CN106830049B - A kind of Cu of nanometer sheet composition9 S5The preparation method of hollow 26 face body - Google Patents
A kind of Cu of nanometer sheet composition9 S5The preparation method of hollow 26 face body Download PDFInfo
- Publication number
- CN106830049B CN106830049B CN201710147840.4A CN201710147840A CN106830049B CN 106830049 B CN106830049 B CN 106830049B CN 201710147840 A CN201710147840 A CN 201710147840A CN 106830049 B CN106830049 B CN 106830049B
- Authority
- CN
- China
- Prior art keywords
- hollow
- mole
- nanometer sheet
- solid
- face body
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/12—Sulfides
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/46—Sulfur-, selenium- or tellurium-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
- C30B7/14—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions the crystallising materials being formed by chemical reactions in the solution
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/30—Three-dimensional structures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Abstract
A kind of Cu of nanometer sheet composition of the present invention9S5The preparation method of hollow 26 face body particle, belongs to the technical field of nano material preparation, and this method is dispersed in ethanol solution using the cuprous polyhedron of solid as presoma, adds NaOH solution and Na2S solution, one step of anion exchange reaction is carried out to the divalent ion of oxygen by the divalent ion of sulphur at a certain temperature and obtains the hollow-core construction particle similar to the cuprous pattern of solid, the pattern of solid polyhedron can be by adjusting the temperature reacted, and the time of reaction is controlled.The present invention is compared with conventional method, there is provided a kind of new synthesis and the new method for preparing semiconductor nano material cage structure, have the advantages that inexpensive, easy to operate, reaction rate is fast, environmental-friendly, low-carbon high-efficiency.The Cu of nanometer sheet composition9S5Hollow 26 face body particle shows the application prospect on water oxidation catalysis with high catalytic activity, and the field such as solar cell, cold electrode and nanotube switch has potential using value.
Description
Technical field
The invention belongs to technical field prepared by nano material, and in particular to a kind of Cu of nanometer sheet composition9S5Hollow 26 face
The preparation method of body particle, such hollow-core construction show good catalytic in base metal photocatalysis water oxygen field
Energy, and the field such as solar cell, cold electrode and nanotube switch have potential using value.
Background technology
In recent years, hollow-core construction particle caused the great interest of people, since it is with inner space, low-density, big ratio
Surface area, compared with stiff stability and Surface Permeability the features such as, catalysis, photoelectric sensor, drug delivery carrier, photonic crystal,
Energy storage device and nanochemistry reaction etc. have important application prospect.The currently strategy on synthesis hollow-core construction
Mainly there are Ken Kedaer effects, acid etch, coordination polymer self-template direct growth and solid thermal decomposition process, prepare such as
Cu7S4、 Fe2O3、MnO、ZnO、TiO2Hollow cage-shape structure particle.But above-mentioned preparation process needs further heat or acid treatment,
Process is complicated, manufacturing cost is high and easily causes environmental pollution.Therefore, cryogenic conditions are developed, environmental-friendly, Fast back-projection algorithm is hollow
The new method of cage structure particle has important academic significance and application value.
