CN109748327A - One kind preparing CuCoO based on MOFs material at low temperature2The method of nanocrystalline material - Google Patents
One kind preparing CuCoO based on MOFs material at low temperature2The method of nanocrystalline material Download PDFInfo
- Publication number
- CN109748327A CN109748327A CN201910138897.7A CN201910138897A CN109748327A CN 109748327 A CN109748327 A CN 109748327A CN 201910138897 A CN201910138897 A CN 201910138897A CN 109748327 A CN109748327 A CN 109748327A
- Authority
- CN
- China
- Prior art keywords
- cucoo
- deionized water
- low temperature
- reaction
- dehydrated alcohol
- 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.)
- Granted
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
It is synthetically prepared nanoscale CuCoO at a lower temperature using hydro-thermal method the present invention relates to a kind of2The method of crystalline material.One kind preparing delafossite structure CuCoO based on MOFs material at low temperature2The method of nanocrystalline material, it is characterized in that including the following steps: with metal-organic framework materials (Metal Organic Frameworks, MOFs material) it is that initial reactant prepares precursors, precursors are put into hydrothermal reaction kettle, after being carried out hydro-thermal reaction 24~48 hours at 100~140 DEG C, reaction product is handled to obtain sediment through eccentric cleaning, sediment drying obtains the delafossite structure CuCoO of 50~200nm size2Nanocrystalline material.Operation of the present invention is simple, and technological parameter is easily controllable, pollution-free, yield is high, has the characteristics that low temperature, quick；It can be widely used in various novel photoelectric function elements.
Description
Technical field
The present invention relates to MOFs materials (Metal Organic Frameworks, metal-organic framework materials), nanometer material
Material is synthetically prepared field, is synthetically prepared nanosized copper hematite structure CuCoO at a lower reaction temperature in particular with hydro-thermal method2
The method of crystalline material.
Background technique
Delafossite type oxide (ABO2, A=Cu, Ag etc., B=Al, Ga, Cr, Co or La etc.) and it is a kind of important transition
Metal oxide materials.Tokyo polytechnical university Hosono professor et al. reports CuAlO in 1997 on Nature for the first time2It is thin
The p-type electric-conducting characteristic of film, room-temperature conductivity are 9.5 × 10-2s·cm-1.By CuAlO2Inspiration of the chemical valence with design philosophy,
Series A BO2Structural material has become the primary study perpetual object of researcher.The ABO of delafossite structure2With hexagonal layer
Shape crystal structure, due to BO6The octahedral different stackings of rib lead to delafossite structure oxide ABO altogether2There are two kinds of crystalline substances of 2H and 3R
Type.As typical p-type semiconductor material, series A BO2Material is successively applied to transparent conductive oxide, too by wide coverage
The field of photoelectric devices such as positive energy battery device, optical electrical catalyst.
CuCoO2Material is a kind of novel cheap, environmental protection ABO2Material.In 3R delafossite phase CuCoO2Lattice in, Cu
With close shell d10 structure, O-Cu-O layer and CoO with dumbbell shaped linear structure6The layer of rib octahedral layer alternating stacking altogether
Shape structure.The CuCoO of 3R crystal form2Cell parameterDue to copper 3d track and oxygen 2p track
Hydridization, cause oxygen atom in valence-band edge localization, and the layers of copper of Hexagonal Close-packed is its main conductive layer, thus the material have
There are biggish optical band gap width and higher conductivity, there is good application prospect in field of photoelectric devices.Currently, state
It is inside and outside to CuCoO2The research report of material is less, can generally be prepared by ion-exchange reactions or high temperature solid state reaction
CuCoO2Crystalline material.But the reaction time is too long or reaction temperature is excessively high, will lead to CuCoO2Material crystals size is larger,
Reaction efficiency is low.For example, 2010, M.Beekman et al. passes through CuCl and LiCoO2Between simple ion exchange solid-state it is anti-
It answers, after reacting 48 hours at 590 DEG C, prepares polycrystalline delafossite oxide CuCoO2Material.2013, Ruttanapun C
Et al. at 1005 DEG C of high temperature, using conventional solid reaction method synthesize delafossite structure CuCoO2Crystalline material.With it is traditional from
Sub- exchange reaction method or high-temperature sintering process are compared, and reactant is placed under special environment (closed, high pressure etc.) hair by hydro-thermal method
GCMS computer reaction, avoids two complicated experimental implementations of high-temperature calcination and ball milling, can greatly improve Product formation efficiency, extensively
The general nanostructure crystalline material that is applied to synthesizes field.Applicant seminar utilized hydrothermal reaction at low temperature in 2017, for the first time anti-
The CuCoO of 2 microns of sizes is synthetically prepared out when to answer temperature be 100 DEG C2Crystalline material, and its electrolysis water oxygen evolution activity is ground
Study carefully.But due to CuCoO2Crystalline material size is larger, and specific surface area is smaller to cause its active sites less, and electrolysis water activity is still
It is to be improved.Further, since nanoscale p-type semiconductor ABO2Materials synthesis prepares extremely difficult, ABO2The scarcity of nanocrystalline material
Seriously restrict the photoelectric device application study of the series material.Only CuGaO at present2、CuCrO2、CuAlO2、CuMnO2、AgCrO2
Etc. the relevant report of several nanocrystalline materials, do not find temporarily about hydro-thermal method synthesis nano CuCoO2The research report of crystalline material
Road.Therefore, it is badly in need of exploring research and development using new material synthesis method, with its crystalline mi morphology and size of Effective Regulation, preparation
The CuCoO of high quality out2Nanocrystalline material.So research and utilization hydro-thermal method prepares CuCoO2Nanocrystalline material is very novel
, p-type ABO is prepared for exploring2Nanocrystalline material and its device, which are applied, has highly important research significance.
