CN106694903B - A kind of CuCl/Cu2The preparation method and products obtained therefrom of O/Cu porous nano-sheets - Google Patents
A kind of CuCl/Cu2The preparation method and products obtained therefrom of O/Cu porous nano-sheets Download PDFInfo
- Publication number
- CN106694903B CN106694903B CN201710041712.1A CN201710041712A CN106694903B CN 106694903 B CN106694903 B CN 106694903B CN 201710041712 A CN201710041712 A CN 201710041712A CN 106694903 B CN106694903 B CN 106694903B
- Authority
- CN
- China
- Prior art keywords
- cucl
- sheets
- porous nano
- preparation
- thermal reaction
- 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.)
- Expired - Fee Related
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
- B22F1/0551—Flake form nanoparticles
-
- 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
Abstract
The invention discloses a kind of CuCl/Cu2The preparation method and products obtained therefrom of O/Cu porous nano-sheets, method are：By copper chloride, NaHCO3, EDTA 2Na be added to the in the mixed solvent of glycerine and ethyl alcohol, stir to get clear solution, clear solution be subjected to solvent thermal reaction, products therefrom centrifugation, washing obtain product.The present invention is by adjusting technological parameters such as reaction system, solvent thermal reaction conditions, under the synergistic effect of surfactant, reducing agent etc., controls CuCl, Cu2The nucleation and growth course of O and Cu obtains uniform pattern, thickness and the adjustable CuCl/Cu in aperture2O/Cu porous nano-sheets.The raw materials used price of this method is low, source is wide, it is strong to react controllability, the product that microscopic appearance is uniform, size distribution ranges are narrow, yield is high only can be obtained by a step solvent thermal reaction, there is higher application value in fields such as photocatalysis, catalysis, air-sensitive, lithium batteries.
Description
Technical field
The present invention relates to a kind of preparation methods of CuCl bases three-phase composite nanostructure, and in particular to a kind of thickness and aperture
Adjustable CuCl/Cu2The preparation method and products obtained therefrom of O/Cu porous nano-sheets, belong to technical field of nanometer material preparation.
Background technology
With the getting worse of the energy and Ecological Environment Crisis, environmental pollution can be reduced using the raw material of nonhazardous, exploration
Green chemical synthesis technique, development meet " environmentally friendly " nano functional material of national energy conservation and emission reduction and circular economy demand
Material is the hot spot of the area researches such as current photocatalysis, catalysis, air-sensitive, lithium battery.Develop novel multiphase composite Nano knot
Structure system is considered as a practicable effective way.
Copper system compound has the characteristics that cheap and easy to get, reactivity is high, selectivity is good, can be recycled, in catalysis, energy
The fields such as source, sensing have huge prospects for commercial application.Wherein, CuCl is that a kind of I-VII types of room temperature zincblende lattce structure are straight
Tape splicing gap wide bandgap semiconductor, in Electro-optical Modulation demodulator, LED, adsorbent, air purifying preparation, optical filter, organic synthesis
Catalyst, lithium battery etc. are widely used.CuCl is nanocrystalline, the synthetic method of film and powder is more, for example, Cu2+/ hydrochloric acid
The reduction reaction method of solution, the vacuum reaction of high temperature tension method, the thermal decomposition method of organocopper compound, Cu monocrystalline/chlorine
Method etc., these building-up processes are required for greatly complex device, pyroreaction, toxic raw materials and solvent, and with pollutant byproducts
It generates, in addition, the problems such as CuCl materials are commonly present poor stability, easy in inactivation, seriously corroded is used alone, significantly limits
The application of CuCl micro Nano materials.The study found that by adding auxiliary agent or ligand, introducing the second phase substance, regulation and control microscopic appearance
Equal many kinds of measures can effectively improve the service life and activity of CuCl, reduce its corrosivity to equipment.For example, " R. C.
Yang, X. J. Lu, X. Huang, Z. M. Chen, X. Zhang, M. D. Xu, Q. W. Song, and L.