CuxS is a kind of typical narrow band gap P-type semiconductor, energy gap 1.2-2.2eV, due to its good photoelectricity
Performance and be widely used in each research field.Such as CuxS is used as photochemical catalyst, by photocatalysis water oxidation reaction,
There is potential application, to solve the problems, such as that energy shortage provides a kind of approach in solar cell；CuxS nano materials have
Good chemical property, is a kind of potential lithium ion battery negative material；Utilize CuxAbilities of the S in terms of photonic absorption
It can be applied in photovoltaic art.People have put into great effort development and have prepared different-shape CuxThe method of S, for example, nanometer
Line, nanometer plate, nanometer sheet etc..Wu computer MSR Information systems are equal using solvent-free thermal local behavior using copper-thiolates polymers as predecessor
Even cuprous sulfide nano wire (Ling C, Yu-Biao C, Li-Ming W.Synthesis of uniform Cu2S
nanowires from copper-thiolate polymer precursors by a solventless
thermolytic method.[J]. Journal of the American Chemical Society,2004,126
(50):16334-5.)；Li computer MSR Information systems are used as inorganic surfaces ligand, column self assembly by introducing Tin (IV)-X complexity bodies
Synthesize cuprous sulfide hexagonal nanometer plate (Xiaomin L, Huaibin S, Jinzhong N, et al.Columnar self-
assembly of Cu2S hexagonal nanoplates induced by tin(IV)-X complex as
inorganic surface ligand.[J].Journal of the American Chemical Society, 2010,
132(37):12778-9.)；Due to special hollow multi-plane structure have the advantages that big, the active position of specific surface area make its
Multiple fields show potential application value.Recently, Tokyo Univ Japan Teranishi groups are with cuprous oxide micro/nano crystal
For templated synthesis CuxS pseudo-crystal nanocages structure (H.-L.Wu, R.Sato, A.Yamaguchi, et al.Formation of
pseudomorphic nanocages from Cu2O nanocrystals through anion exchange
reactions[J].Science, 2016,351(6279):1306-1310.).But above building-up process, there is toxic solvent
Participate, and these preparation process have the shortcomings of spending higher, cumbersome and generation environment to pollute.
The content of the invention
The technical problem to be solved in the present invention is, overcome background technology there are the shortcomings that, there is provided a kind of low cost, operation letter
Single, fast, environmental-friendly, low-carbon high-efficiency the preparation nanometer sheet composition of reaction rate Cu9S5The preparation side of hollow 26 face body particle
Method.
The concrete technical scheme that the present invention takes is as follows：
A kind of Cu of nanometer sheet composition9S5The preparation method of hollow 26 face body, comprises the following steps that：
(1) first by 0.01 mole of CuSO45H2O is stirred with deionized-distilled water, and usage ratio is every 0.01
Mole CuSO45H2O uses 100 milliliters of deionized-distilled waters, is reacted 5-20 minutes in 60 DEG C of stirred in water bath；
(2) 1.5 moles of NaOH are then added, the NaOH that usage ratio is every 1.5 moles is distilled using 25 milliliters of deionizations
The mixed solution of water, cupric sulfate pentahydrate and sodium hydroxide continues to react 5-20 minutes in 60 DEG C of stirred in water bath；
(3) 0.1 mole of ascorbic acid are added again, and usage ratio is every 0.1 mole of ascorbic acid
Using 25 milliliters of deionized-distilled waters, cupric sulfate pentahydrate, sodium hydroxide, ascorbic acid are according to the above-mentioned amount sequentially added
In 60 DEG C of stirred in water bath the reaction was continued 1-1.5h；
(4) extraction reaction liquid precipitate obtain the cuprous Polyhedral Particles of brick-red solid, with deionized-distilled water from
Heart washing is for several times and 60 DEG C are dried in vacuo a few hours；
(5) secondly, by 0.01 mole of solid Cu2O Polyhedral Particles are mixed with ethanol solution, and usage ratio is every 0.01
Mole Cu2O uses 30-50 milliliters of ethanol；
(6) then, 0.0005 moles of NaOH is added, usage ratio is per 1 milliliter of deionization of 0.0005-0.01 moles of use
Distilled water, and reacted in 55-65 DEG C of stirred in water bath；
(7) 0.005 mole of Na is then added2S, usage ratio are every 0.005 mole of Na2S using 10-30 milliliters go from
Sub- distilled water, then reacts the Cu for obtaining nanometer sheet composition for 10-20 minutes in 55-65 DEG C of water-bath9S5Hollow 26 face body particle.
The use of the cuprous polyhedron of solid is presoma, using ethanol solution as solvent, in 55-65 DEG C of water-bath and other
At a temperature of, derive Cu9S5The change of the crystal structure as caused by the change of temperature, cuprous sulfide table is controlled by adding NaOH
Face is not passivated, chemical mobility of the surface higher, adds Na2S, anion is carried out by the divalent ion of sulphur and the divalent ion of oxygen
One step of exchange reaction obtains the Cu with the nanometer sheet composition corresponding to the cuprous polyhedron pattern of solid9S5Hollow 26 face body
Cage structure, further improves the specific surface area of nano material.