Summary of the invention
The object of the present invention is to provide a kind of low temperature preparation delafossite structure CuCoO2The method of nanocrystalline material, this method
Has the characteristics that low temperature, quick.
To achieve the above object, the technical solution used in the present invention is: a kind of low temperature preparation nanosized copper hematite structure
CuCoO2The method of crystalline material, it is characterized in that including the following steps: to come using MOFs material as the source Cu or Co initial reactant
Preparing precursors, (or hydro-thermal reaction presoma is prepared anti-using the MOFs material containing Cu or Co as initial reactant
Answer presoma), precursors are put into hydrothermal reaction kettle, are carried out hydro-thermal reaction 24~48 hours at 100~140 DEG C
Afterwards, reaction product is handled to obtain sediment through eccentric cleaning, sediment drying obtains the CuCoO of delafossite structure2Crystal material
Expect (the CuCoO that crystalline size is about 50~200nm2Crystalline material.
According to the above technical scheme, the precursors the preparation method comprises the following steps: by the source Co reactant and the source Cu reactant
It is added according to mass ratio 1:1~1.3 in the mixed solution of deionized water and dehydrated alcohol, the volume of deionized water and dehydrated alcohol
Than for 1:0.4~3.0, after dissolution is sufficiently stirred in magnetic stirring apparatus (stirring 10~15 minutes), add the source Co reactant or
The NaOH of 10~50 times of the source Cu reactant quality is stirred well to dissolution completely, obtains precursors as mineralizer.
Specifically, the preparation method of the precursors is one of following three kinds (deionized water and dehydrated alcohols
Volume ratio is 1:0.4~3.0):
1) deionized water and dehydrated alcohol is added according to mass ratio 1:1~1.3 in the MOFs material of Co and Cu based compound
Mixed solution in, after stirring and dissolving, add the MOFs material of Co or the NaOH conduct of 10~50 times of Cu based compound quality
Mineralizer, stirring obtain precursors to dissolving completely；
2) deionized water and dehydrated alcohol is added according to mass ratio 1:1~1.3 in the MOFs material of Co based compound and Cu
Mixed solution in, after stirring and dissolving, add 10~50 times of MOFs quality of materials of the NaOH conduct of Co based compound or Cu
Mineralizer, stirring obtain precursors to dissolving completely；
3) deionized water and anhydrous second is added according to mass ratio 1:1~1.3 in the MOFs material of the MOFs material of Co and Cu
In the mixed solution of alcohol, after stirring and dissolving, the MOFs material of Co or 10~50 times of MOFs quality of materials of the NaOH of Cu are added
As mineralizer, stirring obtains precursors to dissolving completely.
According to the above technical scheme, the source Cu reactant is containing Cu2+Compound { such as Cu (NO3)2、CuSO4Etc. water-soluble
Liquid }, or the MOFs material containing Cu.
According to the above technical scheme, the Co reactant is containing Co2+Compound { such as Co (NO3)2、CoSO4Equal aqueous solutions },
Or the MOFs material containing Co.
According to the above technical scheme, in the hydro-thermal reaction, reaction solution is deionized water and dehydrated alcohol in hydrothermal reaction kettle
Mixed solution, consisting of: deionized water and dehydrated alcohol volume ratio are 1:0.4~3.0, deionized water resistivity is 18.24M
Ω cm (25 DEG C), filling rate are 60~75%.
According to the above technical scheme, the method for the eccentric cleaning processing are as follows: successively use deionized water, dilute NH3·H2O (matter
Measure score 1~10%), secondary ordered pair reaction product of dehydrated alcohol progress eccentric cleaning.The wherein successive cleaning of eccentric cleaning liquid
It is sequentially adjustable (to can also be used: deionized water, dilute NH3·H2O, the eccentric cleanings such as deionized water, dehydrated alcohol).
According to the above technical scheme, the method for eccentric cleaning processing are as follows: according to dilute NH3·H2O (mass fraction 1~
10%), deionized water, the order progress eccentric cleaning of dehydrated alcohol.
According to the above technical scheme, the drying are as follows: by eccentric cleaning treated sediment in vacuum drying oven
60 DEG C drying 4~12 hours.
A kind of above-mentioned low temperature preparation delafossite structure CuCoO2The application of nanocrystalline material, it is characterized in that: as novel half
Conductor working electrode material is applied in various photoelectric functional devices.
According to the above technical scheme, described to be applied in various photoelectric functional devices are as follows: solar battery, electrolysis water,
In photoelectrolysis water or photocatalytic device etc..
