CN106830049A - 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 PDF

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CN106830049A
CN106830049A CN201710147840.4A CN201710147840A CN106830049A CN 106830049 A CN106830049 A CN 106830049A CN 201710147840 A CN201710147840 A CN 201710147840A CN 106830049 A CN106830049 A CN 106830049A
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mole
nanometer sheet
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naoh
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CN106830049B (en
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曾毅
金松星
郑伟涛
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Jilin University
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    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G3/00—Compounds of copper
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    • 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
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    • 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
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    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
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    • C01—INORGANIC CHEMISTRY
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    • 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
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    • C01P2006/80—Compositional purity

Abstract

A kind of Cu of nanometer sheet composition of the invention9S5The preparation method of hollow 26 face body particle, belongs to the technical field of nano material preparation, and the method is dispersed in ethanol solution with the cuprous polyhedron of solid as presoma, adds NaOH solution and Na2S solution, the step of anion exchange reaction one is carried out by the divalent ion of sulphur and the divalent ion of oxygen 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 compares with conventional method, there is provided a kind of new synthesis and prepare the new method of semiconductor nano material cage structure, has the advantages that inexpensive, simple to operate, reaction rate is fast, environment-friendly, low-carbon high-efficiency.The Cu of nanometer sheet composition9S5Hollow 26 face body particle shows the application prospect with high catalytic activity on water oxidation catalysis, and the field such as solar cell, cold electrode and nanotube switch has potential using value.

