CN110395769A - A kind of high-purity 3R delafossite structure CuFeO2The preparation method of micro crystal material - Google Patents
A kind of high-purity 3R delafossite structure CuFeO2The preparation method of micro crystal material Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 100
- 239000013081 microcrystal Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 95
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 claims abstract description 62
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- 239000000243 solution Substances 0.000 claims abstract description 33
- 239000011259 mixed solution Substances 0.000 claims abstract description 32
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 32
- 239000000725 suspension Substances 0.000 claims abstract description 32
- 229910016514 CuFeO2 Inorganic materials 0.000 claims abstract description 30
- 230000005291 magnetic effect Effects 0.000 claims abstract description 29
- 238000013019 agitation Methods 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 21
- 239000008367 deionised water Substances 0.000 claims abstract description 21
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 21
- 238000002604 ultrasonography Methods 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 13
- 229910000608 Fe(NO3)3.9H2O Inorganic materials 0.000 claims abstract description 11
- 238000004090 dissolution Methods 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 10
- 239000000428 dust Substances 0.000 claims description 10
- 238000005516 engineering process Methods 0.000 claims description 10
- 238000011049 filling Methods 0.000 claims description 10
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 239000000047 product Substances 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims 1
- 238000006731 degradation reaction Methods 0.000 abstract description 5
- 230000001699 photocatalysis Effects 0.000 abstract description 5
- 230000015556 catabolic process Effects 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000002245 particle Substances 0.000 abstract description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 3
- 238000000354 decomposition reaction Methods 0.000 abstract description 3
- 230000006870 function Effects 0.000 abstract description 3
- 239000001257 hydrogen Substances 0.000 abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 3
- 239000000356 contaminant Substances 0.000 abstract description 2
- 239000003302 ferromagnetic material Substances 0.000 abstract description 2
- 238000010531 catalytic reduction reaction Methods 0.000 abstract 1
- 238000009826 distribution Methods 0.000 abstract 1
- 239000010949 copper Substances 0.000 description 41
- 238000003760 magnetic stirring Methods 0.000 description 33
- 239000000126 substance Substances 0.000 description 10
- 230000035484 reaction time Effects 0.000 description 9
- 238000001816 cooling Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 6
- 229940012189 methyl orange Drugs 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 5
- 239000002957 persistent organic pollutant Substances 0.000 description 4
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000005622 photoelectricity Effects 0.000 description 3
- 230000003595 spectral effect Effects 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 235000003283 Pachira macrocarpa Nutrition 0.000 description 2
- 241001083492 Trapa Species 0.000 description 2
- 235000014364 Trapa natans Nutrition 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 235000009165 saligot Nutrition 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910016516 CuFe2O4 Inorganic materials 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 238000009412 basement excavation Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000010671 solid-state reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/40—Carbon monoxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
-
- 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
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- 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
The present invention discloses a kind of high-purity 3R delafossite structure CuFeO2The preparation method of micro crystal material, by Cu (NO3)2.3H2O and Fe (NO3)3.9H2O is added in deionized water, and magnetic agitation dissolution obtains mixed solution, NaOH solution is added dropwise dropwise in mixed solution, then successively ultrasound, magnetic agitation；It is added dropwise after positive propionic aldehyde again and continues magnetic agitation to forming colloidal suspensions；Colloidal suspensions are added in reaction kettle, 100~180 DEG C of reactions 6~for 24 hours, after reaction, to autoclave body cooled to room temperature, opens autoclave body and take out reaction product, obtain high-purity 3R delafossite structure CuFeO after reaction product washing is dry2Micro crystal material；Operation of the present invention is simple, and technological parameter is easily controllable, pollution-free, yield is high, and grain development is complete, particle diameter distribution is uniform, can be widely used for photocatalytic hydrogen production by water decomposition, degradation of contaminant, photo catalytic reduction CO2, in the photoelectric converting functions material and device such as transparent conductive oxide and ferromagnetic material.
Description
Technical field
The present invention relates to a kind of high-purity 3R delafossite structure CuFeO2The preparation method of micro crystal material belongs to metal oxidation
Object semiconductor material is synthetically prepared field.