The present invention is reacted using low-temperature hydrothermal, and regulation includes in precursors component, reaction temperature and hydrothermal reaction kettle
The filling rate parameter of reaction solution, (100~140 DEG C) by single step reaction method prepare out nanoscale at a lower temperature for the first time
CuCoO2Crystalline material.The source Cu Co is introduced using MOFs material as reactant, develops a kind of CuCoO2Crystalline material is low
Temperature, high yield, the fast preparation method of low cost, for promoting delafossite structure p-type semiconductor material and its in photoelectric device
The application development in field all has highly important learning value.
Compared with prior art, the beneficial effects of the present invention are:
Nanoscale CuCoO is prepared using hydrothermal reaction at low temperature for the first time2Crystalline material has been filled up both at home and abroad about being synthetically prepared
Delafossite structure CuCoO2The research blank of nanocrystalline material is expected to promote p-type ABO2Semiconductor material and its photoelectric device lead
The application development in domain.Also have a characteristic that
(1) this method preparation process is simple, technological parameter is easy to control, experimental repeatability is good, single yield is high.
(2) the reaction raw material sources that this method uses are extensive, cheap, production cost is low.
(3) when reaction temperature is 100~140 DEG C, CuCoO can be prepared2Crystalline material (such as Fig. 1).With reaction
For temperature from when being reduced to 100 DEG C for 140 DEG C, nanocrystalline size is reduced to~50nm (such as Fig. 3) from~150nm (such as Fig. 2).
(4) using XPS to CuCoO2Crystalline material surface-element valence state information carries out test analysis (such as Fig. 4), test knot
Fruit shows that Cu is Cu in compound+, Co Co3+, belong to delafossite (AIBⅢO2) structural material is consistent with document report.
Detailed description of the invention
Fig. 1 is reaction product X ray diffracting spectrum prepared by embodiment 1,2,3,4；Abscissa is the angle of diffraction in figure
Degree, ordinate is relative intensity.It can be seen from the figure that can be prepared when reaction temperature is 100~140 DEG C
CuCoO2Crystalline material, it is delafossite structure CuCoO that corresponding standard diffraction map number, which is #21-0256,2Crystalline material is oikocryst
Phase.
Fig. 2 is CuCoO prepared by embodiment 22Crystalline material scanning electron microscope (SEM) photograph.When reaction temperature is 140 DEG C, benefit
Shooting microscopic appearance photo is observed to reaction product with field emission scanning electron microscope.It can be seen from the figure that prepared
CuCoO2Material crystals size about 100~200nm, microscopic appearance meet typical delafossite structure crystalline material.
Fig. 3 is CuCoO prepared by embodiment 42Crystalline material scanning electron microscope (SEM) photograph.When reaction temperature is 100 DEG C, benefit
Shooting microscopic appearance photo is observed to reaction product with field emission scanning electron microscope.It can be seen from the figure that prepared
CuCoO2Material crystals size about 50~80nm.
Fig. 4 is CuCoO prepared by embodiment 12Crystalline material carries out x-ray photoelectron spectroscopy (XPS) test analysis
As a result, wherein figure a be Cu 2p two characteristic spectral line Cu 2p 3/2 and Cu 2p 1/2, correspond respectively to 933.0eV and
952.7eV, with other ABO2Material C uAlO2、CuFeO2Middle Cu 2p position of spectral line is close, is shown to be Cu+.In addition, can from figure b
To find out two characteristic spectral line Co 2p 3/2 and Co 2p 1/2 of Co 2p, 780.3eV and 795.4eV are corresponded respectively to, with
Co2O3Middle Co 2p characteristic spectral line position is close, is shown to be Co3+。
Specific embodiment
The present invention prepares nanoscale CuCoO using hydro-thermal reaction2Chemicals used in crystalline material mainly includes Co
(NO3)2, methanol, 2-methylimidazole, 1,3,5-Benzenetricarboxylic acid, Cu (NO3)2, NaOH, dehydrated alcohol, NH3·H2O and deionized water etc..
Such as the preparation of the MOFs crystalline material (Cu-BTC) containing Cu: hydrothermal synthesis method is utilized, the Cu- containing Cu is prepared
Cu-BTC powder can be obtained after eccentric cleaning is dry in BTC (for existing literature report method).
Such as the preparation of the MOFs crystalline material (ZIF-67) containing Co: room temperature aging method is utilized, is prepared containing Co's
ZIF-67 powder can be obtained after eccentric cleaning is dry in ZIF-67 (for existing literature report method).
Below with reference to examples and drawings, the invention will be further described, but is not limited to the following content.
Embodiment 1:
A kind of CuCoO of low temperature preparation nanosized copper hematite structure2The method of crystalline material, includes the following steps:
First prepare precursors (or hydro-thermal reaction presoma): by the MOFs crystalline material (ZIF-67) and Cu of Co
(NO3)2(mixed solution of the reaction solution for deionized water and dehydrated alcohol, deionized water are added in reaction solution according to mass ratio 1:1
It is 1:2.5 with dehydrated alcohol volume ratio), after dissolution in magnetic stirrer 10~15 minutes, add ZIF-67 mass 10
NaOH again continues stirring 10~15 minutes to being completely dissolved, obtains precursors as mineralizer.