The operating procedure of the present invention is mainly in two stages：The first step is preparation solid polyhedron cuprous oxide particle mistake
Journey, the uniform mixed aqueous solution in copper source, reducing agent and additive is included using water bath with thermostatic control heating, by adjusting in reaction solution
NaOH concentration synthesizes the solid polyhedron cuprous oxide particle of different-shape；Second step is 60 DEG C of fabricated in situ Cu9S5Process,
Using solid polyhedron cuprous oxide particle as presoma in ethanol solution, under the conditions of 60 DEG C, in NaOH and Na2Under S synergistic effects,
Solid polyhedron cuprous oxide obtains the Cu of nanometer sheet composition by one step of anion exchange reaction9S5Hollow 26 face body, in difference
Under reaction temperature, the Cu of different-shape can obtain9S5Particle, under the differential responses time, can obtain different sizes and similar pattern
Cu9S5Particle.
The present invention has following beneficial effect：
1st, it is inexpensive, synthesized under low temperature.
2nd, easy to operate, reaction rate is fast, and experimental period is short, can Fast back-projection algorithm.
3rd, environmental-friendly, in whole experiment process, no toxic pharmaceuticals addition, avoids the pollution to environment.
4th, low-carbon high-efficiency, utilizes the Cu that solid polyhedron cuprous oxide is template one-step synthesis nanometer sheet composition9S5Hollow 26
Face body, centre are not required to prepare hollow-core construction by etching, and improving efficiency reduces cost.
5th, the Cu for the nanometer sheet composition that prepared by the present invention9S5Hollow 26 face body granule-morphology is controllable and with compared with Large ratio surface
Product and higher chemism.
Brief description of the drawings
Fig. 1 is the scanned photograph figure of the cuprous oxide particle of solid 20 hexahedron structure prepared by embodiment 1.
Fig. 2 is the transmission photo figure of the cuprous oxide particle of solid 20 hexahedron structure prepared by embodiment 1.
Fig. 3 is the X-ray diffractogram of the cuprous oxide particle of solid 20 hexahedron structure prepared by embodiment 1.
Fig. 4 is the Cu of nanometer sheet composition prepared by embodiment 29S5The scanned photograph figure of hollow 26 face body particle.
Fig. 5 is the Cu of nanometer sheet composition prepared by embodiment 29S5The transmission photo figure of hollow 26 face body particle.
Fig. 6 is the Cu of nanometer sheet composition prepared by embodiment 29S5The X-ray diffractogram of hollow 26 face body particle.
Embodiment
The particular content and embodiment for doing invention are further illustrated below in conjunction with example：
First by 0.01 mole of CuSO45H2O is stirred with deionized-distilled water, and usage ratio is rubbed for every 0.01
Your CuSO45H2O uses 100 milliliters of deionized-distilled waters, is reacted 10 minutes in 60 DEG C of stirred in water bath；Then add
1.5 moles of NaOH, usage ratio are that every 1.5 moles of NaOH uses 25 milliliters of deionized-distilled waters, cupric sulfate pentahydrate and hydrogen-oxygen
The mixed solution for changing sodium continues to react 5 minutes in 60 DEG C of stirred in water bath；0.1 mole of ascorbic acid are added again, are used
Amount ratio is that every 0.1 mole of ascorbic acid use 25 milliliters of deionized-distilled waters, cupric sulfate pentahydrate, sodium hydroxide,
Ascorbic acid are according to the above-mentioned amount sequentially added in 60 DEG C of stirred in water bath the reaction was continued 1h；Extraction reaction liquid precipitate obtains
To the brick-red cuprous Polyhedral Particles of solid, with deionized-distilled water centrifuge washing, simultaneously 60 DEG C of vacuum drying numbers are small for several times
When.Secondly, by the solid Cu of 0.01M2O Polyhedral Particles are mixed with ethanol solution, and usage ratio is every 0.01 mole of Cu2O
Use 39 milliliters of ethanol；Then, 0.0005 moles of NaOH is added, usage ratio is every 0.0005 mole of use, 1 milliliter of deionization
Distilled water, and reacted in 60 DEG C of stirred in water bath；Then add 0.005 mole of Na2S, usage ratio are every 0.005 mole
Na2S uses 10 milliliters of deionized-distilled waters, and the Cu for obtaining nanometer sheet composition for 10-20 minutes is then reacted in 60 DEG C of water-baths9S5
Hollow 26 face body particle.