Background technique
CuFeO2As secondary delafossite compound, the zoneofoxidation bottom of generally existing copper deposit, this conclusion be by
Rogers was proposed in 1913.CuFeO2Crystal structure is by the closely packed Cu of two dimension+And Fe3+O6Octahedron is alternately stacked along c-axis
Form, due to the difference of stack manner, it will be respectively formed six side 2H structures (by ... stacked in a manner of ABABAB ...) and water chestnut side 3R
Structure (by ... stacked in a manner of ABCABC ...).Under practical preparation condition, water chestnut side's 3R structure has relatively low formation energy, because
This is more common.CuFeO2With excellent photocatalysis performance, chemical property, photoelectric conversion performance, magnetic performance, thus extensive
Be applied in the fields such as p-type transparent oxide film, diode, solar battery and photocatalysis.Just because of CuFeO2Have
All multipurposes, so the research of synthesis and performance in relation to delafossite has been increasingly becoming the focus of scientist's research.CuFeO2's
Preparation mainly includes solid-state reaction, sol-gel, the methods of hydrothermal synthesis, but synthetic product be all largely 2H structure with
The mixed phase of 3R structure.And the point defects such as copper vacancy, interstitial oxygen concentration and CuO, Cu2O、Fe2O3、CuFe2O4Equal by-products are frequent
It is introduced into.The fact that lead to consequence very serious: the CuFeO provided in document2Basic physicochemical properties are usually inaccurate
It is true and inconsistent, limit the further R and D to the material.
Summary of the invention
In order to solve the above technical problems, the present invention provides a kind of high-purity 3R delafossite structure CuFeO2The system of micro crystal material
Preparation Method avoids the point defect introduced in conventional synthesis process and miscellaneous phase, causes CuFeO2The basic physical chemistry of material
The accuracy of matter parameter the phenomenon that there are deviations, and then detection can be grasped comprehensively and explore its basic physicochemical properties, more
Good its application potential in various novel photoelectric converting function materials and device of excavation.
The invention is realized by the following technical scheme:
A kind of high-purity 3R delafossite structure CuFeO2The preparation method of micro crystal material, the specific steps are as follows:
(1) by Cu (NO3)2.3H2O and Fe (NO3)3.9H2O is added in deionized water according to molar ratio 1:1, magnetic agitation dissolution,
Obtain mixed solution；
(2) NaOH solution is added dropwise dropwise in the mixed solution of step (1), then successively ultrasound, magnetic agitation；
(3) it is added dropwise in the solution of step (2) after positive propionic aldehyde and continues magnetic agitation to forming colloidal suspensions；
(4) colloidal suspensions of step (3) are added in reaction kettle, the filling rate of colloidal suspensions is 85%, seals autoclave body postposition
In temperature programmed control baking oven, reaction temperature is set as 100~180 DEG C, the reaction time is 6~for 24 hours, after reaction, to autoclave body
Cooled to room temperature opens autoclave body and takes out reaction product, obtains high-purity 3R delafossite structure after reaction product washing is dry
CuFeO2Micro crystal material.
Cu (NO in step (1) mixed solution3)2Concentration be 0.5~0.8mol/L.
The speed of agitator of step (1) magnetic stirring apparatus is 300~400 turns/min, stirs 10~15min.
Step (2) NaOH solution is Cu (NO according to NaOH3)2.3H2O and Fe (NO3)3.9H2The 4~10 of the amount of O total material
It is added again.
The concentration of step (2) NaOH solution is 1.5~4mol/L, and rate of addition is 1.5~2.5mL/min.
Step (2) ultrasonic power is 300~400W, 10~15min of ultrasound.
Step (2) and step (3) magnetic agitation rotating speed are 400~500 turns/min, stir 10~15min.
The rate of addition of the positive propionic aldehyde of step (3) is 4~5mL/min, the volume and Cu (NO of the positive propionic aldehyde of addition3)2.3H2O
With Fe (NO3)3.9H2The Molar ratio L:mol of the amount of O total material is 1~2:10.
Step (4) washing is successively using deionized water, dust technology, dehydrated alcohol etc. eccentric cleanings 5~8 times.
Step (4) drying is 60~80 DEG C of dry 10~12h in constant temperature oven.