Above-mentioned precursors are transferred in hydrothermal reaction kettle (generally polytetrafluoroethylene (PTFE)), reaction solution (water is controlled
Reaction solution is deionized water and dehydrated alcohol mixed solution in thermal response kettle, and deionized water and dehydrated alcohol volume ratio are 1:
2.5), deionized water resistivity is 18.24M Ω cm (25 DEG C), filling rate about 70%.Sealing autoclave body is placed on temperature programmed control baking
Hydro-thermal reaction is carried out in case, sets reaction temperature as 140 DEG C, the reaction time is 24 hours.
After reaction, it to autoclave body cooled to room temperature, opens autoclave body and takes out reaction product (obtaining sediment).Reaction
Product (obtaining sediment) successively uses deionized water, dilute NH3·H2O (mass fraction 1%), deionized water, dehydrated alcohol etc. from
The heart cleans 2 times, finally 60 DEG C of heat preservations drying in 12 hours, the CuCoO of available 100~200nm size in vacuum drying oven2It receives
The brilliant material of rice.
Embodiment 2:
A kind of CuCoO of low temperature preparation nanosized copper hematite structure2The method of crystalline material, includes the following steps:
First prepare precursors (or hydro-thermal reaction presoma): by ZIF-67 and Cu (NO3)2According to mass ratio 1:1.2
(reaction solution is the mixed solution of deionized water and dehydrated alcohol, and deionized water is with dehydrated alcohol volume ratio in addition reaction solution
1:2.5), after molten 10~15 minutes solutions are sufficiently stirred in magnetic stirring apparatus, 50 times of ZIF-67 mass of NaOH is added as mine
Agent continues stirring 10~15 minutes to being completely dissolved, obtains precursors.
Above-mentioned precursors are transferred in hydrothermal reaction kettle (generally polytetrafluoroethylene (PTFE)), reaction solution (hydro-thermal is controlled
Reaction solution is deionized water and dehydrated alcohol mixed solution in reaction kettle, and deionized water and dehydrated alcohol volume ratio are 1:2.5),
Deionized water resistivity is 18.24M Ω cm (25 DEG C), filling rate about 75%.Sealing autoclave body is placed in temperature programmed control baking oven
Hydro-thermal reaction is carried out, sets reaction temperature as 140 DEG C, the reaction time is 24 hours.
After reaction, it to autoclave body cooled to room temperature, opens autoclave body and takes out reaction product (obtaining sediment).Reaction
Product (obtaining sediment) successively uses deionized water, dilute NH3·H2O (mass fraction 3%), deionized water, dehydrated alcohol etc. from
The heart cleans 3 times, finally 60 DEG C of heat preservations drying in 8 hours, the CuCoO of available 100~200nm size in vacuum drying oven2It receives
The brilliant material of rice.
Embodiment 3:
A kind of CuCoO of low temperature preparation nanosized copper hematite structure2The method of crystalline material, includes the following steps:
First prepare precursors (or hydro-thermal reaction presoma): by Co base MOF material ZIF-67 and Cu (NO3)2According to
(reaction solution is the mixed solution of deionized water and dehydrated alcohol, deionized water and anhydrous second in mass ratio 1:1.2 addition reaction solution
Alcohol volume ratio is 1:2.5), after dissolution in 10~15 minutes is sufficiently stirred in magnetic stirring apparatus, add Cu (NO3)210 times of quality
NaOH continues stirring 10~15 minutes to being completely dissolved, obtains precursors as mineralizer.
Above-mentioned precursors are transferred in hydrothermal reaction kettle (generally polytetrafluoroethylene (PTFE)), reaction solution (hydro-thermal is controlled
Reaction solution is deionized water and dehydrated alcohol mixed solution in reaction kettle, and deionized water and dehydrated alcohol volume ratio are 1:2.5),
Deionized water resistivity is 18.24M Ω cm (25 DEG C), filling rate about 60%.Sealing autoclave body is placed in temperature programmed control baking oven
Hydro-thermal reaction is carried out, sets reaction temperature as 120 DEG C, the reaction time is 24 hours.
After reaction, it to autoclave body cooled to room temperature, opens autoclave body and takes out reaction product.Reaction product (is sunk
Starch) successively use deionized water, dilute NH3·H2The eccentric cleanings such as O (mass fraction 5%), deionized water, dehydrated alcohol 3 times,
Finally 60 DEG C of heat preservations drying in 8 hours, the CuCoO of available 80~200nm size in vacuum drying oven2Nanocrystalline material.
Embodiment 4:
A kind of CuCoO of low temperature preparation nanosized copper hematite structure2The method of crystalline material, includes the following steps:
First prepare precursors (or hydro-thermal reaction presoma): by ZIF-67 and Cu (NO3)2According to mass ratio 1:1.3
(reaction solution is the mixed solution of deionized water and dehydrated alcohol, and deionized water is with dehydrated alcohol volume ratio in addition reaction solution
1:2.5), after dissolution in 10~15 minutes is sufficiently stirred in magnetic stirring apparatus, Cu (NO is added3)2The NaOH that 50 times of quality is as mine
Agent continues stirring 10~15 minutes to being completely dissolved, obtains precursors.