T. Zhu, Applied Catalysis B:Environmental, 2015,170-171,225-232 " use CuCO3-
Cu(OH)2, glucose be raw material, deionized water is solvent, and Cu has been obtained by solvent-thermal method2O/CuCl cubes of block structure is found
It is with good photocatalysis performance；“S. Liu, H. Y. Hou, X. X. Liu, W. Hu, C. X. Yan, J. X.
Duan, and R. J. Meng, Ceramics International, 2016,42,8310-8315 " are using in situ raw
Regular way prepares CuCl/Cu multistage sclay textures, finds it with excellent lithium battery performance.
Currently, carried out the exploration work of a variety of CuCl bases two-phase composite nanostructures both at home and abroad, but about CuCl/
Cu2The research of O/Cu three-phase composite laminated structures has not been reported.Solvent thermal reaction have many advantages, such as it is easy to operate, reproducible,
If object phase composition and the microscopic appearance of a step solvent thermal reaction Effective Regulation CuCl based compound nano materials can be utilized, not only
The physical and chemical performance of CuCl materials can be significantly improved, generally existing in CuCl nano materials building-up process at this stage can also be solved
The problems such as yield is small, poor controllability, help to realize CuCl/Cu2O/Cu composite nanostructures photocatalysis, catalysis, air-sensitive,
Further applying in the fields such as lithium battery.
Invention content
The present invention provides a kind of CuCl/Cu for deficiency existing for existing method2The preparation method of O/Cu nanometer sheets,
CuCl/Cu has been made using a step solvent thermal reaction in this method2O/Cu three-phase composite nanometer sheet materials, building-up process are easy to control
System, operability is strong, and product morphology is reproducible, and controllability is strong, is conducive to large-scale production.
The present invention also provides CuCl/Cu obtained according to the method described above2O/Cu nanometer sheets, the nanometer sheet is by CuCl/
Cu2O/Cu three-phase composites form, and have no relevant report at present.
The present invention is in state natural sciences fund youth's Projects（Project approval number：51402123）Subsidy
Under completed, specific technical solution is as follows：
A kind of CuCl/Cu2The preparation method of O/Cu porous nano-sheets, it is characterized in that including the following steps：
（1）By copper chloride, NaHCO3, EDTA-2Na be added to the in the mixed solvent of glycerine and ethyl alcohol, stir to get
Bright solution；
（2）By step（1）Clear solution heating, carry out solvent thermal reaction；
（3）After reaction, by product centrifugation, washing, CuCl/Cu is obtained2O/Cu porous nano-sheets.
In the above method, step（1）In, copper chloride, NaHCO3, EDTA-2Na molar ratio be 1：0.6-1.4：0.5-
0.9。
In the above method, step（1）In, the volume ratio of glycerine and ethyl alcohol is 1：0.5-1.5.
In the above method, step（1）In, a concentration of 0.12- of the copper chloride in the in the mixed solvent of glycerine and ethyl alcohol
0.36 mol/L。
In the above method, step（2）In, solvent thermal reaction temperature is 190-220 DEG C, and the reaction time is generally 1-24 h.
In the above method, step（2）In, solvent thermal reaction carries out in confined conditions.
The present invention has only obtained CuCl/Cu by a step solvent thermal reaction2O/Cu three-phase composite nano materials, reactant
System is novel, and reaction process is easily controllable, is joined by techniques such as the composition of control reaction system and content, solvent thermal reaction conditions
Number, can obtain uniform pattern, thickness and the adjustable CuCl/Cu in aperture2O/Cu porous nano-sheets.The present invention reaction system,
The various aspects such as product crystalline phase, product morphology, reaction mechanism all have novelty, have essence not compared with domestic and foreign literature is reported
Together.In the present invention, glycerine is solvent, reducing agent and organic ligand, NaHCO3For weak base source and surfactant, ETDA-
2Na is complexing agent and surfactant, by the additional proportion of each reactant of Reasonable Regulation And Control, under the action of surfactant,
It is initially formed copper glycerolate laminated structure by solvent thermal reaction, then using the copper glycerolate laminated structure as soft template, the third three
The Cu in copper glycerolate laminated structure can be effectively facilitated in the reproducibility solvent environment that alcohol and ethyl alcohol provide2+To Cu+Transformation, one
Part Cu+With the Cl in solution-Reaction forms CuCl, the Cu of another part+With the OH in solution-Reaction forms Cu2O, also one
Part Cu+It is further reduced to form Cu simple substance.In this series of oxidation reduction reaction process, product morphology maintains copper glycerolate
The nanometer chip architecture of template, it is whole that porosity is presented, it finally obtains containing CuCl, Cu2Tri- kinds of crystal phase structures of O and Cu it is polynary multiple
Close nano material.
