen generation efficiency under 420nm monochromatic light and has reached 31.1%, is much higher than pureThe zinc sulphide of phase and the cuprous sulfide of pure phase.
Claims (7)
1. a preparation method for the zinc sulphide copper nano-wire visible light catalyst of cuprous ion doping, its spyLevy and be, comprise the following steps: wire copper nano-wire is scattered in water, adds zinc source, stir allEven, then add sulphur source, after stirring, be placed in microwave reaction kettle, with the intensification of 10～30 DEG C/minSpeed intensification 5-10min, microwave power is 500-1200w, initial pressure is 0-35bar, reaction temperatureFor 150-200 DEG C, the reaction time is 10-60min, is cooled to after room temperature, and washing is to neutral, also centrifugalVacuum drying, obtains the zinc sulphide copper nano-wire visible light catalyst that cuprous ion adulterates; Wire copper nanometerRatio 1:0.5～the 1:10 of line and the amount of substance in zinc source; Sulphur source with the ratio of the total amount of substance of zinc-copper is1:1～5:1。
2. the system of the zinc sulphide copper nano-wire visible light catalyst of cuprous ion doping described in claim 1Preparation Method, is characterized in that, the concrete steps of the preparation of described wire copper nano-wire are:
By cationic surface active agent softex kw and organic amine solvent cetylamineUnder 150-200 DEG C of condition, dissolve completely, obtain solution A; Acetylacetone copper is completely molten as copper sourceIn solution A, stir 3～5 minutes, the solution B obtaining, adds the silicon chip that is coated with platinum in solution BAs catalyst, put into water heating kettle, under 140～200 DEG C of conditions, react 5～20 hours, coolingTo room temperature, clean 3～5 times, 50-80 DEG C of vacuum drying 2-8 hour of gained solid, obtains wire copper and receivesRice noodles.
3. the system of the zinc sulphide copper nano-wire visible light catalyst of cuprous ion doping described in claim 1Preparation Method, is characterized in that, described zinc source comprise zinc nitrate, zinc chloride, zinc sulfate, zinc acetate,Zinc acetylacetonate, zinc dihydrogen phosphate.
4. the system of the zinc sulphide copper nano-wire visible light catalyst of cuprous ion doping described in claim 1Preparation Method, is characterized in that, described sulphur source comprises vulcanized sodium, thiocarbamide, thioacetamide, half GuangPropylhomoserin, lauryl mercaptan.
5. described in claim 1, the zinc sulphide copper nano-wire visible light catalyst of cuprous ion doping is used forDecompose aquatic products hydrogen.
6. described in claim 1, the zinc sulphide copper nano-wire visible light catalyst of cuprous ion doping is used forThe method of decomposing aquatic products hydrogen, is characterized in that, concrete steps are as follows: by the sulfuration of cuprous ion dopingZinc-copper nano wire visible light catalyst is scattered in the mixed solution of water and hole trapping agents, except dereactionAir in system, radiation of visible light 1-1.5h under nitrogen or the protection of inert gas atmosphere, visible wavelengthFor 420nm.
7. method claimed in claim 6, is characterized in that, described hole trapping agents comprise methyl alcohol,Sodium oxalate, ammonium oxalate, disodium ethylene diamine tetraacetate, tetrasodium ethylenediamine tetraacetate, vulcanized sodium, sulfuric acidSodium, sodium sulfite, lactic acid and their mixture.
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| CN104959626B (en) * | 2015-06-30 | 2017-02-22 | 厦门大学 | Method for preparing multifunctional core-shell nano-material by using alloy to wrap copper nanowires |
| CN108069390A (en) * | 2017-12-11 | 2018-05-25 | 河南师范大学 | The method that zinc sulphide photochemical catalyst photocatalysis lactic acid aqueous solution prepares hydrogen |
| CN109126824B (en) * | 2018-09-18 | 2021-09-14 | 张玉英 | Metal/nonmetal doped zinc sulfide copper photocatalyst and preparation method thereof |
| CN109174127A (en) * | 2018-09-18 | 2019-01-11 | 张玉英 | A kind of photocatalytic water prepares the composite photo-catalyst and preparation method of fuel cell hydrogen |
| CN109647533B (en) * | 2018-11-08 | 2020-07-31 | 华南农业大学 | Floatable magnetic polymer composite material and preparation method and application thereof |
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| CN102787347A (en) * | 2012-09-04 | 2012-11-21 | 上海师范大学 | Preparation method of overlong copper nanowire and conductive copper nanowire film |
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| CN102787347A (en) * | 2012-09-04 | 2012-11-21 | 上海师范大学 | Preparation method of overlong copper nanowire and conductive copper nanowire film |
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