Above-mentioned precursors are transferred in hydrothermal reaction kettle (generally polytetrafluoroethylene (PTFE)), reaction solution (hydro-thermal is controlled
Reaction solution is deionized water and dehydrated alcohol mixed solution in reaction kettle, and deionized water and dehydrated alcohol volume ratio are 1:2.5),
Deionized water resistivity is 18.24M Ω cm (25 DEG C) filling rate about 75%.Sealing autoclave body be placed in temperature programmed control baking oven into
Row hydro-thermal reaction sets reaction temperature as 100 DEG C, and the reaction time is 24~48 hours.
After reaction, it to autoclave body cooled to room temperature, opens autoclave body and takes out reaction product.Reaction product (is sunk
Starch) successively use deionized water, dilute NH3·H2The eccentric cleanings such as O (mass fraction 10%), deionized water, dehydrated alcohol 3 times,
Finally 60 DEG C of heat preservations drying in 8 hours, the CuCoO of available 50~80nm size in vacuum drying oven2Nanocrystalline material.
Embodiment 5:
A kind of CuCoO of low temperature preparation nanosized copper hematite structure2The method of crystalline material, includes the following steps:
First prepare precursors (or hydro-thermal reaction presoma): by ZIF-67 and Cu (NO3)2According to mass ratio 1:1.2
(reaction solution is the mixed solution of deionized water and dehydrated alcohol, and deionized water is with dehydrated alcohol volume ratio in addition reaction solution
1:0.4), after dissolution in magnetic stirrer 10~15 minutes, Cu (NO is added3)2The NaOH that 30 times of quality is as mineralising
Agent continues stirring 10~15 minutes to being completely dissolved, obtains precursors.
Above-mentioned precursors are transferred in hydrothermal reaction kettle (generally polytetrafluoroethylene (PTFE)), reaction solution (hydro-thermal is controlled
Reaction solution is deionized water and dehydrated alcohol mixed solution in reaction kettle, and deionized water and dehydrated alcohol volume ratio are 1:0.4),
Deionized water resistivity is 18.24M Ω cm (25 DEG C), filling rate about 75%.Sealing autoclave body is placed in temperature programmed control baking oven
Hydro-thermal reaction is carried out, sets reaction temperature as 100 DEG C, the reaction time is 48 hours.
After reaction, it to autoclave body cooled to room temperature, opens autoclave body and takes out reaction product.Reaction product (is sunk
Starch) successively use deionized water, dilute NH3·H2The eccentric cleanings such as O (mass fraction 5%), deionized water, dehydrated alcohol 4 times,
Finally 60 DEG C of heat preservations drying in 12 hours, available CuCoO in vacuum drying oven2Nanocrystalline material.
Embodiment 6:
A kind of CuCoO of low temperature preparation nanosized copper hematite structure2The method of crystalline material, includes the following steps:
First prepare precursors (or hydro-thermal reaction presoma): by Co (NO3)2With the MOFs crystalline material (Cu- of Cu
BTC) (mixed solution of the reaction solution for deionized water and dehydrated alcohol, deionized water are added in reaction solution according to mass ratio 1:1.2
It is 1:1 with dehydrated alcohol volume ratio), after dissolution in magnetic stirrer 10~15 minutes, add 10 times of Cu-BTC mass
NaOH as mineralizer, continue stirring 10~15 minutes to being completely dissolved, obtain precursors.
Above-mentioned precursors are transferred in hydrothermal reaction kettle (generally polytetrafluoroethylene (PTFE)), reaction solution (hydro-thermal is controlled
Reaction solution is deionized water and dehydrated alcohol mixed solution in reaction kettle, and deionized water and dehydrated alcohol volume ratio are 1:1), it goes
Ionized water resistivity is 18.24M Ω cm (25 DEG C), filling rate about 70%.Sealing autoclave body be placed in temperature programmed control baking oven into
Row hydro-thermal reaction sets reaction temperature as 140 DEG C, and the reaction time is 24 hours.
After reaction, it to autoclave body cooled to room temperature, opens autoclave body and takes out reaction product.Reaction product (is sunk
Starch) successively use deionized water, dilute NH3·H2The eccentric cleanings such as O (mass fraction 5%), deionized water, dehydrated alcohol 4 times,
Finally 60 DEG C of heat preservations drying in 12 hours, available CuCoO in vacuum drying oven2Nanocrystalline material.
Embodiment 7:
A kind of CuCoO of low temperature preparation nanosized copper hematite structure2The method of crystalline material, includes the following steps:
First prepare precursors (or hydro-thermal reaction presoma): by the MOFs crystalline material (ZIF-67) of Co and Cu
MOFs crystalline material (Cu-BTC) is according to (reaction solution is deionized water and dehydrated alcohol in mass ratio 1:1.2 addition reaction solution
Mixed solution, deionized water and dehydrated alcohol volume ratio are 1:3.0), after dissolution in magnetic stirrer 10~15 minutes, then
The NaOH for being added 10 times of Cu-BTC mass continues stirring 10~15 minutes to being completely dissolved, obtains reaction precursor as mineralizer
Body.
