CN103934005A - Cuprous ion-doped zinc sulfide copper nanowire visible-light-driven photocatalyst as well as preparation method and application thereof - Google Patents
Cuprous ion-doped zinc sulfide copper nanowire visible-light-driven photocatalyst as well as preparation method and application thereof Download PDFInfo
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- CN103934005A CN103934005A CN201410181986.7A CN201410181986A CN103934005A CN 103934005 A CN103934005 A CN 103934005A CN 201410181986 A CN201410181986 A CN 201410181986A CN 103934005 A CN103934005 A CN 103934005A
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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 rapid synthesis method and applications of a cuprous ion-doped zinc sulfide copper nanowire visible-light-driven photocatalyst. The cuprous ion-doped zinc sulfide copper nanowire visible-light-driven photocatalyst with high visible-light activity is rapidly synthesized through sulfuration of a sulfur source and cleaning by the pressure microwave-assisted synthesis method with water as a solvent, bivalent zinc salt as a zinc source and copper nanowires as a substrate. The catalyst disclosed by the invention has the advantages that the preparation method is simple and environmental pollution is not produced in the preparation process; a zinc sulfide energy band structure is changed through the doping of cuprous ions, so that the photoresponse of the catalyst is expanded to a visible region; the separating efficiency of electron-hole pairs is increased through the electron conduction capacity of the copper nanowires, so that the quantum efficiency of similar materials is greatly increased in the absence of noble metal; the catalyst can be widely applied to the fields of water-photolysis hydrogen production, solar cells, antibiosis, photocatalytic treatment of pollutants and the like.
Description
Technical field
The present invention relates to photocatalyst technology field, be specifically related to zinc sulphide copper nano-wire visible light catalyst of a kind of cuprous ion doping 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 China's the Implement of sustainable development is built a harmonious society and had great importance.Photocatalysis technology is the emerging technology growing up the nearly more than ten years, and its main application fields is oxynitrides etc. in degradable organic pollutant, preparation hydrogen energy source, oxidation air.There is the advantages such as reaction condition gentleness, energy consumption is low, secondary pollution is few, aspect environment and the energy, there is very important application prospect.And in various photochemical catalysts, titanium dioxide research is the most extensive.Anatase phase titanium dioxide, its energy gap is 3.2eV, has stronger redox ability and has the characteristics such as high chemical stability with respect to other photochemical catalyst.Zinc sulphide, as traditional fluorescent material, has also obtained research widely, and its energy gap is 3.6eV, 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.Therefore develop a kind of highly active visible light-responded property photochemical catalyst and have great meaning.In this respect, carry out cation doping by hydro-thermal reaction and can effectively change semiconductor energy band structure, thereby make the absorption band blue shift of ultraviolet light catalyst to visible region, realize visible light catalytic reaction.
And utilize microwave chemical synthetic technology, and can reach and rapidly object be heated, make product reach better crystallinity degree, the advantages such as uniform doping.This patent is by pressure microwave-hydrothermal method, utilize microwave to carry out rapid and uniform heating to the aqueous solution that contains He Liu source, zinc source, under relatively mild condition, on copper nano-wire, wrap up fast zinc sulphide and be doped into cuprous ion, forming good visible-light-responsive photocatalyst.
Summary of the invention
The object of the invention is to for the existing defect of prior art and the market demand, a kind of zinc sulphide copper nano-wire visible light catalyst of cuprous ion doping and preparation method and application simple, with low cost thereof are provided.
The concrete preparation method of the zinc sulphide copper nano-wire visible light catalyst of cuprous ion doping of the present invention, comprise the steps: wire copper nano-wire to be scattered in water, add zinc source, stir, add again sulphur source, after stirring, be placed in microwave reaction kettle, with the heating rate intensification 5-10min of 10～30 DEG C/min, microwave power is 500-1200w, initial pressure is 0-35bar, reaction temperature is 150-200 DEG C, reaction time is 10-60min, be cooled to after room temperature, washing is to neutral, centrifugal and vacuum drying, obtain the zinc sulphide copper nano-wire visible light catalyst of cuprous ion doping.
The zinc sulphide copper nano-wire visible light catalyst of the cuprous ion doping that said method makes, is characterized in that, zinc sulphide is wrapped in the outside nucleocapsid structure that forms of copper nano-wire, and cuprous particle is at zinc sulphide surface doping.
In said method, the concrete steps of the preparation of wire copper nano-wire are: cationic surface active agent softex kw (CTAB) and organic amine solvent cetylamine (HDA) are dissolved completely under 150-200 DEG C of condition, obtain solution A; Acetylacetone copper is dissolved in solution A completely as copper source, stir 3～5 minutes, the blackish green solution B obtaining, add the silicon chip that is coated with noble metal platinum as catalyst in solution B, put into water heating kettle, under 140～200 DEG C of conditions, react 5～20 hours, be cooled to room temperature, clean 3～5 times, 50-80 DEG C of vacuum drying 2-8 hour of gained solid, obtains wire copper nano-wire.