Compared with prior art, the present invention there are also following prominent effects:
(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, and environmental pollution is small, cheap, production cost is low.
(3) when reaction temperature is 100~180 DEG C, the 3R delafossite structure CuFeO of very high purity can be obtained2Crystallite
As reaction temperature changes significant change does not occur for material, crystallite dimension, and particle size is at 2 μm or so, but the knot of crystal grain
Crystalline substance improves with the raising of reaction temperature.
(4) present invention can all prepare high-purity 3R delafossite by single step reaction method at a lower temperature or in the short period
Structure C uFeO2Micro crystal material, a kind of high-purity 3R delafossite structure CuFeO developed for the first time2Micro crystal material high yield, it is low at
This fast preparation method, for promoting CuFeO2Semiconductor material and its in photocatalytic hydrogen production by water decomposition, degradation of contaminant, light
Restore CO2, the photoelectric functionals transition material and devices field such as transparent conductive oxide and ferromagnetic material application development, have ten
Divide important learning value and application prospect.
Detailed description of the invention
Fig. 1 is the X ray diffracting spectrum for the material that embodiment 1-5 is prepared,
Fig. 2 is embodiment 1 and the material X ray diffracting spectrum that embodiment 6-8 is prepared；
Fig. 3 is the scanning electron microscope (SEM) photograph for the material that embodiment 1-5 is prepared；
Fig. 4 is the scanning electron microscope (SEM) photograph for the material that embodiment 1 and embodiment 6-8 are prepared；
Fig. 5 is the x-ray photoelectron spectroscopy figure for the material that embodiment 1 is prepared；
Fig. 6 is the rate diagram of the degradable organic pollutant methyl orange for the material that embodiment 1 is prepared；
Fig. 7 is the photoelectricity flow graph for the material that embodiment 1 is prepared.
Specific embodiment
Invention is further described in detail in the following with reference to the drawings and specific embodiments, but protection scope of the present invention is simultaneously
It is not limited to the content.
Embodiment 1
A kind of high-purity 3R delafossite structure CuFeO2The preparation method of micro crystal material, the specific steps are as follows:
(1) by Cu (NO3)2.3H2O and Fe (NO3)3.9H2O is added in deionized water according to molar ratio 1:1, in magnetic stirring apparatus
15min dissolution is sufficiently stirred, the speed of agitator of magnetic stirring apparatus is 300 turns/min, obtains mixed solution, Cu in mixed solution
(NO3)2Concentration be 0.5mol/L；
(2) NaOH solution is added dropwise in the mixed solution of step (1), the concentration of NaOH solution is 4mol/L, rate of addition
For 1.5mL/min, the amount amount of the substance of NaOH is according to Cu (NO3)2.3H2O and Fe (NO3)3.9H29 times of progress of the amount of O total material
Addition, then successively ultrasound 12min, magnetic agitation 12min, ultrasonic power 350W, the speed of agitator of magnetic stirring apparatus are 450
Turn/min；
(3) it is added dropwise in the solution of step (2) after positive propionic aldehyde and continues magnetic agitation to forming colloidal suspensions, the dropwise addition of positive propionic aldehyde
Speed is 4.5mL/min, and the speed of agitator of magnetic stirring apparatus is 450 turns/min, stirs 12min；The volume of the positive propionic aldehyde of addition
With Cu (NO3)2.3H2O and Fe (NO3)3.9H2The Molar ratio L:mol of the amount of O total material is 2:10；
(4) colloidal suspensions of step (3) are added in reaction kettle, the filling rate of colloidal suspensions is 85%, seals autoclave body postposition
In temperature programmed control baking oven, reaction temperature is set as 180 DEG C, the reaction time is for 24 hours, after reaction, to autoclave body natural cooling
To room temperature, open autoclave body and take out reaction product, reaction product washing successively using deionized water, dust technology, dehydrated alcohol etc. from
The heart cleans 6 times, obtains high-purity 3R delafossite structure CuFeO after then 80 DEG C of dry 10h are dry in constant temperature oven2Crystallite material
Material.