Above-mentioned precursors are transferred in hydrothermal reaction kettle (generally polytetrafluoroethylene (PTFE)), reaction solution (hydro-thermal is controlled
Reaction solution is deionized water and dehydrated alcohol mixed solution in reaction kettle, and deionized water and dehydrated alcohol volume ratio are 1:3.0),
Deionized water resistivity is 18.24M Ω cm (25 DEG C), filling rate about 70%.Sealing autoclave body is placed in temperature programmed control baking oven
Hydro-thermal reaction is carried out, sets reaction temperature as 140 DEG C, the reaction time is 24 hours.
After reaction, it to autoclave body cooled to room temperature, opens autoclave body and takes out reaction product.Reaction product (is sunk
Starch) successively using deionized water, dehydrated alcohol etc. eccentric cleanings 4 times, finally in vacuum drying oven 60 DEG C heat preservation 12 hours it is dry
It is dry, available CuCoO2Nanocrystalline material.
Embodiment 8:
Delafossite structure CuCoO prepared by above-described embodiment 1-72The purposes of nanocrystalline material is primarily referred to as half
It is used in the photoelectric functional device of conducting oxide as electrode material.By CuCoO2Particle is using film deposition techniques (such as silk
Net print process, thermal spraying decomposition method etc.), CuCoO is prepared on the surface electro-conductive glass (FTO)2Thin-film material is used as solar-electricity
Pond (dyestuff/quantum dot sensitized, perovskite solar battery etc.) electrode material.For example, proportionally adding CuCoO2It is nanocrystalline
(1.0g), ethyl cellulose (5.0g), terpinol (6.0g), dehydrated alcohol (30.0g) etc. pass through ultrasonic disperse and revolving etc.
The CuCoO of different solid contents is obtained after reason2Slurry, it is thermally treated then using silk screen print method in conductive glass surface brush film
After sintering removal organic matter, CuCoO is finally obtained2Electrode film material.
Embodiment 9:
Delafossite structure CuCoO prepared by above-described embodiment 1-72The purposes of nanocrystalline material is primarily referred to as half
It is used in the photoelectric functional device of conducting oxide as electrode material.By CuCoO2Particle is using film deposition techniques (as dripped
Coating, thermal spraying decomposition method etc.), the loaded Cu CoO on working electrode surface or the surface electro-conductive glass (FTO)2Nanocrystalline material
Material is used as electrode catalyst agent material in photoelectrochemical cell.For example, proportionally adding CuCoO2Nanocrystalline (2.0g),
Nafion (10.0g), isopropanol (12.0g), H2O (50.0g) etc. prepares certain density CuCoO by ultrasonic disperse2It receives
Rice crystalline suspension liquid, adjustment suspension vol can prepare the CuCoO of different carrying capacity2Working electrode material can be used as catalysis
Agent electrode material is used in the analysis oxygen experiment of optical electrical solution elutriation hydrogen.
Obviously, those skilled in the art can be to delafossite structure CuCoO of the invention2The hydro-thermal system of nanocrystalline material
Preparation Method and its nanocrystalline material carry out various modification and variations without departing from the spirit and scope of the present invention.For example, using containing
One or more of Cu or MOFs containing Co and its derivative are used as reactant, introduce the source Cu or the source Co and to carry out hydro-thermal anti-
It answers.If in this way, to these modifications and changes of the present invention belong to claim of the invention and its equivalent technical scope it
Interior, then the present invention is also intended to include these modifications and variations.
Claims (10)
1. a kind of low temperature preparation nanosized copper hematite structure CuCoO2The method of crystalline material, it is characterized in that include the following steps: with
MOFs material prepares precursors as the source Cu or Co initial reactant, and precursors are put into hydrothermal reaction kettle,
After carrying out hydro-thermal reaction 24~48 hours at 100~140 DEG C, reaction product is handled to obtain sediment through eccentric cleaning, be sunk
Starch drying, obtains the CuCoO of delafossite structure2Crystalline material.
2. a kind of low temperature preparation delafossite structure CuCoO according to claim 12The method of nanocrystalline material, feature
Be: the precursors the preparation method comprises the following steps: by the source Co reactant and the source Cu reactant according to mass ratio 1:1~1.3 plus
In the mixed solution for entering deionized water and dehydrated alcohol, the volume ratio of deionized water and dehydrated alcohol is 1:0.4~3, in magnetic force
After dissolution is sufficiently stirred in blender, the NaOH of 10~50 times of the source Co reactant or the source Cu reactant quality is added as mineralising
Agent is stirred well to dissolution completely, obtains precursors.
3. a kind of low temperature preparation delafossite structure CuCoO according to claim 22The method of nanocrystalline material, feature
Be: the source Cu reactant is containing Cu2+Compound or MOFs material containing Cu.
4. a kind of low temperature preparation delafossite structure CuCoO according to claim 22The method of nanocrystalline material, feature
Be: the Co reactant is containing Co2+Compound or MOFs material containing Co.