Description

A kind of Cu of nanometer sheet composition9S5The preparation method of hollow 26 face body
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 shows good catalytic in base metal photocatalysis water oxygen field Can, and the field such as solar cell, cold electrode and nanotube switch has potential using value.
Background technology
In recent years, hollow-core construction particle caused the great interest of people, because it has 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, The aspect such as energy storage device and nanochemistry reaction has important application prospect.The current strategy on synthesizing hollow-core construction It is main to have 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, preparation cost is high and easily causes environmental pollution.Therefore, development cryogenic conditions, environment-friendly, Fast back-projection algorithm are 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, and energy gap is 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；Using CuxAbilities of the S in terms of photonic absorption 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 with 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 part, column self assembly sulphur by introducing Tin (IV)-X complexity bodies Change cuprous 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.)；Have the advantages that specific surface area is big due to special hollow multi-plane structure, position makes it in multiple fields for activity Show potential application value.Recently, Tokyo Univ Japan Teranishi groups close by template of cuprous oxide micro/nano crystal Into 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, has toxic solvent to join With wherein, and these preparation process exist and spend higher, cumbersome and generation environment the shortcomings of pollute.
The content of the invention
The technical problem to be solved in the present invention is the shortcoming for overcoming background technology to exist, there is provided a kind of low cost, operation letter Single, reaction rate is fast, environment-friendly, low-carbon high-efficiency preparation nanometer sheet composition 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 mixes with deionized-distilled water stirring, 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 subsequently added, usage ratio is that every 1.5 moles of NaOH uses 25 milliliters of deionizations to distill Water, cupric sulfate pentahydrate continues to be reacted 5-20 minutes in 60 DEG C of stirred in water bath with the mixed solution of NaOH；
(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, NaOH, ascorbic acid are according to the above-mentioned amount for sequentially adding Continue to react 1-1.5h in 60 DEG C of stirred in water bath；
(4) extract 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 vacuum dried a few hours；
(5) secondly, by the solid Cu of 0.01M2O Polyhedral Particles mix with ethanol solution, and usage ratio is every 0.01 to rub Your Cu2O uses 30-50 milliliters of ethanol；
(6) and then, add 0.0005 moles of NaOH, usage ratio is 1 milliliter of deionization of every 0.0005-0.01 moles of use Distilled water, and in 55-65 DEG C of stirred in water bath reaction；
(7) it is subsequently added 0.005 mole of Na2S, usage ratio is every 0.005 mole of Na2S using 10-30 milliliters go from Sub- distilled water, then reaction obtains the Cu of nanometer sheet composition for 10-20 minutes in 55-65 DEG C of water-bath9S5Hollow 26 face body particle.
Using the cuprous polyhedron of solid be presoma, with 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 caused by the change of temperature, cuprous sulfide table is controlled by adding NaOH Face is not passivated, and chemical mobility of the surface is higher, adds Na2S, anion is carried out by the divalent ion of sulphur and the divalent ion of oxygen The step of exchange reaction one obtains the Cu constituted with the nanometer sheet corresponding to the cuprous polyhedron pattern of solid9S5Hollow 26 face body Cage structure, further improves the specific surface area of nano material.
Operating procedure of the invention is main in two stages：The first step is preparation solid polyhedron cuprous oxide particle mistake Journey, using water bath with thermostatic control uniform mixed aqueous solution of the heating comprising copper source, reducing agent and additive, by adjusting reaction solution in NaOH concentration synthesizes the solid polyhedron cuprous oxide particle of different-shape；Second step is 60 DEG C of fabricated in situ Cu9S5Process, With solid polyhedron cuprous oxide particle as presoma in ethanol solution, under the conditions of 60 DEG C, in NaOH and Na2Under S synergies, Solid polyhedron cuprous oxide obtains the Cu that nanometer sheet is constituted by the step of anion exchange reaction one9S5Hollow 26 face body, in difference Under reaction temperature, the Cu of different-shape is can obtain9S5Particle, under the differential responses time, can obtain different size and similar pattern Cu9S5Particle.