The CuCl/Cu obtained according to the method for the present invention2O/Cu porous nano-sheets form and pattern is special, are also protected in the present invention
Within the scope of shield.
CuCl/Cu produced by the present invention2O/Cu porous nano-sheets, size are 0.06-2.5 μm, and the thickness of nanometer sheet is
5-100 nm, aperture are 1-20 nm.Wherein, aperture can be measured by transmission electron microscope or ratio surface area instrument.
Type of the present invention by adjusting mantoquita, NaHCO3, EDTA-2Na additional proportion and concentration, the group of mixed solvent
At technological parameters such as, solvent heat conditions, under the synergistic effect of surfactant, reducing agent etc., CuCl, Cu are controlled2O's and Cu
Nucleation and growth course obtain uniform pattern, thickness and the adjustable CuCl/Cu in aperture2O/Cu porous nano-sheets, reactant
The selection of system is to CuCl/Cu2The forming process of O/Cu porous nano-sheets plays an important roll with pattern control.Reactant of the present invention
System and building-up process are practical, technology path and reaction mechanism strong innovation.
The present invention is prepared for CuCl/Cu using a step solvent thermal reaction process2O/Cu three-phase composite nano materials, original used
Material is common agents, and price is low, and source is wide, and reaction controllability is strong, and easy to operate, the microscopic appearance of product is uniform, repeated
Good, size distribution ranges are narrow, and yield is high, have higher application value in fields such as photocatalysis, catalysis, air-sensitive, lithium batteries.
Description of the drawings
Fig. 1 is the CuCl/Cu that the embodiment of the present invention 1 synthesizes2The X-ray diffraction of O/Cu porous nano-sheets（XRD）Collection of illustrative plates.
Fig. 2 is the CuCl/Cu that the embodiment of the present invention 1 synthesizes2The scanning electron microscope of O/Cu porous nano-sheets（SEM）Picture.
Fig. 3 is the CuCl/Cu that the embodiment of the present invention 1 synthesizes2The transmission electron microscope of O/Cu porous nano-sheets（TEM）Picture.
Specific implementation mode
Below by embodiment, the present invention will be further elaborated, and following the description is only for explaining the present invention, not
Its content is defined.
Embodiment 1
1.1 by the Copper dichloride dihydrate of 0.852 g（CuCl2∙2H2O）, 0.425 g NaHCO3, 1.316 g EDTA-
2Na is added to the in the mixed solvent of 12.5 mL glycerine and 12.5 mL ethyl alcohol, stirs to get clear solution；
1.2 are transferred to above-mentioned solution in reaction kettle, and 16 h are reacted at 200 DEG C；
1.3 products obtain CuCl/Cu after centrifugation and washing2O/Cu porous nano-sheets.
The phase structure of product and microscopic appearance are as shown in Figs. 1-3.Fig. 1 is the XRD spectrum of product, it is found that all
X-ray diffraction peak value respectively with JCPDS cards（06-0344,05-0667,04-0836）It is consistent, corresponds to CuCl, Cu2O
With Cu crystalline phases, it was demonstrated that exist simultaneously CuCl, Cu in products therefrom2O and Cu is CuCl/Cu2O/Cu three-phase composite structures；Fig. 2 and 3
It is SEM the and TEM photos of product respectively, it is found that the microscopic appearance of product shown in SEM and TEM pictures is consistent, and is
The size of the uniform porous nano chip architecture of good dispersion, pattern, nanometer sheet is 0.18-0.25 μm, and thickness is 37-43 nm,
Aperture is 2.5-6.0 nm.