5. a kind of CuCoO of low temperature preparation delafossite structure according to claim 12The method of nanocrystalline material, feature
Be: in the hydro-thermal reaction, reaction solution is deionized water and dehydrated alcohol mixed solution in hydrothermal reaction kettle, consisting of: going
Ionized water and dehydrated alcohol volume ratio are 1:0.4~3.0, and deionized water resistivity is 18.24M Ω cm (25 DEG C), filling
Rate is 60~75%.
6. a kind of low temperature preparation delafossite structure CuCoO according to claim 12The method of nanocrystalline material, feature
It is: the method for the eccentric cleaning processing are as follows: successively use deionized water, dilute NH3·H2O, the secondary ordered pair of dehydrated alcohol, which reacts, produces
Object carries out eccentric cleaning.
7. a kind of low temperature preparation delafossite structure CuCoO according to claim 12The method of nanocrystalline material, feature
It is: the method for the eccentric cleaning processing are as follows: according to dilute NH3·H2O, deionized water, dehydrated alcohol order be centrifuged it is clear
It washes.
8. a kind of low temperature preparation delafossite structure CuCoO according to claim 12The method of nanocrystalline material, feature
It is: the drying are as follows: by eccentric cleaning treated sediment 60 DEG C drying 4~12 hours in vacuum drying oven.
9. a kind of low temperature preparation delafossite structure CuCoO as described in claim 12The application of nanocrystalline material, it is characterized in that:
It is applied in various photoelectric functional devices as novel semi-conductor working electrode material.
10. a kind of low temperature preparation delafossite structure CuCoO as claimed in claim 92The application of nanocrystalline material, it is characterized in that:
Described applies in various photoelectric functional devices are as follows: in solar battery, electrolysis water, photoelectrolysis water or photocatalytic device.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910138897.7A CN109748327B (en) | 2019-02-25 | 2019-02-25 | Low-temperature preparation of CuCoO based on MOFs material2Method for producing nanocrystalline material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910138897.7A CN109748327B (en) | 2019-02-25 | 2019-02-25 | Low-temperature preparation of CuCoO based on MOFs material2Method for producing nanocrystalline material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109748327A true CN109748327A (en) | 2019-05-14 |
| CN109748327B CN109748327B (en) | 2020-08-04 |
Family
ID=66407685
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910138897.7A Active CN109748327B (en) | 2019-02-25 | 2019-02-25 | Low-temperature preparation of CuCoO based on MOFs material2Method for producing nanocrystalline material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109748327B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110993739A (en) * | 2019-12-13 | 2020-04-10 | 陕西易莱德新材料科技有限公司 | Production method of membrane electrode for solar cell |
| CN110980791A (en) * | 2019-12-05 | 2020-04-10 | 武汉理工大学 | P type delafossite structure CuScO2Crystalline material, method for the production thereof and use thereof |
| CN114113582A (en) * | 2021-12-20 | 2022-03-01 | 云南大学 | Metal organic framework nanoenzyme biological probe and ELISA kit |
| CN114177911A (en) * | 2021-12-10 | 2022-03-15 | 湖南大学 | Carbon-supported multi-metal oxide catalyst and preparation method and application thereof |
| CN115679471A (en) * | 2022-12-09 | 2023-02-03 | 福州市福塑科学技术研究所有限公司 | Preparation method of rod-shaped hollow nano copper oxide antibacterial wear-resistant polyamide fiber |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120149560A1 (en) * | 2010-12-08 | 2012-06-14 | Electronics And Telecommunications Research Institute | Method of manufacturing porous metal oxide |
| CN103922421A (en) * | 2014-05-13 | 2014-07-16 | 西北大学 | Method for preparing alpha-Fe2O3 |
| CN104058461A (en) * | 2014-07-04 | 2014-09-24 | 武汉理工大学 | Low-temperature preparation method for CuFeO2 crystal material of delafossite structure |
| CN104659358A (en) * | 2015-01-30 | 2015-05-27 | 南京工业大学 | Preparation method of hollow nickel cobaltate nano polyhedron |
| CN107098401A (en) * | 2017-06-02 | 2017-08-29 | 武汉理工大学 | A kind of delafossite structure CuCoO2Crystalline material and its low temperature preparation method |
| CN108666544A (en) * | 2018-04-18 | 2018-10-16 | 燕山大学 | One kind is derived with MOF prepares carbon coating CoTiO3The synthetic method of nano microcrystalline material |
| CN108715457A (en) * | 2018-06-21 | 2018-10-30 | 福州大学 | Based on MOF template controlledly synthesis nano structure of zinc oxide gas sensors |
-
2019
- 2019-02-25 CN CN201910138897.7A patent/CN109748327B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120149560A1 (en) * | 2010-12-08 | 2012-06-14 | Electronics And Telecommunications Research Institute | Method of manufacturing porous metal oxide |