The present invention has following beneficial effect：
1st, low cost, synthesizes under low temperature.
2nd, simple to operate, reaction rate is fast, and experimental period is short, can Fast back-projection algorithm.
3rd, it is environment-friendly, in whole experiment process, without toxic pharmaceuticals addition, it is to avoid the pollution to environment.
4th, low-carbon high-efficiency, is the Cu that template one-step synthesis nanometer sheet is constituted using solid polyhedron cuprous oxide9S5Hollow 26 Face body, centre is not required to, by etching preparation hollow-core construction, improve efficiency reduces cost.
The Cu of the nanometer sheet composition that the 5th, prepared by the present invention9S5Hollow 26 face body granule-morphology is controllable and with compared with Large ratio surface Product and chemism higher.
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.
Specific embodiment
The particular content and implementation method for doing invention are further illustrated below in conjunction with example：
First by 0.01 mole of CuSO45H2The stirring of O and deionized-distilled water mixes, and usage ratio is every 0.01 to rub Your CuSO45H2O uses 100 milliliters of deionized-distilled waters, is reacted 10 minutes in 60 DEG C of stirred in water bath；It is subsequently added 1.5 Moles of NaOH, usage ratio is every 1.5 first by 0.01 mole of CuSO45H2O mixes with deionized-distilled water stirring, uses Amount ratio is every 0.01 mole of CuSO45H2O uses 100 milliliters of deionized-distilled waters, in 60 DEG C of stirred in water bath reactions 10 Minute；1.5 moles of NaOH are subsequently added, usage ratio is that every 1.5 moles of NaOH uses 25 milliliters of deionized-distilled waters, five water Copper sulphate continues to be reacted 5 minutes in 60 DEG C of stirred in water bath with the mixed solution of NaOH；0.1 mole is added again Ascorbic acid, usage ratio is that every 0.1 mole of ascorbic acid use 25 milliliters of deionized-distilled waters, five water sulphur Sour copper, NaOH, ascorbic acid continue to react 1h according to the above-mentioned amount for sequentially adding in 60 DEG C of stirred in water bath；Carry Extract reaction solution precipitation and obtain the cuprous Polyhedral Particles of brick-red solid, with deionized-distilled water centrifuge washing for several times and 60 DEG C vacuum drying a few hours.Secondly, by the solid Cu of 0.01M2O Polyhedral Particles mix with ethanol solution, and usage ratio is every 0.01 mole of Cu2O uses 39 milliliters of ethanol；Then, 0.0005 moles of NaOH is added, usage ratio is every 0.0005 mole to be made With 1 milliliter of deionized-distilled water, and in 60 DEG C of stirred in water bath reactions；It is subsequently added 0.005 mole of Na2S, usage ratio is every 0.005 mole of Na2S uses 10 milliliters of deionized-distilled waters, and then reaction obtains nanometer sheet in 10-20 minutes in 60 DEG C of water-baths The Cu of composition9S5Hollow 26 face body particle.
Embodiment 1：
By 0.01M CuSO45H2In flask, 60 DEG C of stirrings of heating water bath mix O and 100mL deionized-distilled waters, Reaction 10min, is added dropwise 25mL and contains 1.5M NaOH, reacts 5min, 25mL is added dropwise and contains 0.1M ascorbic acid, reacts 1h.Reaction naturally cools to room temperature after terminating, and brick-red solid 20 hexahedron structure copper oxidule precipitation is obtained in flask With remaining reaction solution, it is separated, washed, be vacuum dried with deionized water and ethanol after obtain solid 20 hexahedron structure Cuprous oxide particle, its scanned photograph figure, transmission photo figure and X-ray diffractogram see accompanying drawing 1, accompanying drawing 2 and accompanying drawing 3 respectively. Crystal structure is for Emission in Cubic and crystallinity is preferably, and the standard card (JCPDS No.05-0667) with cuprous oxide is completely corresponding, There is no any miscellaneous peak, illustrate the cuprous oxide that sample is high-purity.
Embodiment 2：
The solid Cu of the 0.01M that will be obtained in embodiment 12O Polyhedral Particles are mixing with 39mL ethanol solutions, and water-bath adds Under 60 DEG C of stirrings of heat, 1mL is added to contain 0.0005M NaOH, subsequent 10mL contains 0.005M Na2S, reacts 10min, adds room Warm lower 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 Solution, it is separated, washed, be vacuum dried with deionized water and ethanol after obtain nanometer sheet composition Cu9S5Hollow 26 face body Grain, its scanned photograph figure, transmission photo figure and X-ray diffractogram are shown in accompanying drawing 4, accompanying drawing 5 and accompanying drawing 6 respectively.Because Cu9S5Be by Monocrystalline cuprous oxide nano particle is obtained by the method for anion exchange, during conversion.The symmetry of lattice is also sent out Change has been given birth to, multiple twin structure has been formd, so its X-ray diffractogram is made up of two or more crystal grain of same substance, And Cu9S5Standard card (JCPDS No.47-1748) match.

