CN1558425A - Process for preparing orientation arrangement zinc sulfide and zinc oxide nano cable composite material - Google Patents
Process for preparing orientation arrangement zinc sulfide and zinc oxide nano cable composite material Download PDFInfo
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- CN1558425A CN1558425A CNA2004100159847A CN200410015984A CN1558425A CN 1558425 A CN1558425 A CN 1558425A CN A2004100159847 A CNA2004100159847 A CN A2004100159847A CN 200410015984 A CN200410015984 A CN 200410015984A CN 1558425 A CN1558425 A CN 1558425A
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Abstract
The invention disclose a process for preparing orientation arrangement zinc sulfide and zinc oxide nanometer cable composite material by utilizing chemical solution method for preparing nano rod orientation arrangement zinc oxide nano material first, then vulcanizing the zinc oxide crystal arrangement which comprises, dissolving the thioacetamide in deionized water, agitating till the solution is clarified, immersing the pre-prepared zinc oxide film in nano rod arrangement into reaction liquid, elevating temperature to 130 deg. C, reacting 11-12 hours. The jacketing of the composite material is formed by zinc sulfide nanocrystalline, and the cable inner core is formed by non-reacted zinc sulfide nanocrystalline.
Description
Technical field
The present invention relates to a kind of preparation method who aligns zinc sulphide-zinc oxide nano cable composite material, adopt the chemical solution growth method to prepare zinc sulphide-zinc oxide nanometer composite material that nano-cable aligns.
Background technology
Along with the development of nanometer technology, it is ripe that the research of nano material is tending towards gradually, and the application of nano material is also more extensive.Yet because the performance of nano material depends mainly on the structure of its intrinsic body material, the application with nano material of single structure will be very restricted.Therefore, press for and synthesize function nano material with multiple performance.For realizing such purpose, a kind of way is that two or more nano materials are combined, and realizes the multifunction of nano material.Yet, simply different nano materials is mixed, be difficult to it is disperseed uniformly, and the performance of composite material is the simple superposition of each material property also, can not produce new performance.Therefore, the nano material of the composite construction that preparation makes new advances, for the range of application that enlarges nano material, and the developing new capability has great importance.
Nano zine oxide is a kind of good semi-conducting material, it is owing to have bigger energy gap width (3.37eV, similar with gallium nitride) and have performances such as good luminous, opto-electronic conversion, UV absorption, be widely used in luminescent material, photoelectric conversion material, rubber, pottery, coating, daily-use chemical industry material, can be used for making gas sensitive, lighting electrode, rubber additive, gas sensor, UV-preventing material, transformer and multiple Optical devices.The pattern of nano zine oxide crystal is the key factor that influences material property.Calendar year 2001, reported on the authority magazine Science under the room temperature that zinc oxide nanowire is arranged can produce to swash and penetrated phenomenon and cause people's extensive concern, thereby made the focus in the nano materials research field of being arranged as of one-dimensional zinc oxide nanometer material (nanometer rods, nano wire, nanotube etc.).At present, one-dimension zinc oxide nanocrystal arrangement materials such as preparing of multiple preparation method success is bar-shaped, wire, comprise gas phase synthesis method, for example chemical vapor deposition (CVD), magnetron sputtering method, spray pyrolysis, pulsed laser deposition (PLD), atomic-layer epitaxial growth method and molecular beam epitaxy etc., solution synthetic method comprises sol-gal process, Hydrolyze method, hydro thermal method, antiphase emulsifiable method, the precipitation method and electrochemical deposition method.
Under zinc oxide was compared, zinc sulphide also was a kind of good semi-conducting material.When the energy gap of zinc sulphide reached 3.6eV.0K, the band gap of its body material was 325nm; Because the heat balance phonon is filled, its effective band gap is about 339nm during 300K.It has piezoelectricity and thermoelectric property, and is the optical conductor with 340nm maximum wavelength.Solid-state ZnS is penetrated by ultraviolet radiation (being lower than 335nm), negative electrode to open, X ray, gamma-rays and electric field (electroluminescence) produce radiation when exciting, and is a kind of good fluorescent material.In addition, nanometer along with semi-conducting material, can not only cause absorbing wavelength and fluorescent emission generation blue shift, can also produce the optical nonlinearity response, and the redox ability of enhancing nano particle, have more excellent photoelectric catalytically active, will be used widely at aspects such as luminescent material, nonlinear optical material, catalysis materials.