In the preparation method of the zinc sulphide copper nano-wire visible light catalyst of above-mentioned cuprous ion doping, the ratio 1:0.5～1:10 of wire 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, sulphur source 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, described zinc source comprises zinc nitrate, zinc chloride, zinc sulfate, zinc acetate, zinc acetylacetonate, zinc dihydrogen phosphate.
In the preparation method of the zinc sulphide copper nano-wire visible light catalyst of above-mentioned cuprous ion doping, described sulphur source 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 products hydrogen.
Concrete steps are as follows:
The zinc sulphide copper nano-wire visible light catalyst of cuprous ion doping is scattered in the mixed solution of water and hole trapping agents, removes the air in reaction system, radiation of visible light 1-1.5h under nitrogen or the protection of inert gas atmosphere, the preferred 420nm of visible wavelength.
Described hole trapping agents comprises methyl alcohol, sodium oxalate, ammonium oxalate, disodium ethylene diamine tetraacetate, tetrasodium ethylenediamine tetraacetate, vulcanized sodium, sodium sulphate, sodium sulfite, lactic acid and their mixture, and 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 the X-ray diffraction of measuring on Rigaku Rigaku D/Max-RB type X-ray diffractometer to carry out the structural analysis of sample; Adopt specific area and the pore structure of the automatic physical adsorption appearance working sample of MicromeriticsTriStar II3020 type; The stereoscan photograph that adopts Japanese Hitachi S-4800 type scanning electron Electronic Speculum to obtain; The transmission electron microscope photo that adopts Japanese JEOL JEM-2100 type transmission electron microscope to obtain.
The present invention compared with prior art, has the following advantages and outstanding effect: chemical reagent used in the present invention is common agents, cheap and easy to get.With at present need to be with compared with various high-temperature roasting doping techniques, preparation technology is simple, easy to operate, the pollution of generation is few, synthetic catalyst hydrogen output is large, 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 loads on hydrogen generation efficiency under 420nm monochromatic light and has reached 31.1%, is much higher than the zinc sulphide of pure phase and the cuprous sulfide of pure phase.
Brief description of the drawings
Fig. 1 is the XRD collection of illustrative plates (insertion figure is the XRD collection of illustrative plates that copper nano-wire vulcanizes sample under the same conditions) of the zinc sulphide copper nano-wire visible light catalyst of the obtained cuprous ion doping of embodiment 1, in XRD figure, each diffraction maximum is corresponding one by one with six side's phase zincblende zinc sulphide and elemental copper, show to contain in sample zincblende zinc sulphide and elemental copper, the peak of cuprous sulfide is not obvious, but in insertion figure, comprise the peak of cuprous sulfide and copper simple substance, also prove to contain in sample cuprous sulfide.
Fig. 2 is the nitrogen Adsorption and desorption isotherms of the prepared copper ion doped zinc sulphide copper nano-wire visible light catalyst of embodiment 1, and illustration is BJH graph of pore diameter distribution.In figure, the specific area of show sample is 8.183m
2/ g.
Fig. 3 is the field emission scanning electron microscope figure of the prepared copper ion doped zinc sulphide copper nano-wire visible light catalyst of embodiment 1.Visible in figure, sample is wire, is divided into inside and outside double-decker.
Fig. 4 is the transmission electron microscope picture of the prepared copper ion doped zinc sulphide copper nano-wire visible light catalyst of embodiment 1.Picture further proves the double wrapped nucleocapsid structure of sample, and its internal layer is copper nano-wire one-dimentional structure, and outer wrap the zincblende zinc sulphide of the cuprous ion that adulterated.
Detailed description of the invention
Be making further detailed, clear and complete description of how realizing below in conjunction with specific embodiment to the present invention, listed embodiment is only further described the present invention, not thereby limiting the invention:
Embodiment 1
Cationic surface active agent softex kw (CTAB) and organic amine solvent cetylamine (HDA) are dissolved completely under 180 DEG C of conditions, obtain solution A; Acetylacetone copper is dissolved in solution A completely as copper source, stir 3～5 minutes, the blackish green solution B obtaining, add the silicon chip that is coated with noble metal platinum as catalyst in solution B, put into water heating kettle, under 180 DEG C of conditions, react 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 5mmol zinc acetate and 14mmol thiocarbamide, after stirring.Proceed in microwave reaction kettle.Heating-up time is 10min, and microwave power is 1200w, and initial pressure is 35bar, and reaction temperature is 150 DEG C, and the reaction time is 30min, to be cooled to room temperature.Wash neutrality with water, centrifugal and vacuum drying.