| CN103922421A (en) * | 2014-05-13 | 2014-07-16 | 西北大学 | Method for preparing alpha-Fe2O3 |
| CN104058461A (en) * | 2014-07-04 | 2014-09-24 | 武汉理工大学 | Low-temperature preparation method for CuFeO2 crystal material of delafossite structure |
| CN104659358A (en) * | 2015-01-30 | 2015-05-27 | 南京工业大学 | Preparation method of hollow nickel cobaltate nano polyhedron |
| CN107098401A (en) * | 2017-06-02 | 2017-08-29 | 武汉理工大学 | A kind of delafossite structure CuCoO2Crystalline material and its low temperature preparation method |
| CN108666544A (en) * | 2018-04-18 | 2018-10-16 | 燕山大学 | One kind is derived with MOF prepares carbon coating CoTiO3The synthetic method of nano microcrystalline material |
| CN108715457A (en) * | 2018-06-21 | 2018-10-30 | 福州大学 | Based on MOF template controlledly synthesis nano structure of zinc oxide gas sensors |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110980791A (en) * | 2019-12-05 | 2020-04-10 | 武汉理工大学 | P type delafossite structure CuScO2Crystalline material, method for the production thereof and use thereof |
| CN110993739A (en) * | 2019-12-13 | 2020-04-10 | 陕西易莱德新材料科技有限公司 | Production method of membrane electrode for solar cell |
| CN114177911A (en) * | 2021-12-10 | 2022-03-15 | 湖南大学 | Carbon-supported multi-metal oxide catalyst and preparation method and application thereof |
| CN114113582A (en) * | 2021-12-20 | 2022-03-01 | 云南大学 | Metal organic framework nanoenzyme biological probe and ELISA kit |
| CN114113582B (en) * | 2021-12-20 | 2022-09-16 | 云南大学 | Metal organic framework nanoenzyme biological probe and ELISA kit |
| CN115679471A (en) * | 2022-12-09 | 2023-02-03 | 福州市福塑科学技术研究所有限公司 | Preparation method of rod-shaped hollow nano copper oxide antibacterial wear-resistant polyamide fiber |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109748327B (en) | 2020-08-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109748327A (en) | One kind preparing CuCoO based on MOFs material at low temperature2The method of nanocrystalline material | |
| CN104058461B (en) | A kind of delafossite structure CuFeO2The low temperature preparation method of crystalline material | |
| CN102491417B (en) | Method for preparing ball-flower-shaped gamma-bismuth trioxide powder | |
| CN105463566B (en) | A kind of epitaxial growth MoSe2‑XnSemThe liquid phase process of hetero nano structure | |
| Guo et al. | Hierarchical TiO 2–CuInS 2 core–shell nanoarrays for photoelectrochemical water splitting | |
| CN107098401B (en) | A kind of delafossite structure CuCoO2Crystalline material and its low temperature preparation method | |
| Chen et al. | Synthesis of {010}-faceted anatase TiO 2 nanoparticles from layered titanate for dye-sensitized solar cells | |
| CN113087016A (en) | Preparation method of rod-shaped bismuth sulfide/reduced graphene oxide composite material | |
| Feng et al. | Switchable synthesis of p-and n-type Cu–In–S grooved pyramid-like microcrystals for unassisted photoelectrochemical water splitting | |
| Lu et al. | Efficient all p-type heterojunction photocathodes for photoelectrochemical water splitting | |
| CN103880081A (en) | Preparation method for delafossite-structure AgCrO2 nanocrystalline material | |
| CN105366714A (en) | Synthetic method of stannic oxide nanoflower array | |
| CN105664921B (en) | A kind of nanometer W0.4Mo0.6O3The preparation method of high-performance optical catalyst | |
| CN102897722B (en) | Alpha-In2Se3 nano-grade flower-ball solvothermal synthesizing method | |
| Choi et al. | Hydrothermal synthesis and photocatalytic properties of CuGaO2/ZnO hexagonal platelet hybrids | |
| CN109694101A (en) | A kind of SnO2@ZnO nano composite material and preparation method | |
| CN103101964A (en) | Preparation method of zinc oxide nanoflower of spiauterite structure | |
| Li et al. | Synthesis of TiO2-SrTiO3 hetero-structured nanorod arrays and their photoelectrical performance in all-solid-state dye-sensitized solar cells | |
| CN112588303A (en) | Preparation method of selenium-bismuth oxide nanosheet and heterojunction type photoelectrode based on preparation method | |
| CN107337233A (en) | A kind of method of one step vulcanization method synthesis of titanium dioxide and titanium disulfide composite | |
| Zhang et al. | Bi2O2S topological transformation and in-situ regrowth of [hk1]-oriented SbBiS3-xSex 2D skeleton structure for construction of efficient quasi-two-dimensional Sb2S3-xSex-based heterojunction photoanodes | |
| CN110563036A (en) | bismuth oxide nano material rich in oxygen vacancy and preparation method thereof | |
| CN109755028A (en) | A kind of nickelous selenide applied to supercapacitor/nickel hydroxide composite material and preparation method | |
| Zhou et al. | Synthesis of hierarchical structure cuprous oxide by a novel two-step hydrothermal method and the effect of its addition on the photovoltaic properties of ZnO-based dye-sensitized solar cells | |
| CN110950311B (en) | Preparation method of nickel selenide micro-nano flower, product and application 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 |