Because performance such as the photoelectricity that zinc oxide and zinc sulfide nano-material are outstanding and they have application potential on the nano-device in future, in recent years, zinc oxide-zinc sulphide composite material has been subjected to more attention, and has obtained some achievements by methods such as solution synthesize.Yet present prepared zinc oxide-zinc sulfide nano composite material mainly is confined to spherical shell-core nanometer structure aspect, and the nano-powder of these dispersions is difficult to its directed processing is applied on the nano-device.Under comparing, arrange the nano film material that assembles by the nanocrystal of one-dimentional structure and then have the feasibility of processing.At present, have nano materials such as one-dimentional structure (nanometer rods, nanotube, nano wire) zinc oxide preparing by the several different methods success.Recently, the Nano Letter magazine of American Chemical Society has been delivered the article of arranging sulfuration about zinc oxide nano rod, has opened up the new direction of preparation zinc oxide-zinc sulphide composite material.This composite construction is a kind of construction of cable.Cable core is a zinc oxide material, and crust is made up of zinc sulphide (being obtained by the zinc oxide sulfuration).Yet, the preparation method that this report adopts (referring to sulfuration) is a high-temperature gas sulfuration method, the zinc oxide nano-crystal arrangement material that soon prepares is in advance put into the steam of hydrogen sulfide gas or elemental sulfur, zinc sulphide-zinc oxide nanometer composite material that the preparation nano-cable aligns under 500～600 degrees centigrade of reactions.This method needs harsh conditions such as high temperature is airtight, realizes difficulty, cost is high, controllability is low.Recently, the Advance Materials magazine of German Willy publishing house has been delivered the method that adopts the sulfuration of hydrogen sulfide saturated solution, success zinc oxide nano-belt is sulfided into zinc oxide-zinc sulfide nano cable.This solwution method reaction temperature is low, simple to operate, and cost is low, and is effective.Yet the method activity of this solution sulfuration is low, only is fit to the sulfuration of the powder body material under the low concentration, is difficult to be applied in large tracts of land, the arrangement of highdensity zinc oxide.Therefore, press for a kind of simple method at present large tracts of land, the arrangement of high density zinc oxide nano-crystal are vulcanized, prepare the novel nano-material of zinc oxide-zinc sulfide nano cable composite construction.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, a kind of preparation method who aligns zinc sulphide-zinc oxide nano cable composite material is provided, easy and simple to handle, can arrange large tracts of land, high density zinc oxide nano-crystal cheaply and vulcanize, the NEW TYPE OF COMPOSITE nano material of preparing has more practicality.
For realizing such purpose, in the technical scheme of the present invention, at first adopt chemical solution method to prepare nanometer rods and align nano zinc oxide material, adopt chemical solution method sulfidation-oxidation zinc crystal then.In the tetrafluoroethene container, the sulphur source is dissolved in certain solvent according to certain concentration, is stirred to the solution clarification.The zinc oxide that will prepare in advance (nanometer rods arrangement) film vertically is immersed in the reaction solution again, be warming up to 130 ℃, react the zinc sulphide-zinc oxide nanometer composite material that can obtain nano-cable in 11-12 hour and align and arrange the nano film material that constitutes.The crust of preparing zinc sulphide-zinc oxide nanometer composite material that nano-cable aligns is to be made of zinc sulfide nano crystal, and the average grain diameter of crystal is 80 nanometers.The inner core of cable is made up of unreacted zinc oxide nano-crystal, and the average diameter of crystal is 300 nanometers.
Preparation method of the present invention comprises following concrete steps:
1. nanometer rods aligns the preparation of nano zinc oxide material:
A) preparation of chemically grown reactant liquor: zinc salt, thiocarbamide, ammoniacal liquor and ammonium salt are dissolved in deionized water by a certain percentage, be prepared into the film growth reactant liquor, contain zinc salt 0.01mol, 25% (mass ratio) ammoniacal liquor 5ml, thiocarbamide 0.01mol and ammonium salt 0.002mol in every 100ml aqueous solution;
The said zinc salt of the present invention is a zinc nitrate hexahydrate; Ammonium salt is an ammonium chloride.