Embodiment 2
A kind of high-purity 3R delafossite structure CuFeO2The preparation method of micro crystal material, the specific steps are as follows:
(1) by Cu (NO3)2.3H2O and Fe (NO3)3.9H2O is added in deionized water according to molar ratio 1:1, in magnetic stirring apparatus
12min dissolution is sufficiently stirred, the speed of agitator of magnetic stirring apparatus is 350 turns/min, obtains mixed solution, Cu in mixed solution
(NO3)2Concentration be 0.6mol/L；
(2) NaOH solution is added dropwise in the mixed solution of step (1), the concentration of NaOH solution is 2mol/L, rate of addition
For 2.5mL/min, the amount of the substance of NaOH is according to Cu (NO3)2.3H2O and Fe (NO3)3.9H26 times of the amount of O total material are added
Adding, then successively ultrasound 15min, magnetic agitation 15min, ultrasonic power 300W, the speed of agitator of magnetic stirring apparatus is 400 turns/
min；
(3) it is added dropwise in the solution of step (2) after positive propionic aldehyde and continues magnetic agitation to forming colloidal suspensions, the dropwise addition of positive propionic aldehyde
Speed is 5mL/min, and the speed of agitator of magnetic stirring apparatus is 500 turns/min, stirs 10min；Addition positive propionic aldehyde volume with
Cu(NO3)2.3H2O and Fe (NO3)3.9H2The Molar ratio L:mol of the amount of O total material is 1.5:10；
(4) colloidal suspensions of step (3) are added in reaction kettle, the filling rate of colloidal suspensions is 85%, seals autoclave body postposition
In temperature programmed control baking oven, reaction temperature is set as 160 DEG C, the reaction time is for 24 hours, after reaction, to autoclave body natural cooling
To room temperature, open autoclave body and take out reaction product, reaction product washing successively using deionized water, dust technology, dehydrated alcohol etc. from
The heart cleans 7 times, obtains high-purity 3R delafossite structure CuFeO after then 70 DEG C of dry 11h are dry in constant temperature oven2Crystallite material
Material.
Embodiment 3
A kind of high-purity 3R delafossite structure CuFeO2The preparation method of micro crystal material, the specific steps are as follows:
(1) by Cu (NO3)2.3H2O and Fe (NO3)3.9H2O is added in deionized water according to molar ratio 1:1, in magnetic stirring apparatus
11min dissolution is sufficiently stirred, the speed of agitator of magnetic stirring apparatus is 400 turns/min, obtains mixed solution, Cu in mixed solution
(NO3)2Concentration be 0.7mol/L；
(2) NaOH solution is added dropwise in the mixed solution of step (1), the concentration of NaOH solution is 3mol/L, rate of addition
For 2mL/min, the amount of the substance of NaOH is according to Cu (NO3)2.3H2O and Fe (NO3)3.9H25 times of the amount of O total material are added
Adding, then successively ultrasound 15min, magnetic agitation 15min, ultrasonic power 300W, the speed of agitator of magnetic stirring apparatus is 400 turns/
min；
(3) it is added dropwise in the solution of step (2) after positive propionic aldehyde and continues magnetic agitation to forming colloidal suspensions, the dropwise addition of positive propionic aldehyde
Speed is 4mL/min, and the speed of agitator of magnetic stirring apparatus is 400 turns/min, stirs 15min；Addition positive propionic aldehyde volume with
Cu(NO3)2.3H2O and Fe (NO3)3.9H2The Molar ratio L:mol of the amount of O total material is 1:10；
(4) colloidal suspensions of step (3) are added in reaction kettle, the filling rate of colloidal suspensions is 85%, seals autoclave body postposition
In temperature programmed control baking oven, reaction temperature is set as 140 DEG C, the reaction time is for 24 hours, after reaction, to autoclave body natural cooling
To room temperature, open autoclave body and take out reaction product, reaction product washing successively using deionized water, dust technology, dehydrated alcohol etc. from
The heart cleans 8 times, obtains high-purity 3R delafossite structure CuFeO after then 80 DEG C of dry 12h are dry in constant temperature oven2Crystallite material
Material.