Fig. 1 is the XRD collection of illustrative plates (insertion figure is the XRD collection of illustrative plates that copper nano-wire vulcanizes sample under the same conditions) of the zinc sulphide copper nano-wire visible light catalyst of the obtained cuprous ion doping of embodiment 1, in XRD figure, each diffraction maximum is corresponding one by one with six side's phase zincblende zinc sulphide and elemental copper, show to contain in sample zincblende zinc sulphide and elemental copper, the peak of cuprous sulfide is not obvious, but in insertion figure, comprise the peak of cuprous sulfide and copper simple substance, also prove to contain in sample cuprous sulfide.
Fig. 2 is the nitrogen Adsorption and desorption isotherms of the prepared copper ion doped zinc sulphide copper nano-wire visible light catalyst of embodiment 1, and illustration is BJH graph of pore diameter distribution.In figure, the specific area of show sample is 8.183m
2/ g.
Fig. 3 is the field emission scanning electron microscope figure of the prepared copper ion doped zinc sulphide copper nano-wire visible light catalyst of embodiment 1.Visible in figure, sample is wire, is divided into inside and outside double-decker.
Fig. 4 is the transmission electron microscope picture of the prepared copper ion doped zinc sulphide copper nano-wire visible light catalyst of embodiment 1.Picture further proves the double wrapped nucleocapsid structure of sample, and its internal layer is copper nano-wire 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, embodiment 2,3,4 is respectively 1mmol, 3mmol, 5mmol, and the phase composition of products obtained therefrom thing is consistent, and microscopic appearance is similar, specific 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, embodiment 5,6,7,8,9 is respectively zinc nitrate, zinc chloride, zinc sulfate, zinc acetylacetonate, zinc dihydrogen phosphate, the phase composition of products therefrom thing is identical, on specific area, product hydrogen activity, all have any different, wherein there is the highest product hydrogen activity taking zinc acetate as the sample in zinc source.
Embodiment 10,11,12,13,14
Difference from Example 1 is only sulphur used source difference, embodiment 10,11,12,13,14 is respectively vulcanized sodium, thiocarbamide, thioacetamide, cysteine, lauryl mercaptan, the phase composition of products therefrom thing is identical, on specific area, product hydrogen activity, all have any different, wherein there is the highest product hydrogen activity taking thiocarbamide as the sample in sulphur source.
Embodiment 15,16,17,18,19,20
Difference from Example 1 is only microwave reaction temperature difference, embodiment 15,16,17,18,19,20 is respectively 140 DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 190 DEG C, 200 DEG C, the phase composition of products obtained therefrom thing is consistent, microscopic appearance is similar, specific area has certain difference, wherein has the highest product hydrogen activity with 150 DEG C of reaction temperatures.
Take sample 500mg that embodiment 1 makes in 100mL three-necked bottle, add 0.35M vulcanized sodium, the 0.25M sodium sulfite mixed solution of 80mL, ultrasonic being uniformly dispersed.The in the situation that of magnetic agitation, logical whole reactor nitrogen 10min is removed to the air in reaction system and reactor, and be placed in illumination 1h under 420nm monochromatic visible light lamp.With gas sample collector by sealing sillicon rubber blocking measure the gas in 0.5mL reactor, then utilize gas chromatograph detect H
2amount.
Result shows that the zinc sulphide copper nano-wire visible light catalyst non precious metal of the prepared cuprous ion doping of the present embodiment loads on hydrogen generation efficiency under 420nm monochromatic light and reached 31.1%, is much higher than the zinc sulphide of pure phase and the cuprous sulfide of pure phase.
Claims (10)
1. a zinc sulphide copper nano-wire visible light catalyst for cuprous ion doping, is characterized in that, zinc sulphide is wrapped in the outside nucleocapsid structure that forms of copper nano-wire, and cuprous ion is at zinc sulphide surface doping.
2. the preparation method of the zinc sulphide copper nano-wire visible light catalyst of a cuprous ion doping, it is characterized in that, comprise the following steps: wire copper nano-wire is scattered in water, add zinc source, stir, add again sulphur source, after stirring, be placed in microwave reaction kettle, with the heating rate intensification 5-10min of 10～30 DEG C/min, microwave power is 500-1200w, initial pressure is 0-35bar, reaction temperature is 150-200 DEG C, reaction time is 10-60min, be cooled to after room temperature, washing is to neutral, centrifugal and vacuum drying, obtain the zinc sulphide copper nano-wire visible light catalyst of cuprous ion doping.