B) preliminary treatment of substrate: at first quartz substrate was immersed in 98% the concentrated sulfuric acid of boiling 5～10 hours, was immersed in then in the acetone ultrasonic 30～60 minutes, next use a large amount of deionized water rinsings, at last substrate is dried in vacuum drying oven, stand-by.
C) nanometer rods aligns the synthetic of nano zinc oxide material: before reaction, at first substrate is soaked in the above-mentioned chemically grown reaction solution for preparing; Reaction system is warming up to 94～97 ℃ again, heating rate 10～20 degree/minute, reacted 45～60 minutes down at 94～97 ℃.Reaction finishes the back cools off fast with frozen water, substrate is put in deionized water for ultrasonic 1～2 minute then, use a large amount of deionized water rinsings, can obtain nanometer rods and aligns nano zinc oxide material through drying naturally after the washing repeatedly.
2. synthetic (sulfuration of zinc oxide) of zinc sulphide-zinc oxide nanometer composite material of aligning of nano-cable:
A) preparation of vulcanization reaction solution: the sulphur source is dissolved in the deionized water, is stirred to the solution clarification, can be prepared into vulcanization reaction solution.Wherein, the sulphur source is a thioacetamide, and the concentration in sulphur source is 1.5 grams/100 ml waters.
B) synthetic (sulfuration of zinc oxide) of zinc sulphide-zinc oxide nanometer composite material of aligning of nano-cable: the zinc oxide nano film that will prepare in advance vertically is immersed in the above-mentioned vulcanization reaction solution for preparing, closed reaction vessel, pack in the stainless steel cauldron, be warming up to 130 ℃, reacted 11-12 hour, reaction naturally cools to normal temperature after finishing, take out the sample deionized water rinsing, can obtain zinc sulphide-zinc oxide nanometer composite material that nano-cable aligns through drying naturally after repeatedly washing.
The inventive method is simple to operate, efficient is high, and the chemical solution method reaction temperature of employing is low, only needs 130 ℃, and solvent adopts prevailing deionized water, and cost is low, pollution is little, helps environmental protection.Use the inventive method, can realize that large tracts of land transforms, promptly align the transformation that zinc sulphide-zinc oxide nanometer composite material that nano zinc oxide material aligns to nano-cable is arranged from nanometer rods.Zinc sulphide-zinc oxide nanometer composite material of preparing has novel cable shape composite construction, and has good fluorescence property.
Description of drawings
The x-ray diffraction pattern of the nano zinc oxide material that the nanometer rods that Fig. 1 is adopted for the embodiment of the invention 1 aligns.
The x-ray diffraction pattern that the zinc sulphide that Fig. 2 aligns for the embodiment of the invention 1 resulting nano-cable-zinc oxide nanometer composite material is arranged.
The nanometer rods that Fig. 3 is adopted for the embodiment of the invention 1 aligns the electron scanning micrograph of nano zinc oxide material.
The electron scanning micrograph of zinc sulphide-zinc oxide nanometer composite material that Fig. 4 aligns for the embodiment of the invention 1 resulting nano-cable.
The scanning electron microscopy enlarged photograph of zinc sulphide-zinc oxide nanometer composite material that Fig. 5 aligns for the embodiment of the invention 1 resulting nano-cable.
The EDS spectrogram of zinc sulphide-zinc oxide nanometer composite material that Fig. 6 aligns for the embodiment of the invention 1 resulting nano-cable.
The transmission electron microscope photo of zinc sulphide-zinc oxide nanometer composite material that Fig. 7 aligns for the embodiment of the invention 1 resulting nano-cable.
The fluorescence spectrum figure of zinc sulphide-zinc oxide nanometer composite material that Fig. 8 aligns for the embodiment of the invention 1 resulting nano-cable.
Embodiment:
The following examples are to further specify of the present invention, rather than limit the scope of the invention.
Embodiment 1
1. the preparation of the nano zinc oxide material that aligns of nanometer rods:
A) preparation of chemically grown reactant liquor: zinc nitrate hexahydrate, thiocarbamide, ammoniacal liquor and ammonium chloride are dissolved in deionized water by a certain percentage, be prepared into the film growth reactant liquor, contain zinc nitrate hexahydrate 0.01mol, 25% (mass ratio) ammoniacal liquor 5ml, thiocarbamide 0.01mol and ammonium chloride 0.002mol in every 100ml aqueous solution;
B) preliminary treatment of substrate: at first quartz substrate was immersed in 98% the concentrated sulfuric acid of boiling 10 hours, was immersed in then in the acetone ultrasonic 60 minutes, next use a large amount of deionized water rinsings, at last substrate is dried in vacuum drying oven, stand-by.