Embodiment 4
A kind of high-purity 3R delafossite structure CuFeO2The preparation method of micro crystal material, the specific steps are as follows:
(1) by Cu (NO3)2.3H2O and Fe (NO3)3.9H2O is added in deionized water according to molar ratio 1:1, in magnetic stirring apparatus
15min dissolution is sufficiently stirred, the speed of agitator of magnetic stirring apparatus is 300 turns/min, obtains mixed solution, Cu in mixed solution
(NO3)2Concentration be 0.8mol/L；
(2) NaOH solution is added dropwise in the mixed solution of step (1), the concentration of NaOH solution is 2.5mol/L, and speed is added dropwise
Degree is 2mL/min, and the amount of the substance of NaOH is according to Cu (NO3)2.3H2O and Fe (NO3)3.9H28 times of progress of the amount of O total material
Addition, then successively ultrasound 10min, magnetic agitation 10min, ultrasonic power 400W, the speed of agitator of magnetic stirring apparatus are 400
Turn/min；
(3) it is added dropwise in the solution of step (2) after positive propionic aldehyde and continues magnetic agitation to forming colloidal suspensions, the dropwise addition of positive propionic aldehyde
Speed is 5mL/min, and the speed of agitator of magnetic stirring apparatus is 400 turns/min, stirs 10min；Addition positive propionic aldehyde volume with
Cu(NO3)2.3H2O and Fe (NO3)3.9H2The Molar ratio L:mol of the amount of O total material is 2:10；
(4) colloidal suspensions of step (3) are added in reaction kettle, the filling rate of colloidal suspensions is 85%, seals autoclave body postposition
In temperature programmed control baking oven, reaction temperature is set as 120 DEG C, the reaction time is for 24 hours, after reaction, to autoclave body natural cooling
To room temperature, open autoclave body and take out reaction product, reaction product washing successively using deionized water, dust technology, dehydrated alcohol etc. from
The heart cleans 5 times, obtains high-purity 3R delafossite structure CuFeO after then 70 DEG C of dry 11h are dry in constant temperature oven2Crystallite material
Material.
Embodiment 5
A kind of high-purity 3R delafossite structure CuFeO2The preparation method of micro crystal material, the specific steps are as follows:
(1) by Cu (NO3)2.3H2O and Fe (NO3)3.9H2O is added in deionized water according to molar ratio 1:1, in magnetic stirring apparatus
13min dissolution is sufficiently stirred, the speed of agitator of magnetic stirring apparatus is 400 turns/min, obtains mixed solution, Cu in mixed solution
(NO3)2Concentration be 0.7mol/L；
(2) NaOH solution is added dropwise in the mixed solution of step (1), the concentration of NaOH solution is 3.5mol/L, and speed is added dropwise
Degree is 1.5mL/min, and the amount of the substance of NaOH is according to Cu (NO3)2.3H2O and Fe (NO3)3.9H28 times of the amount of O total material into
Row addition, then successively ultrasound 10min, magnetic agitation 10min, ultrasonic power 350W, the speed of agitator of magnetic stirring apparatus are 450
Turn/min；
(3) it is added dropwise in the solution of step (2) after positive propionic aldehyde and continues magnetic agitation to forming colloidal suspensions, the drop of positive propionic aldehyde
Acceleration is 4mL/min, and the speed of agitator of magnetic stirring apparatus is 400 turns/min, stirs 15min；The volume of the positive propionic aldehyde of addition
With Cu (NO3)2.3H2O and Fe (NO3)3.9H2The Molar ratio L:mol of the amount of O total material is 2:10；
(4) colloidal suspensions of step (3) are added in reaction kettle, the filling rate of colloidal suspensions is 85%, seals autoclave body postposition
In temperature programmed control baking oven, reaction temperature is set as 100 DEG C, the reaction time is for 24 hours, after reaction, to autoclave body natural cooling
To room temperature, open autoclave body and take out reaction product, reaction product washing successively using deionized water, dust technology, dehydrated alcohol etc. from
The heart cleans 8 times, obtains high-purity 3R delafossite structure CuFeO after then 60 DEG C of dry 12h are dry in constant temperature oven2Crystallite material
Material.