Claims (2)

1. the Cu that a kind of nanometer sheet is constituted9S5The preparation method of hollow 26 face body, comprises the following steps that：
(1) first by 0.01 mole of CuSO45H2O mixes with deionized-distilled water stirring, 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 subsequently added, usage ratio is that every 1.5 moles of NaOH uses 25 milliliters of deionized-distilled waters, five Brochanite continues to be reacted 5-20 minutes in 60 DEG C of stirred in water bath with the mixed solution of NaOH；
(3) 0.1 mole of ascorbic acid are added again, and usage ratio is that every 0.1 mole of ascorbic acid are used 25 milliliters of deionized-distilled waters, cupric sulfate pentahydrate, NaOH, ascorbic acid are according to the above-mentioned amount for sequentially adding 60 DEG C stirred in water bath continues to react 1-1.5h；
(4) extract reaction liquid precipitate and obtain the cuprous Polyhedral Particles of brick-red solid, be centrifuged with deionized-distilled water and washed Wash for several times and 60 DEG C are vacuum dried a few hours；
(5) secondly, by the solid Cu of 0.01M2O Polyhedral Particles mix with ethanol solution, and usage ratio is every 0.01 mole Cu2O uses 30-50 milliliters of ethanol；
(6) and then, add 0.0005 moles of NaOH, usage ratio is the distillation of 1 milliliter of deionization of every 0.0005-0.01 moles of use Water, and in 55-65 DEG C of stirred in water bath reaction；
(7) it is subsequently added 0.005 mole of Na2S, usage ratio is every 0.005 mole of Na2S is steamed using 10-30 milliliters of deionization Distilled water, then reaction obtains the Cu of nanometer sheet composition for 10-20 minutes in 55-65 DEG C of water-bath9S5Hollow 26 face body particle.
2. the Cu that a kind of nanometer sheet according to claim 1 is constituted9S5The preparation method of hollow 26 face body, it is characterised in that The use of the cuprous polyhedron of solid is presoma, with 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 caused by the change of temperature, controls cuprous sulfide surface not blunt by adding NaOH Change, chemical mobility of the surface is higher, add Na2S, anion exchange reaction is carried out by the divalent ion of sulphur and the divalent ion of oxygen One step obtains the Cu constituted with the nanometer sheet corresponding to the cuprous polyhedron pattern of solid9S5The cage structure of hollow 26 face body, Further improve the specific surface area of nano material.
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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109465017A (en) * 2018-11-19 2019-03-15 黑龙江大学 A kind of seven bronze medals-eight of four vulcanization vulcanize controllable method for preparing and the application of nine bronze medal heterojunction structure hollow cubic body catalysts
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
CN111286037A (en) * 2020-03-03 2020-06-16 西安交通大学 Preparation method of morphology-controllable low-dimensional copper-based conjugated polymer nano thermoelectric material
CN112366298A (en) * 2020-10-19 2021-02-12 杭州职业技术学院 Carbon-assembled zinc sulfide cobalt sulfide hollow nano polyhedral framework material and preparation and application thereof
CN112366312A (en) * 2020-10-19 2021-02-12 杭州职业技术学院 Carbon-assembled zinc sulfide hollow nano polyhedral honeycomb material and preparation and application thereof
CN113058600A (en) * 2021-03-29 2021-07-02 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
CN115212897A (en) * 2022-07-26 2022-10-21 河北工业大学 Self-standing nano porous copper-loaded nonacopper pentasulfide nanosheet 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

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104495908A (en) * 2014-12-31 2015-04-08 湖南稀土金属材料研究院 Preparation method of cuprous sulfide powder, and cuprous sulfide powder
CN104689796A (en) * 2013-12-04 2015-06-10 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

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104689796A (en) * 2013-12-04 2015-06-10 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
CN104495908A (en) * 2014-12-31 2015-04-08 湖南稀土金属材料研究院 Preparation method of cuprous sulfide powder, and cuprous sulfide powder

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
QIWEI TIAN,ET AL.: "Hydrophilic Cu9S5 Nanocrystals A Photothermal Agent with a 25.7% Heat Conversion Efficiency for Photothermal Ablation of Cancer Cells in Vivo", 《ACS NANO》 *
李静 等: "微纳米Cu9S5的溶剂热合成及其光学性能", 《化工新型材料》 *
高嵩等: "原位聚合－化学镀制备Cu9S5/PANI涤纶导电纤维", 《电镀与涂饰》 *

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109465017A (en) * 2018-11-19 2019-03-15 黑龙江大学 A kind of seven bronze medals-eight of four vulcanization vulcanize controllable method for preparing and the application of nine bronze medal heterojunction structure hollow cubic body catalysts
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
CN111286037A (en) * 2020-03-03 2020-06-16 西安交通大学 Preparation method of morphology-controllable low-dimensional copper-based conjugated polymer nano thermoelectric material
CN112366298A (en) * 2020-10-19 2021-02-12 杭州职业技术学院 Carbon-assembled zinc sulfide cobalt sulfide hollow nano polyhedral framework material and preparation and application thereof
CN112366312A (en) * 2020-10-19 2021-02-12 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
CN113058600A (en) * 2021-03-29 2021-07-02 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
CN115212897A (en) * 2022-07-26 2022-10-21 河北工业大学 Self-standing nano porous copper-loaded nonacopper pentasulfide nanosheet composite 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

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