C) nanometer rods aligns the synthetic of nano zinc oxide material: before reaction, at first substrate is soaked in the above-mentioned chemically grown reaction solution for preparing; Reaction system is warming up to 95 ℃ again, heating rate 15 degree/minute, reacted 60 minutes down at 95 ℃.Reaction finishes the back cools off fast with frozen water, substrate is put in deionized water for ultrasonic 1 minute then, use a large amount of deionized water rinsings, can obtain nanometer rods and aligns nano zinc oxide material through drying naturally after the washing repeatedly.
2. synthetic (sulfuration of zinc oxide) of zinc sulphide-zinc oxide nanometer composite material of aligning of nano-cable:
A) preparation of vulcanization reaction solution: 3 gram thioacetamides are dissolved in 200 ml deionized water, are stirred to the solution clarification, can be prepared into vulcanization reaction solution.
B) synthetic (sulfuration of zinc oxide) of zinc sulphide-zinc oxide nanometer composite material of aligning of nano-cable: from the above-mentioned vulcanization reaction solution for preparing, take out 30 milliliters, pour in 40 milliliters the tetrafluoroethene inner bag, the zinc oxide nano film for preparing in advance vertically is immersed in the vulcanization reaction solution, airtight water heater container, pack in the stainless steel cauldron, be warming up to 130 ℃, reacted 12 hours, reaction naturally cools to normal temperature after finishing, take out the sample deionized water rinsing, can obtain zinc sulphide-zinc oxide nanometer composite material that nano-cable aligns through drying naturally after repeatedly washing.
X-ray diffraction spectrogram such as Fig. 1 of the zinc-oxide film that adopts, prepared as seen from Figure 1 zinc oxide are hexagonal crystal shape (36-1451), and strength ratio [101] crystal face of crystal face [002] is a lot of by force, illustrate that zincite crystal is along good orientation is axially arranged.The x-ray diffraction pattern of zinc sulphide-zinc oxide nanometer composite material that resulting nano-cable aligns such as Fig. 2, prepared as seen from the figure nano thin-film have two kinds of crystal-zinc oxide and zinc sulphide simultaneously.The crystalline form of zinc oxide still is hexagonal crystal shape (JCPDS No.36-1451), and the crystalline form of zinc sulphide is cubic-crystal (JCPDS No.05-0566).The nanometer rods that is adopted aligns electron scanning micrograph such as Fig. 3 of nano zinc oxide material, and prepared as seen from the figure zinc oxide is the one-dimensional rod-like crystal, and these crystal are along axially be arranged in thin-film material on quartz substrate.Electron scanning micrograph such as Fig. 4 and Fig. 5 of zinc sulphide-zinc oxide nanometer composite material that the resulting nano-cable in sulfuration back aligns, the surface of nanometer rods has become graininess as seen from the figure, particle grain size average out to 100 nanometers, energy spectrum analysis (EDS, Fig. 6) particle that shows the surface is made up of zinc and two kinds of elements of sulphur, do not have oxygen element, the instruction card flooring is a zinc sulphide.And XRD shows that the prepared film material is made up of zinc oxide and two kinds of crystal of zinc sulphide, because the depth ratio zinc sulphide that XRD surveys is dark, therefore, can characterize the composition of whole crystal.In sum, prepared nano material is a kind of composite material of the construction of cable, and crust is a zinc sulfide nano-material, and inner core is a zinc oxide nano-crystal.This construction of cable can arrive by the projection electron microscopy observation, as Fig. 7.Fig. 8 is the fluorescence spectrum figure that the zinc sulphide that aligns of resulting nano-cable-zinc oxide nanometer composite material is arranged.As seen from the figure, the nano thin-film of the prepared construction of cable has fluorescent effect in 360 nanometers, 450 nanometers and 485 nanometers.