Embodiment 6
A kind of high-purity 3R delafossite structure CuFeO2The preparation method of micro crystal material, the specific steps are as follows:
(1) by Cu (NO3)2.3H2O and Fe (NO3)3.9H2O is added in deionized water according to molar ratio 1:1, in magnetic stirring apparatus
In 15min dissolution is sufficiently stirred, the speed of agitator of magnetic stirring apparatus is 300 turns/min, obtains mixed solution, Cu in mixed solution
(NO3)2Concentration be 0.8mol/L；
(2) NaOH solution is added dropwise in the mixed solution of step (1), the concentration of NaOH solution is 4mol/L, rate of addition
For 1.5mL/min, the amount of the substance of NaOH is according to Cu (NO3)2.3H2O and Fe (NO3)3.9H210 times of the amount of O total material into
Row addition, then successively ultrasound 15min, magnetic agitation 12min, ultrasonic power 300W, the speed of agitator of magnetic stirring apparatus are 450
Turn/min；
(3) it is added dropwise in the solution of step (2) after positive propionic aldehyde and continues magnetic agitation to forming colloidal suspensions, the dropwise addition of positive propionic aldehyde
Speed is 5mL/min, and the speed of agitator of magnetic stirring apparatus is 500 turns/min, stirs 10min；Addition positive propionic aldehyde volume with
Cu(NO3)2.3H2O and Fe (NO3)3.9H2The Molar ratio L:mol of the amount of O total material is 1:10；
(4) colloidal suspensions of step (3) are added in reaction kettle, the filling rate of colloidal suspensions is 85%, seals autoclave body postposition
In temperature programmed control baking oven, reaction temperature is set as 180 DEG C, reaction time 6h is naturally cooled to autoclave body after reaction
Room temperature opens autoclave body and takes out reaction product, and reaction product washing is successively using the centrifugation such as deionized water, dust technology, dehydrated alcohol
Cleaning 5 times obtains high-purity 3R delafossite structure CuFeO after then 80 DEG C of dry 10h are dry in constant temperature oven2Crystallite material
Material.
Embodiment 7
A kind of high-purity 3R delafossite structure CuFeO2The preparation method of micro crystal material, the specific steps are as follows:
(1) by Cu (NO3)2.3H2O and Fe (NO3)3.9H2O is added in deionized water according to molar ratio 1:1, in magnetic stirring apparatus
In 10min dissolution is sufficiently stirred, the speed of agitator of magnetic stirring apparatus is 400 turns/min, obtains mixed solution, Cu in mixed solution
(NO3)2Concentration be 0.7mol/L；
(2) NaOH solution is added dropwise in the mixed solution of step (1), the concentration of NaOH solution is 1.8mol/L, and speed is added dropwise
Degree is 2.5mL/min, and the amount of the substance of NaOH is according to Cu (NO3)2.3H2O and Fe (NO3)3.9H210 times of the amount of O total material
It is added, then successively ultrasound 10min, magnetic agitation 15min, the speed of agitator of ultrasonic power 400W, magnetic stirring apparatus are
400 turns/min；
(3) it is added dropwise in the solution of step (2) after positive propionic aldehyde and continues magnetic agitation to forming colloidal suspensions, the dropwise addition of positive propionic aldehyde
Speed is 4mL/min, and the speed of agitator of magnetic stirring apparatus is 400 turns/min, stirs 15min；Addition positive propionic aldehyde volume with
Cu(NO3)2.3H2O and Fe (NO3)3.9H2The Molar ratio L:mol of the amount of O total material is 1.5:10；
(4) colloidal suspensions of step (3) are added in reaction kettle, the filling rate of colloidal suspensions is 85%, seals autoclave body postposition
In temperature programmed control baking oven, reaction temperature is set as 180 DEG C, reaction time 12h, after reaction, to autoclave body natural cooling
To room temperature, open autoclave body and take out reaction product, reaction product washing successively using deionized water, dust technology, dehydrated alcohol etc. from
The heart cleans 5 times, obtains high-purity 3R delafossite structure CuFeO after then 60 DEG C of dry 12h are dry in constant temperature oven2Crystallite material
Material.