Embodiment 2
2.1 by the CuCl of 0.560 g2∙2H2O, the NaHCO of 0.168 g3, 0.623 g EDTA-2Na be added to 15.0
The in the mixed solvent of mL glycerine and 10.0 mL ethyl alcohol, stirs to get clear solution；
2.2 are transferred to above-mentioned solution in reaction kettle, and 2 h are reacted at 190 DEG C；
2.3 products obtain CuCl/Cu after centrifugation and washing2O/Cu porous nano-sheets.The size of nanometer sheet is
0.08-0.13 μm, thickness is 7-11 nm, and aperture is 1.1-2.3 nm.
Embodiment 3
3.1 by the CuCl of 1.868 g2∙2H2O, the NaHCO of 1.273 g3, 3.625 g EDTA-2Na be added to 10.4
The in the mixed solvent of mL glycerine and 20.6 mL ethyl alcohol, stirs to get clear solution；
3.2 are transferred to above-mentioned solution in reaction kettle, and 23 h are reacted at 220 DEG C；
3.3 products obtain CuCl/Cu after centrifugation and washing2O/Cu porous nano-sheets.The size of nanometer sheet is
1.8-2.2 μm, thickness is 88-94 nm, and aperture is 12.0-18.0 nm.
Embodiment 4
4.1 by the CuCl of 1.254 g2∙2H2O, the NaHCO of 0.618 g3, 1.642 g EDTA-2Na be added to 14.0
The in the mixed solvent of mL glycerine and 12.0 mL ethyl alcohol, stirs to get clear solution；
4.2 are transferred to above-mentioned solution in reaction kettle, and 10 h are reacted at 200 DEG C；
4.3 products obtain CuCl/Cu after centrifugation and washing2O/Cu porous nano-sheets.The size of nanometer sheet is
0.10-0.15 μm, thickness is 22-28 nm, and aperture is 1.9-5.1 nm.
Embodiment 5
5.1 by the CuCl of 1.248 g2∙2H2O, the NaHCO of 0.738 g3, 2.179 g EDTA-2Na be added to 18.0
The in the mixed solvent of mL glycerine and 13.5 mL ethyl alcohol, stirs to get clear solution；
5.2 are transferred to above-mentioned solution in reaction kettle, and 20 h are reacted at 210 DEG C；
5.3 products obtain CuCl/Cu after centrifugation and washing2O/Cu porous nano-sheets.The size of nanometer sheet is
1.4-1.8 μm, thickness is 63-70 nm, and aperture is 7.0-13.0 nm.
Embodiment 6
6.1 by the CuCl of 0.930 g2∙2H2O, the NaHCO of 0.367 g3, 1.523 g EDTA-2Na be added to 14.0
The in the mixed solvent of mL glycerine and 16.0 mL ethyl alcohol, stirs to get clear solution；
6.2 are transferred to above-mentioned solution in reaction kettle, and 4 h are reacted at 220 DEG C；
6.3 products obtain CuCl/Cu after centrifugation and washing2O/Cu porous nano-sheets.The size of nanometer sheet is
0.9-1.5 μm, thickness is 54-60 nm, and aperture is 5.2-10.5 nm.
Comparative example 1
1.1 by the CuCl of 1.254 g2∙2H2O, the NaHCO of 0.618 g3It is added to 14.0 mL glycerine and 12.0 mL second
The in the mixed solvent of alcohol, stirs to get clear solution；
1.2 the same as embodiment 4；
1.3 products obtain random pattern, reunite that apparent, size distribution ranges are big after centrifugation and washing
（0.15-0.85 μm）CuCl/Cu2O/Cu blocky-shaped particles, are unable to get CuCl/Cu2O/Cu porous nano chip architectures.Explanation
The introducing of EDTA-2Na directly affects the forming process and size of product morphology.
Comparative example 2
2.1 by the CuCl of 1.254 g2∙2H2O, the ammonium hydroxide of 20 wt%（0.0074 mol NH3·H2O）, 1.642 g
EDTA-2Na is added to the in the mixed solvent of 13.0 mL ethyl alcohol and 13.0ml ethylene glycol, stirs to get clear solution；
2.2 the same as embodiment 4；
It is big to obtain bad dispersibility, random pattern, size distribution ranges after centrifugation and washing for 2.3 products
（0.45-3.65 μm）CuO/Cu2O blocky-shaped particles, are unable to get CuCl/Cu2O/Cu porous nano chip architectures.Illustrate transparent molten
The composition of liquid directly affects the crystalline phase composition and microscopic appearance of product.
Comparative example 3
3.1 by the CuCl of 2.686 g2∙2H2O, the NaHCO of 0.395 g3, 8.798 g EDTA-2Na be added to 5.0 mL
The in the mixed solvent of glycerine and 21.0 mL ethyl alcohol, stirs to get clear solution；
3.2 the same as embodiment 4；
3.3 products obtain random pattern, reunite that apparent, size distribution ranges are big after centrifugation and washing
（0.35-2.55 μm）CuCl/Cu2O/Cu blocky-shaped particles, are unable to get CuCl/Cu2O/Cu porous nano chip architectures.Illustrate anti-
The concentration of system is answered to directly affect the forming process and size of product morphology.
Comparative example 4
4.1 by the Gerhardite of 1.777g（Cu(NO3)2∙3H2O）, 0.618 g NaHCO3, 1.642 g
EDTA-2Na is added to the in the mixed solvent of 14.0 mL glycerine and 12.0 mL ethyl alcohol, stirs to get clear solution；
4.2 the same as embodiment 4；
4.3 products obtain random pattern, reunite that apparent, size distribution ranges are big after centrifugation and washing
（0.25-2.95 μm）Cu2O/Cu blocky-shaped particles.Illustrate that the type of reaction raw materials also has a major impact product pattern.
Claims (5)
1. a kind of CuCl/Cu2The preparation method of O/Cu porous nano-sheets, it is characterized in that including the following steps：
（1）By copper chloride, NaHCO3, EDTA-2Na be added to the in the mixed solvent of glycerine and ethyl alcohol, stir to get transparent molten
Liquid；
（2）By step（1）Clear solution heating, carry out solvent thermal reaction；
（3）After reaction, by product centrifugation, washing, CuCl/Cu is obtained2O/Cu porous nano-sheets；
Copper chloride, NaHCO3, EDTA-2Na molar ratio be 1：0.6-1.4：0.5-0.9；
The volume ratio of glycerine and ethyl alcohol is 1：0.5-1.5；
Solvent thermal reaction temperature is 190-220 DEG C, and the reaction time is 1-24 h.
2. preparation method according to claim 1, it is characterized in that：In the mixed solvent of the copper chloride in glycerine and ethyl alcohol
A concentration of 0.12-0.36 mol/L.
3. preparation method according to claim 1, it is characterized in that：Solvent thermal reaction carries out in confined conditions.
4. preparation method according to claim 1,2 or 3, it is characterized in that：Gained CuCl/Cu2The ruler of O/Cu porous nano-sheets
Very little is 0.06-2.5 μm, and the thickness of nanometer sheet is 5-100 nm, and aperture is 1-20 nm.
5. according to the CuCl/Cu described in any one of claim 1-42CuCl/ made from the preparation method of O/Cu porous nano-sheets
Cu2O/Cu porous nano-sheets.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710041712.1A CN106694903B (en) | 2017-01-20 | 2017-01-20 | A kind of CuCl/Cu2The preparation method and products obtained therefrom of O/Cu porous nano-sheets |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710041712.1A CN106694903B (en) | 2017-01-20 | 2017-01-20 | A kind of CuCl/Cu2The preparation method and products obtained therefrom of O/Cu porous nano-sheets |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106694903A CN106694903A (en) | 2017-05-24 |
| CN106694903B true CN106694903B (en) | 2018-09-14 |
Family
ID=58908512
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710041712.1A Expired - Fee Related CN106694903B (en) | 2017-01-20 | 2017-01-20 | A kind of CuCl/Cu2The preparation method and products obtained therefrom of O/Cu porous nano-sheets |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106694903B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111482175B (en) * | 2020-05-09 | 2022-10-28 | 中国科学技术大学 | Preparation method of copper/cuprous oxide heterojunction nanosheet catalyst |
| CN113059173B (en) * | 2021-03-23 | 2022-02-08 | 西北有色金属研究院 | Preparation method of foliated porous copper nanosheet |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7087100B2 (en) * | 2001-01-31 | 2006-08-08 | General Electric Company | Preparation of nanosized copper and copper compounds |
| CN102137728B (en) * | 2008-08-29 | 2013-09-11 | 石原产业株式会社 | Metallic copper dispersion, process for producing the metallic copper dispersion, electrode, wiring pattern, and coating film formed using the metallic copper dispersion, decorative article and antimicrobial article with the coating film formed there |
| CN102962468A (en) * | 2011-09-01 | 2013-03-13 | 中国科学院福建物质结构研究所 | Preparation method for catalyst of nano-copper particles |
| CN102642864B (en) * | 2012-04-25 | 2014-04-02 | 中国科学院合肥物质科学研究院 | Method for preparing crystal-phase-controllable monodispersed Cu2ZnSnS4 nanocrystalline |
| US10507524B2 (en) * | 2013-07-25 | 2019-12-17 | Ishihara Sangyo Kaisha, Ltd. | Metallic copper dispersion, method for manufacturing same, and usage for same |
| CN105845948B (en) * | 2016-04-07 | 2018-02-27 | 河南师范大学 | A kind of preparation method of flower-shaped copper/cupric oxide Micron-nano composites carried noble metal fuel-cell catalyst |
-
2017
- 2017-01-20 CN CN201710041712.1A patent/CN106694903B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN106694903A (en) | 2017-05-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102849798B (en) | Molybdenum disulfide nano-sheet film material and its preparation methods | |
| Li et al. | A facile approach for the tunable fabrication of BiOBr photocatalysts with high activity and stability | |
| CN107262116B (en) | Hierarchical structure MoS2/Cu2S composite material and preparation method thereof | |
| CN104959044A (en) | Synthetic method of metal organic skeleton membrane | |
| Gu et al. | Single-crystalline α-Fe2O3 with hierarchical structures: Controllable synthesis, formation mechanism and photocatalytic properties | |
| CN103754954B (en) | Preparation method of iron molybdenum oxide (II) nanocube | |
| CN103601177B (en) | Method for preparing graphene from solid organic acid by using alkali metal salt as catalyst | |
| CN112536046B (en) | Preparation method of flaky indium zinc sulfide photocatalyst with efficient reduction activity | |
| CN102389949B (en) | A kind of preparation method of sea urchin-shaped nanometer copper particles | |
| CN108620601B (en) | Method for preparing flaky Cu nanocrystalline at room temperature | |
| CN102641736A (en) | Sea urchin shaped copper oxide catalyst, as well as preparation method and application thereof | |
| CN106694903B (en) | A kind of CuCl/Cu2The preparation method and products obtained therefrom of O/Cu porous nano-sheets | |
| CN103601178B (en) | Method for synthesizing graphene from solid organic acid | |
| CN108695499B (en) | A kind of nanocomposite of the hierarchical structure of controllable epitaxial growth, preparation method and applications | |
| Mao et al. | A new route for synthesizing VO2 (B) nanoribbons and 1D vanadium-based nanostructures | |
| CN106378170A (en) | A graphitic carbon nitride/silver carbonate/silver bromide ternary composite nano-material, a preparing method thereof and uses of the nano-material | |
| CN108465489A (en) | A kind of Fe3O4@ZIF-8 core-shell types composite material and preparation methods and catalytic applications | |
| CN108554407A (en) | Nano-copper base catalyst and preparation method thereof | |
| CN102557107A (en) | Method for preparing flower-shaped copper sulfide (CuS) nanocrystal | |
| CN113562760B (en) | Phase-state-controllable preparation method and application of CdS nano-materials in different phase states | |
| CN109134877B (en) | Optical functional composite material, preparation method and tandem photocatalysis application thereof | |
| CN105084409B (en) | It is a kind of（200）Crystal face exposes the synthetic method of single dispersing CuO nanometer sheet | |
| CN108855217B (en) | Preparation method and application of copper-based metal organic framework nano sheet | |
| CN106602083A (en) | Synthesis method for Cu-N-C catalyst by hydrothermal method | |
| CN107511488B (en) | A kind of 3-dimensional metal palladium nano sheet fast preparation method based on etching assisting growth |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20180914 Termination date: 20220120 |