Embodiment 2
1. nanometer rods aligns the preparation of nano zinc oxide material:
A) preparation of chemically grown reactant liquor: zinc nitrate hexahydrate, thiocarbamide, ammoniacal liquor and ammonium chloride are dissolved in deionized water by a certain percentage, be prepared into the film growth reactant liquor, contain zinc nitrate hexahydrate 0.01mol, 25% (mass ratio) ammoniacal liquor 5ml, thiocarbamide 0.01mol and ammonium chloride 0.002mol in every 100ml aqueous solution;
B) preliminary treatment of substrate: at first quartz substrate was immersed in 98% the concentrated sulfuric acid of boiling 10 hours, was immersed in then in the acetone ultrasonic 60 minutes, next use a large amount of deionized water rinsings, at last substrate is dried in vacuum drying oven, stand-by.
C) nanometer rods aligns the synthetic of nano zinc oxide material: before reaction, at first substrate is soaked in the above-mentioned chemically grown reaction solution for preparing; Reaction system is warming up to 95 ℃ again, heating rate 15 degree/minute, reacted 60 minutes down at 95 ℃.Reaction finishes the back cools off fast with frozen water, substrate is put in deionized water for ultrasonic 1 minute then, use a large amount of deionized water rinsings, can obtain nanometer rods and aligns nano zinc oxide material through drying naturally after the washing repeatedly.
2. synthetic (sulfuration of zinc oxide) of zinc sulphide-zinc oxide nanometer composite material of aligning of nano-cable:
A) preparation of vulcanization reaction solution: 1.5 gram thioacetamides are dissolved in 100 ml deionized water, are stirred to the solution clarification, can be prepared into vulcanization reaction solution.
B) synthetic (sulfuration of zinc oxide) of zinc sulphide-zinc oxide nanometer composite material of aligning of nano-cable: from the above-mentioned vulcanization reaction solution for preparing, take out 30 milliliters, pour in 40 milliliters the tetrafluoroethene inner bag, the zinc oxide nano film for preparing in advance vertically is immersed in the vulcanization reaction solution, airtight water heater container, pack in the stainless steel cauldron, be warming up to 130 ℃, reacted 11.5 hours, reaction naturally cools to normal temperature after finishing, take out the sample deionized water rinsing, can obtain zinc sulphide-zinc oxide nanometer composite material that nano-cable aligns through drying naturally after repeatedly washing.
Embodiment 3
1. nanometer rods aligns the preparation of nano zinc oxide material:
A) preparation of chemically grown reactant liquor: zinc nitrate hexahydrate, thiocarbamide, ammoniacal liquor and ammonium chloride are dissolved in deionized water by a certain percentage, be prepared into the film growth reactant liquor, contain zinc nitrate hexahydrate 0.01mol, 25% (mass ratio) ammoniacal liquor 5ml, thiocarbamide 0.01mol and ammonium chloride 0.002mol in every 100ml aqueous solution;
B) preliminary treatment of substrate: at first quartz substrate was immersed in 98% the concentrated sulfuric acid of boiling 10 hours, was immersed in then in the acetone ultrasonic 60 minutes, next use a large amount of deionized water rinsings, at last substrate is dried in vacuum drying oven, stand-by.
C) nanometer rods aligns the synthetic of nano zinc oxide material: before reaction, at first substrate is soaked in the above-mentioned chemically grown reaction solution for preparing; Reaction system is warming up to 95 ℃ again, heating rate 15 degree/minute, reacted 60 minutes down at 95 ℃.Reaction finishes the back cools off fast with frozen water, substrate is put in deionized water for ultrasonic 1 minute then, use a large amount of deionized water rinsings, can obtain nanometer rods and aligns nano zinc oxide material through drying naturally after the washing repeatedly.
2. synthetic (sulfuration of zinc oxide) of zinc sulphide-zinc oxide nanometer composite material of aligning of nano-cable:
A) preparation of vulcanization reaction solution: 1.5 gram thioacetamides are dissolved in 100 ml deionized water, are stirred to the solution clarification, can be prepared into vulcanization reaction solution.
B) synthetic (sulfuration of zinc oxide) of zinc sulphide-zinc oxide nanometer composite material of aligning of nano-cable: from the above-mentioned vulcanization reaction solution for preparing, take out 30 milliliters, pour in 40 milliliters the tetrafluoroethene inner bag, the zinc oxide nano film for preparing in advance vertically is immersed in the vulcanization reaction solution, airtight water heater container, pack in the stainless steel cauldron, be warming up to 130 ℃, reacted 11 hours, reaction naturally cools to normal temperature after finishing, take out the sample deionized water rinsing, can obtain zinc sulphide-zinc oxide nanometer composite material that nano-cable aligns through drying naturally after repeatedly washing.