3. the preparation method of the zinc sulphide copper nano-wire visible light catalyst of cuprous ion doping described in claim 2, is characterized in that, the concrete steps of the preparation of described wire copper nano-wire are:
Cationic surface active agent softex kw and organic amine solvent cetylamine are dissolved completely under 150-200 DEG C of condition, obtain solution A; Acetylacetone copper is dissolved in solution A completely as copper source, stir 3～5 minutes, the solution B obtaining, add the silicon chip that is coated with platinum as catalyst in solution B, put into water heating kettle, under 140～200 DEG C of conditions, react 5～20 hours, be cooled to room temperature, clean 3～5 times, 50-80 DEG C of vacuum drying 2-8 hour of gained solid, obtains wire copper nano-wire.
4. the preparation method of the zinc sulphide copper nano-wire visible light catalyst of cuprous ion doping described in claim 2, is characterized in that, the ratio 1:0.5～1:10 of wire copper nano-wire and the amount of substance in zinc source.
5. the preparation method of the zinc sulphide copper nano-wire visible light catalyst of cuprous ion doping described in claim 2, is characterized in that, sulphur source is 1:1～5:1 with the ratio of the total amount of substance of zinc-copper.
6. the preparation method of the zinc sulphide copper nano-wire visible light catalyst of cuprous ion doping described in claim 2, is characterized in that, described zinc source comprises zinc nitrate, zinc chloride, zinc sulfate, zinc acetate, zinc acetylacetonate, zinc dihydrogen phosphate.
7. the preparation method of the zinc sulphide copper nano-wire visible light catalyst of cuprous ion doping described in claim 2, is characterized in that, described sulphur source comprises vulcanized sodium, thiocarbamide, thioacetamide, cysteine, lauryl mercaptan.
8. described in claim 1, the zinc sulphide copper nano-wire visible light catalyst of cuprous ion doping is used for decomposing aquatic products hydrogen.
9. the method for the zinc sulphide copper nano-wire visible light catalyst of cuprous ion doping for decomposing aquatic products hydrogen described in claim 1; it is characterized in that; concrete steps are as follows: the zinc sulphide copper nano-wire visible light catalyst of cuprous ion doping is scattered in the mixed solution of water and hole trapping agents; remove the air in reaction system; radiation of visible light 1-1.5h under nitrogen or the protection of inert gas atmosphere, visible wavelength is 420nm.
10. method claimed in claim 9, it is characterized in that, described hole trapping agents comprises methyl alcohol, sodium oxalate, ammonium oxalate, disodium ethylene diamine tetraacetate, tetrasodium ethylenediamine tetraacetate, vulcanized sodium, sodium sulphate, sodium sulfite, lactic acid and their mixture, and wherein optimum is the mixed solution of 0.35M vulcanized sodium and 0.25M sodium sulfite.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104959626A (en) * | 2015-06-30 | 2015-10-07 | 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 |
| CN109126824A (en) * | 2018-09-18 | 2019-01-04 | 张玉英 | A kind of the zinc sulphide bronzing catalyst and preparation method of metal/non-metal doping |
| 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 |
| CN109647533A (en) * | 2018-11-08 | 2019-04-19 | 华南农业大学 | A kind of floatable magnetic high-molecular composite material and preparation method and application |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
2014
- 2014-04-30 CN CN201410181986.7A patent/CN103934005B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Non-Patent Citations (3)
| Title |
|---|
| LINGDONG SUN ET AL: ""ZnS nanoparticles doped with Cu(I) by controlling coordination and precipitation in aqueous solution"", 《J.MATER.CHEM》, 31 December 1999 (1999-12-31), pages 1655 - 1657 * |
| M. MARANDI ET AL: ""Fast two-step microwave-activated synthesis of Mn doped ZnS nanocrystals: Comparison of the luminescence and doping process with thermochemical approach"", 《JOURNAL OFLUMINESCENCE》, 30 November 2010 (2010-11-30), pages 721 - 726, XP028185895, DOI: doi:10.1016/j.jlumin.2010.11.025 * |
| 楚婷婷: ""贵金属可控制性沉积及其对CdS可见光分解水产氢的影响"", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》, 15 February 2014 (2014-02-15), pages 2 - 4 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104959626A (en) * | 2015-06-30 | 2015-10-07 | 厦门大学 | Method for preparing multifunctional core-shell nano-material by using alloy to wrap copper nanowires |
| 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 |
| CN109126824A (en) * | 2018-09-18 | 2019-01-04 | 张玉英 | A kind of the zinc sulphide bronzing catalyst and preparation method of metal/non-metal doping |
| 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 |
| CN109126824B (en) * | 2018-09-18 | 2021-09-14 | 张玉英 | Metal/nonmetal doped zinc sulfide copper photocatalyst and preparation method thereof |
| CN109647533A (en) * | 2018-11-08 | 2019-04-19 | 华南农业大学 | A kind of floatable magnetic high-molecular composite material and preparation method and application |
| 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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