Embodiment 1：
By 0.01M CuSO45H2In flask, 60 DEG C of heating water bath is stirred O and 100mL deionized-distilled waters,
10min is reacted, 25mL is added dropwise and contains 1.5M NaOH, reacts 5min, 25mL is added dropwise and contains 0.1M ascorbic acid, reacts
1h.Cooled to room temperature after reaction, obtains brick-red solid 20 hexahedron structure copper oxidule precipitation in flask
With remaining reaction solution, solid 20 hexahedron structure is obtained after separating, washed, be dried in vacuo with deionized water and ethanol
Cuprous oxide particle, its scanned photograph figure, transmission photo figure and X-ray diffractogram see attached drawing 1, attached drawing 2 and attached drawing 3 respectively.
Crystal structure is Emission in Cubic and crystallinity is preferable, completely corresponding with the standard card (JCPDS No.05-0667) of cuprous oxide,
There is no any miscellaneous peak, illustrate the cuprous oxide that sample is high-purity.
By the solid Cu of 0.01M obtained above2O Polyhedral Particles are being mixed with 39mL ethanol solutions, heating water bath 60
DEG C stirring under, add 1mL contain 0.0005M NaOH, subsequent 10mL contains 0.005M Na2S, reacts 10min, adds at room temperature
Standing time is changed to 21 days, and the Cu of the nanometer sheet composition of black is obtained in bottle9S5Hollow 26 face body precipitation and remaining reaction are molten
Liquid, obtains the Cu of nanometer sheet composition after separating, washed, be dried in vacuo with deionized water and ethanol9S5Hollow 26 face body particle,
Its scanned photograph figure, transmission photo figure and X-ray diffractogram are shown in attached drawing 4, attached drawing 5 and attached drawing 6 respectively.Because Cu9S5It is by monocrystalline
Cuprous oxide nano particle is obtained by the method for anion exchange, during conversion.The symmetry of lattice also there occurs
Change, form multiple twin structure, so its X-ray diffractogram is made of two or more crystal grain of same substance, and
Cu9S5Standard card (JCPDS No.47-1748) match.
Claims (2)
- A kind of 1. Cu of nanometer sheet composition9S5The preparation method of hollow 26 face body, comprises the following steps that：(1) first by 0.01 mole of CuSO45H2O is stirred with deionized-distilled water, and usage ratio is every 0.01 mole CuSO45H2O uses 100 milliliters of deionized-distilled waters, is reacted 5-20 minutes in 60 DEG C of stirred in water bath；(2) 1.5 moles of NaOH are then added, usage ratio is that every 1.5 moles of NaOH uses 25 milliliters of deionized-distilled waters, five The mixed solution of brochanite and sodium hydroxide continues to react 5-20 minutes in 60 DEG C of stirred in water bath；(3) 0.1 mole of ascorbic acid are added again, and the ascorbic acid that usage ratio is every 0.1 mole are used 25 milliliters of deionized-distilled waters, cupric sulfate pentahydrate, sodium hydroxide, ascorbic acid are according to the above-mentioned amount sequentially added 60 DEG C stirred in water bath the reaction was continued 1-1.5h；(4) extraction reaction liquid precipitate obtains the cuprous Polyhedral Particles of brick-red solid, is washed with deionized-distilled water centrifugation Wash for several times and 60 DEG C are dried in vacuo a few hours；(5) secondly, by 0.01 mole of solid Cu2O Polyhedral Particles are mixed with ethanol solution, and usage ratio is every 0.01 mole Cu2O uses 30-50 milliliters of ethanol；(6) then, 0.0005 moles of NaOH is added, usage ratio is per 1 milliliter of deionization distillation of 0.0005-0.01 moles of use Water, and reacted in 55-65 DEG C of stirred in water bath；(7) 0.005 mole of Na is then added2S, usage ratio are every 0.005 mole of Na2S is steamed using 10-30 milliliters of deionizations Distilled water, then reacts the Cu for obtaining nanometer sheet composition for 10-20 minutes in 55-65 DEG C of water-bath9S5Hollow 26 face body particle.