Embodiment 8
A kind of high-purity 3R delafossite structure CuFeO2The preparation method of micro crystal material, the specific steps are as follows:
(1) by Cu (NO3)2.3H2O and Fe (NO3)3.9H2O is added in deionized water according to molar ratio 1:1, in magnetic stirring apparatus
10min dissolution is sufficiently stirred, the speed of agitator of magnetic stirring apparatus is 400 turns/min, obtains mixed solution, Cu in mixed solution
(NO3)2Concentration be 0.6mol/L；
(2) NaOH solution is added dropwise in the mixed solution of step (1), the concentration of NaOH solution is 3mol/L, rate of addition
For 1.5mL/min, the amount of the substance of NaOH is according to Cu (NO3)2.3H2O and Fe (NO3)3.9H210 times of the amount of O total material into
Row addition, then successively ultrasound 10min, magnetic agitation 10min, ultrasonic power 300W, the speed of agitator of magnetic stirring apparatus are 500
Turn/min；
(3) it is added dropwise in the solution of step (2) after positive propionic aldehyde and continues magnetic agitation to forming colloidal suspensions, the dropwise addition of positive propionic aldehyde
Speed is 5mL/min, and the speed of agitator of magnetic stirring apparatus is 400 turns/min, stirs 15min；Addition positive propionic aldehyde volume with
Cu(NO3)2.3H2O and Fe (NO3)3.9H2The Molar ratio L:mol of the amount of O total material is 2:10；
(4) colloidal suspensions of step (3) are added in reaction kettle, the filling rate of colloidal suspensions is 85%, seals autoclave body postposition
In temperature programmed control baking oven, reaction temperature is set as 180 DEG C, reaction time 18h, after reaction, to autoclave body natural cooling
To room temperature, open autoclave body and take out reaction product, reaction product washing successively using deionized water, dust technology, dehydrated alcohol etc. from
The heart cleans 8 times, obtains high-purity 3R delafossite structure CuFeO after then 70 DEG C of dry 11h are dry in constant temperature oven2Crystallite material
Material.
It is as shown in Figure 1 the X ray diffracting spectrum of the embodiment 1-5 material prepared；Abscissa is angle of diffraction in figure,
Ordinate is relative intensity, it can be seen from the figure that embodiment 1-5 prepares CuFeO2Crystalline material, corresponding standard diffraction
Map number is #75-2146, for the CuFeO with 3R delafossite structure2, material crystalline is good, purity is high.
It is illustrated in figure 2 embodiment 1 and material X ray diffracting spectrum that embodiment 6-8 is prepared；Abscissa is to spread out in figure
Firing angle degree, ordinate are relative intensity, it can be seen from the figure that embodiment 1 and embodiment 7-9 can prepare CuFeO2It is brilliant
Body material, corresponding standard diffraction map number is #75-2146, for the CuFeO with 3R delafossite structure2。
It is illustrated in figure 3 the scanning electron microscope (SEM) photograph for the material that embodiment 1-5 is prepared；It can be seen from the figure that with reaction
CuFeO prepared by the change of temperature2Significant change do not occur for material particle size, about partial size be 2 μm or so sheet knot
Structure, microscopic appearance are mostly hexagonal flake (section is layer structure), meet typical delafossite material crystal structure.
It is illustrated in figure 4 embodiment 1 and the scanning electron microscope (SEM) photograph of material that embodiment 6-8 is prepared；It can be seen from the figure that
CuFeO prepared by change with the reaction time2Significant change does not occur for material particle size, and about partial size is 2 μm or so
Laminated structure, microscopic appearance is mostly hexagonal flake.
It is illustrated in figure 5 the x-ray photoelectron spectroscopy figure (XPS) for the material that embodiment 1 is prepared, wherein figure a is
CuFeO2The full spectrum of material；Scheme two characteristic spectral line Cu-2p that b is Cu2p3/2And Cu-2p1/2, correspond respectively to 932.5eV and
952.4eV, interior illustration are the Auger peak of Cu in 569.3eV, eliminate zeroth order Cu, are shown to be Cu1+；Figure c can be seen that Fe-2p's
Two characteristic spectral line Fe-2p3/2And Fe-2p1/2, 711.2eV and 724.8eV are corresponded respectively to, Fe is shown to be3+；Scheming d is O-2s's
Feature spectral peak, in conjunction with can be respectively in 528.2, tri- 529.8,531.6eV feature locations, this be consistent with document report.