Claims (2)
1. a preparation method who aligns zinc sulphide-zinc oxide nano cable composite material is characterized in that comprising the steps:
1) nanometer rods aligns the preparation of nano zinc oxide material: with zinc salt, thiocarbamide, ammoniacal liquor and ammonium salt are dissolved in deionized water in proportion, be prepared into the film growth reactant liquor, contain zinc salt 0.01mol in every 100ml aqueous solution, mass ratio is 25% ammoniacal liquor 5ml, thiocarbamide 0.01mol and ammonium salt 0.002mol, substrate was immersed in 98% the concentrated sulfuric acid of boiling 5～10 hours, be immersed in then in the acetone ultrasonic 30～60 minutes, after drying with deionized water rinsing, soak in the reactant liquor for preparing, reaction system is warming up to 94～97 ℃ again, heating rate 10～20 degree/minute, reacted 45～60 minutes down at 94～97 ℃, reaction finishes back cooling fast, substrate was put in deionized water for ultrasonic 1～2 minute then,, obtains nanometer rods and align nano zinc oxide material with drying naturally behind the deionized water wash;
2) zinc sulphide-zinc oxide nanometer composite material of aligning of nano-cable is synthetic: with concentration is that the thioacetamides of 1.5 grams/100 ml waters are dissolved in the deionized water, be stirred to the solution clarification, be prepared into vulcanization reaction solution, the zinc oxide nano film for preparing vertically is immersed in the vulcanization reaction solution, closed reaction vessel, pack in the stainless steel cauldron, be warming up to 130 ℃, reacted 11-12 hour, reaction naturally cools to normal temperature after finishing, take out sample and dry naturally after with deionized water rinsing, promptly obtain zinc sulphide-zinc oxide nanometer composite material that nano-cable aligns.
2. the preparation method who aligns zinc sulphide-zinc oxide nano cable composite material as claimed in claim 1 is characterized in that described zinc salt is a zinc nitrate hexahydrate, and ammonium salt is an ammonium chloride.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101607689B (en) * | 2008-06-17 | 2010-12-22 | 国家纳米科学中心 | Zinc oxide and zinc sulfide nano-belt composite heterogenous junction material and preparation method |
| CN102503171A (en) * | 2011-10-31 | 2012-06-20 | 南京大学 | Preparation method of branched zinc oxide nanowire array film |
| CN108754528A (en) * | 2018-06-08 | 2018-11-06 | 西北大学 | A kind of high-performance photocatalysis nano material |
| CN114436639A (en) * | 2020-11-04 | 2022-05-06 | 天津理工大学 | ZnO-based thermoelectric ceramic with high thermoelectric performance and preparation method thereof |
| CN114558592A (en) * | 2022-03-09 | 2022-05-31 | 北方民族大学 | ZnO/ZnS nanorod core-shell structure photocatalyst and preparation method thereof |
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2004
- 2004-01-19 CN CN 200410015984 patent/CN1257514C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101607689B (en) * | 2008-06-17 | 2010-12-22 | 国家纳米科学中心 | Zinc oxide and zinc sulfide nano-belt composite heterogenous junction material and preparation method |
| CN102503171A (en) * | 2011-10-31 | 2012-06-20 | 南京大学 | Preparation method of branched zinc oxide nanowire array film |
| CN108754528A (en) * | 2018-06-08 | 2018-11-06 | 西北大学 | A kind of high-performance photocatalysis nano material |
| CN114436639A (en) * | 2020-11-04 | 2022-05-06 | 天津理工大学 | ZnO-based thermoelectric ceramic with high thermoelectric performance and preparation method thereof |
| CN114558592A (en) * | 2022-03-09 | 2022-05-31 | 北方民族大学 | ZnO/ZnS nanorod core-shell structure photocatalyst and preparation method thereof |
| CN114558592B (en) * | 2022-03-09 | 2023-11-14 | 北方民族大学 | ZnO/ZnS nano-rod core-shell structure photocatalyst and preparation method thereof |
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