- A kind of 2. Cu of nanometer sheet composition according to claim 19S5The preparation method of hollow 26 face body, it is characterised in that The use of the cuprous polyhedron of solid is presoma, using ethanol solution as solvent, in 55-65 DEG C of water-bath and at a temperature of other, Derive Cu9S5The change of the crystal structure as caused by the change of temperature, by add NaOH control cuprous sulfide surface not by Passivation, chemical mobility of the surface higher, adds Na2S, and it is anti-to carry out anion exchange by the divalent ion of sulphur and the divalent ion of oxygen A step is answered to obtain the Cu with the nanometer sheet composition corresponding to the cuprous polyhedron pattern of solid9S5The caged knot of hollow 26 face body Structure, further improves the specific surface area of nano material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710147840.4A CN106830049B (en) | 2017-03-14 | 2017-03-14 | A kind of Cu of nanometer sheet composition9 S5The preparation method of hollow 26 face body |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710147840.4A CN106830049B (en) | 2017-03-14 | 2017-03-14 | A kind of Cu of nanometer sheet composition9 S5The preparation method of hollow 26 face body |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106830049A CN106830049A (en) | 2017-06-13 |
| CN106830049B true CN106830049B (en) | 2018-04-17 |
Family
ID=59143493
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710147840.4A Expired - Fee Related CN106830049B (en) | 2017-03-14 | 2017-03-14 | A kind of Cu of nanometer sheet composition9 S5The preparation method of hollow 26 face body |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106830049B (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109465017B (en) * | 2018-11-19 | 2021-06-08 | 黑龙江大学 | Controllable preparation method and application of heptacopper tetrasulfide-nonacopper octasulfide heterostructure hollow cubic catalyst |
| CN110980796A (en) * | 2019-12-27 | 2020-04-10 | 上海保鼎科技服务有限公司 | Cu assembled by thin sheets7S4Nano flower material and preparation method and application thereof |
| CN111286037B (en) * | 2020-03-03 | 2021-05-28 | 西安交通大学 | Preparation method of morphology-controllable low-dimensional copper-based conjugated polymer nano thermoelectric material |
| CN112366312B (en) * | 2020-10-19 | 2021-10-08 | 杭州职业技术学院 | Carbon-assembled zinc sulfide hollow nano polyhedral honeycomb material and preparation and application thereof |
| CN112366298B (en) * | 2020-10-19 | 2021-10-08 | 杭州职业技术学院 | Carbon-assembled zinc sulfide cobalt sulfide hollow nano polyhedral framework material and preparation and application thereof |
| CN113058600B (en) * | 2021-03-29 | 2022-03-04 | 蚌埠学院 | Controllable preparation method of copper oxide-cuprous oxide nano compound |
| CN113441156A (en) * | 2021-06-24 | 2021-09-28 | 青岛科技大学 | Hollowed-out spherical structure Cu2O/Cu9S5Photocatalytic material and preparation method and application thereof |
| CN115212897B (en) * | 2022-07-26 | 2023-07-14 | 河北工业大学 | Self-supporting nano porous copper loaded nine copper pentasulfide nano sheet composite material and preparation method and application thereof |
| CN115779931A (en) * | 2022-12-07 | 2023-03-14 | 云南师范大学 | Heterojunction photocatalytic material based on cubic cuprous oxide and preparation method thereof |
| CN116651467A (en) * | 2023-06-02 | 2023-08-29 | 常州大学 | Hollow Cu 2-x S@ cadmium manganese sulfide composite photocatalyst and preparation method and application thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104689796B (en) * | 2013-12-04 | 2017-02-08 | 中国科学院大连化学物理研究所 | Nano cuprous sulfide modified monolithic column material and preparation method thereof |