It is illustrated in figure 6 the rate diagram of the degradable organic pollutant methyl orange for the material that embodiment 1 is prepared, it is single
CuFeO2Material is degraded to 0 to methyl orange in 600min under conditions of no light；Embodiment 1 is prepared
CuFeO2-H2O2System has 10% degradation in 600min to organic pollutant methyl orange；Embodiment 1 is prepared
CuFeO2- H2O2Illumination system has 93% to organic pollutant methyl orange in 600min under the Xenon light shining of 300W
Degradation；In entire degradation process, when illumination is mapped to CuFeO2On material, CuFeO2Material internal generates photo-generate electron-hole pairs,
H2O2The role for serving as electronics sacrifice agent, after light induced electron is captured, remaining photohole is transferred to CuFeO2Material surface oxygen
Change methyl orange, is decomposed.
If Fig. 7 is the photoelectricity flow graph of material that embodiment 1 is prepared, it can be seen from fig 7a that CuFeO2Material has
Preferable photoelectric converting function, can effective hydrogen production by water decomposition, as Fig. 7 b further demonstrates that CuFeO2Material turns as photoelectricity
Conversion materials have preferable stability.
Claims (10)
1. a kind of high-purity 3R delafossite structure CuFeO2The preparation method of micro crystal material, which is characterized in that specific step is as follows:
(1) by Cu (NO3)2.3H2O and Fe (NO3)3.9H2O is added in deionized water according to molar ratio 1:1, magnetic agitation dissolution,
Obtain mixed solution；
(2) NaOH solution is added dropwise dropwise in the mixed solution of step (1), then successively ultrasound, magnetic agitation；
(3) it is added dropwise in the solution of step (2) after positive propionic aldehyde and continues magnetic agitation to forming colloidal suspensions；
(4) colloidal suspensions of step (3) are added in reaction kettle, the filling rate of colloidal suspensions is 85%, after sealing autoclave body
100~180 DEG C of reactions 6~for 24 hours, after reaction, to autoclave body cooled to room temperature, opens autoclave body and take out reaction product, instead
High-purity 3R delafossite structure CuFeO is obtained after answering product washing dry2Micro crystal material.
2. high-purity 3R delafossite structure CuFeO according to claim 12The preparation method of micro crystal material, which is characterized in that
Cu (NO in step (1) mixed solution3)2Concentration be 0.5~0.8mol/L.
3. high-purity 3R delafossite structure CuFeO according to claim 12The preparation method of micro crystal material, which is characterized in that
Step (1) magnetic agitation rotating speed is 300~400 turns/min, stirs 10~15min.
4. high-purity 3R delafossite structure CuFeO according to claim 12The preparation method of micro crystal material, which is characterized in that
Step (2) NaOH solution is Cu (NO according to NaOH3)2.3H2O and Fe (NO3)3.9H24~10 times of the amount of O total material are added
Add.
5. high-purity 3R delafossite structure CuFeO according to claim 12The preparation method of micro crystal material, which is characterized in that
The concentration of step (2) NaOH solution is 1.5~4mol/L, and rate of addition is 1.5~2.5mL/min.
6. high-purity 3R delafossite structure CuFeO according to claim 12The preparation method of micro crystal material, which is characterized in that
Step (2) ultrasonic power is 300~400W, 10~15min of ultrasound.
7. high-purity 3R delafossite structure CuFeO according to claim 12The preparation method of micro crystal material, which is characterized in that
Step (2) and step (3) magnetic agitation rotating speed are 400~500 turns/min, stir 10~15min.
8. high-purity 3R delafossite structure CuFeO according to claim 12The preparation method of micro crystal material, which is characterized in that
The rate of addition of the positive propionic aldehyde of step (3) is 4~5mL/min, the volume and Cu (NO of the positive propionic aldehyde of addition3)2.3H2O and Fe
(NO3)3.9H2The Molar ratio L:mol of the amount of O total material is 1~2:10.
9. high-purity 3R delafossite structure CuFeO according to claim 12The preparation method of micro crystal material, which is characterized in that
Step (4) washing is successively using deionized water, dust technology, dehydrated alcohol etc. eccentric cleanings 5~8 times.
10. high-purity 3R delafossite structure CuFeO according to claim 12The preparation method of micro crystal material, which is characterized in that
Step (4) drying is in 60~80 DEG C of dry 10~12h.
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