| CN104495908B (en) * | 2014-12-31 | 2016-06-08 | 湖南稀土金属材料研究院 | Cuprous sulfide raw powder's production technology and cuprous sulfide powder body |
-
2017
- 2017-03-14 CN CN201710147840.4A patent/CN106830049B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN106830049A (en) | 2017-06-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106830049B (en) | A kind of Cu of nanometer sheet composition9 S5The preparation method of hollow 26 face body | |
| Prasad et al. | Recent advances in MXenes supported semiconductors based photocatalysts: Properties, synthesis and photocatalytic applications | |
| CN108380224B (en) | Nickel-cobalt sulfide @ bimetal nickel-iron hydroxide core-shell heterostructure nanotube array material and preparation method and application thereof | |
| Prakash et al. | Green synthesis of bismuth based nanoparticles and its applications-A review | |
| CN106498430A (en) | Low energy consumption electrochemistry hydrogen generating system based on dual-functional nanometer array electrode | |
| CN107012474A (en) | A kind of method of large-scale solar energy photocatalysis-photoelectrocatalysis hydrogen production by water decomposition | |
| CN108579724B (en) | Bismuth vanadate nanotube crystal array growing on transparent conductive substrate in [010] direction and preparation and application thereof | |
| CN108671907B (en) | Platinum/titanium dioxide nanoflower composite material and preparation method and application thereof | |
| CN110016691B (en) | WO (WO)3/Fe2O3/Mn3O4Preparation method of composite photo-anode film | |
| CN105645459A (en) | Surface modified urchin-shaped ZnO/TiO2 composite material and preparation method thereof | |
| CN108394935B (en) | A kind of method of space confinement method synthesis of carbon/molybdenum disulfide individual layer nanometer sheet | |
| CN104607216B (en) | The one-step method for synthesizing of phosphorus aluminum codope type conductive zinc oxide nanocatalyst | |
| CN104588045A (en) | Ultra-thin BiOCl nano-sheet, preparation method and application thereof | |
| CN102234133B (en) | Semiconductor compound porous wall titanium dioxide hollow sphere material and preparation method thereof | |
| CN107185547A (en) | A kind of C/Fe FeVO4Composite photo-catalyst and its preparation method and application | |
| CN109201083A (en) | A kind of nano flower-like vanadium disulfide/difunctional composite electrocatalyst of hydroxyl vanadium oxide and preparation method thereof | |
| CN109437313A (en) | The controllable ultra-fine CuFeO of size2Nanometer sheet and its preparation and application | |
| CN110104623A (en) | A kind of preparation method of the four phosphatization cobalt of rich phosphorus transition metal phosphide of different-shape | |
| CN108940329A (en) | A kind of preparation method of high activity NiFe-LDHs catalyst | |
| CN107321372A (en) | The preparation method of CoS nano particles/N doping RGO liberation of hydrogen composites | |
| CN108906020A (en) | A kind of preparation method of titanium dioxide-zinc oxide composite catalyzing material | |
| CN103482675A (en) | Preparation method of cuprous oxide having hollow polyhedral structure | |
| CN109052344A (en) | A kind of preparation method of graphite phase carbon nitride/nickel oxide composite material | |
| CN104925846A (en) | Preparation method of nano copper oxide and application of nano copper oxide in lithium ion battery | |
| CN106955699B (en) | A kind of high-efficiency solar fixed nitrogen catalysis material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20180417 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |