CN103880081B - A kind of delafossite structure AgCrO 2the preparation method of nanocrystalline material - Google Patents

A kind of delafossite structure AgCrO 2the preparation method of nanocrystalline material Download PDF

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CN103880081B
CN103880081B CN201410120837.XA CN201410120837A CN103880081B CN 103880081 B CN103880081 B CN 103880081B CN 201410120837 A CN201410120837 A CN 201410120837A CN 103880081 B CN103880081 B CN 103880081B
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agcro
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nanocrystalline material
hydrothermal
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熊德华
李宏
田守勤
陶海征
赵修建
常海梅
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Wuhan University of Technology WUT
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    • 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
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Abstract

Delafossite structure AgCrO disclosed by the invention 2the preparation method of nanocrystalline material is that one prepares delafossite structure AgCrO fast 2the low-temperature hydro-thermal synthesis of nanocrystalline material, it utilizes low-temperature hydrothermal to react, regulation and control comprise the filling ratio parameter of reaction solution in precursors component, temperature of reaction and hydrothermal reaction kettle, react 36 ~ 60 hours at 190 ~ 230 DEG C, by reaction product after repeatedly eccentric cleaning process, in vacuum drying oven, 60 DEG C of dryings 24 ~ 48 hours, finally obtain the AgCrO of 10 ~ 20nm size 2nanocrystalline material.Present method is simple to operate, and processing parameter is easy to control, pollution-free, productive rate is high, can be widely used in the photoelectric functional devices such as transparent conductive oxide.

Description

A kind of delafossite structure AgCrO 2the preparation method of nanocrystalline material
Technical field
The present invention relates to nano material synthesis preparation field, particularly utilize hydrothermal method to synthesize preparation AgCrO at a lower temperature 2nanocrystalline material.
Background technology
1997, the people such as Tokyo polytechnical university professor Hosono reported first based on chemical valence band modification Design Theory and prepare delafossite (ABO on Nature 2) the intrinsically p-type CuAlO of structure 2film.By CuAlO 2the inspiration of chemical design thought, series A BO 2structural semiconductor material (A=Cu or Ag; B=Al, Ga, In, Sc, Y, Cr, Co or La etc.) become the primary study perpetual object of p-type TCO.But, at present about ABO 2the research report of material focuses mostly in p-type dense film, and nano level ABO 2the report of crystalline material is considerably less, limits ABO 2material is as the application of mesoporous photocathode thin-film material in photoelectrochemistry fields such as dye-sensitized solar cells.
With common to utilize high-temperature solid phase reaction method to prepare Cu base delafossite structure material different, due to Ag 2o thermostability poor (~ 300 DEG C), causes being difficult to by high-temperature solid phase reaction method synthesizing series Ag base delafossite structure material.So, the series A g base ABO reported 2material (A=Ag, B=In, Al, Ga, Cr etc.) adopts ion exchange reaction method, hydro-thermal reaction legal system standby more.Ion exchange reaction method generally can in two steps, but the method temperature of reaction is high, long reaction time, particle size large (~ 200nm).As adopted exchange of particles legal system for AgCrO 2time, present about 650 ~ 800 DEG C sintering of general requirement 12 hours preparation LiCrO 2, and then ion exchange reaction is utilized 12 hours under 320 DEG C of degree, just can prepare AgCrO 2material.In addition, hydrothermal method reaction is very complicated, reaction conditions is more responsive, such as reactant presoma component, pH value, quality, reaction times, temperature, pressure, additive etc. all can produce a very large impact reaction product pattern, thing phase, size, causes the optimising and adjustment of hydrothermal reaction condition more difficult.The hydro-thermal reaction that utilizes as reported is reacted 12 hours under the extreme severe condition of 400 DEG C of-40MPa, the AgCrO prepared 2scantling about 2 μm.At present, although can by a step hydrothermal synthesis reaction method at a lower temperature (210 DEG C) prepare series A g base ABO 2material is (as AgAlO 2), but also do not find to prepare nano level Ag base ABO about hydrothermal method 2any relevant report of material.
In view of the Ag base ABO reported at present 2material crystals size is comparatively large, reaches nanoscale far away, makes to fail to find full expression to the nano effect of the crystalline structure of material, pattern, PhotoelectrochemicalProperties Properties that size is relevant.So be badly in need of stepping up to carry out nano level Ag base ABO 2the fundamental research of structural semiconductor material and preparation technology's exploitation, grasp its characteristic of semiconductor of regulation and control, to be applicable in various novel photoelectric functional device comprehensively.
Summary of the invention
Technical problem to be solved by this invention is: provide one to prepare delafossite structure AgCrO fast 2the low-temperature hydro-thermal synthesis of material, to prepare nano level AgCrO 2crystalline material.
The present invention solves its technical problem and adopts following technical scheme:
Delafossite structure AgCrO provided by the invention 2the preparation method of nanocrystalline material is that one prepares delafossite structure AgCrO fast 2the low-temperature hydro-thermal synthesis of nanocrystalline material, it utilizes low-temperature hydrothermal to react, regulation and control comprise the filling ratio parameter of reaction solution in precursors component, temperature of reaction and hydrothermal reaction kettle, react at 190 ~ 230 DEG C after 36 ~ 60 hours, by reaction product through repeatedly eccentric cleaning process, obtain nano level AgCrO 2crystalline material.
Described precursors can be AgNO 3with Cr (NO 3) 3the aqueous solution, or other are containing Ag +and Cr 3+compound, as Ag 2o, CrCl 3deng.
Described precursors can be made up of following method: first at room temperature by AgNO 3with Cr (NO 3) 3add in deionized water according to mol ratio 0.9 ~ 1.1:1, after the abundant stirring and dissolving of magnetic stirring apparatus; The NaOH adding 3 ~ 5 times of molar weights is again as mineralizer, stand-by after being stirred well to dissolving completely.
Described regulation and control filling ratio, refers to that the filling ratio of adjusting hydrothermal reaction kettle for reaction liquid can be 65 ~ 75%.
Described eccentric cleaning process, its method can be: adopt deionized water, rare HNO successively 3, rare NH 3h 2the secondary ordered pair reaction product of O, dehydrated alcohol carries out eccentric cleaning; This order also can adjust according to processing requirement, as adopted deionized water, rare NH successively 3h 2o, rare HNO 3, dehydrated alcohol cleaning order.
Delafossite structure AgCrO prepared by aforesaid method provided by the invention 2nanocrystalline material, its purposes is: the application in the photoelectric functional device of transparent conductive oxide.
The photoelectric functional device of described transparent conductive oxide can refer to dye-sensitized solar cells or photoelectrochemical cell.
The present invention utilizes hydrothermal synthesis reaction, at a lower temperature (190 DEG C) by single step reaction legal system standby go out nano level AgCrO 2crystalline material.Develop a kind of AgCrO first 2the fast preparation method of nanocrystalline material high yield, low cost, for promotion delafossite structure p-type semiconductor material and the application development at field of photoelectric devices thereof, all has very important learning value.
Compared with prior art, its unusual effect mainly contains in the present invention: prepare nano level AgCrO first 2crystalline material, has filled up the research both at home and abroad about nanometer Ag base delafossite structure semiconductor material blank.
The present invention mainly contains following feature:
(1) the method preparation technology is simple, processing parameter easily controls, experimental repeatability good, single output is high.
(2) the reaction raw material sources of the method use is extensive, and all reactants are all inorganics, and cheap, production cost is low.
(3) when temperature of reaction is 190 ~ 230 DEG C, all AgCrO can be obtained 2crystalline material (as Fig. 1).Along with temperature of reaction be reduced to 190 DEG C from 230 DEG C time, nanocrystalline size from 20 ~ 50nm(as Fig. 2) be reduced to 10 ~ 20nm(as Fig. 3).
Accompanying drawing explanation
The reaction product X ray diffracting spectrum of Fig. 1 prepared by embodiment 1,2,3; In figure, X-coordinate is angle of diffraction, and ordinate zou is relative intensity.As can be seen from the figure, when temperature of reaction is 190 ~ 230 DEG C, all CuCrO can be prepared 2crystalline material, corresponding standard diffraction collection of illustrative plates is numbered 70-1703.Each diffraction peak intensity is more weak, and peak position halfwidth is comparatively large, and hint gained reaction product is nanometer scale crystalline material.
The AgCrO of Fig. 2 prepared by embodiment 1 2nanocrystalline transmission electron microscope picture.When temperature of reaction is 230 DEG C, utilize transmission electron microscope to reaction product observation shooting microscopic appearance photo.As can be seen from the figure, prepared CuCrO 2material crystals size about 20 ~ 50nm, microscopic appearance is hexagonal flake (cross section is laminate structure), meets typical delafossite material crystal structure.
The AgCrO of Fig. 3 prepared by embodiment 3 2nanocrystalline transmission electron microscope picture.When temperature of reaction is 190 DEG C, utilize transmission electron microscope to reaction product observation shooting microscopic appearance photo.As can be seen from the figure, prepared CuCrO 2material crystals size about 10 ~ 20nm, microscopic appearance is hexagonal flake.
The AgCrO of Fig. 4 prepared by embodiment 4 2nanocrystalline EDS power spectrum Surface scan test result, Si derives from sample preparation and uses at the bottom of silicon wafer-based, and Pt derives from sample preparation spray platinum plated film, and the X-ray energy spectrum analysis utilizing field emission scanning electron microscope subsidiary is tested its composition.As can be seen from the figure: nanocrystalline material has Ag, Cr, O tri-kinds elementary composition; Wherein Ag:Cr=0.88:1 is close to Ag/Cr=0.9 in initial reactant.
Embodiment
The pharmaceutical chemicals that hydro-thermal reaction presoma of the present invention uses, mainly comprises AgNO 3, Cr (NO 3) 3, NaOH, dehydrated alcohol, HNO 3, NH 3h 2o and deionized water etc.First prepare precursors, then transfer in hydrothermal reaction kettle, after sealing, be incubated for some time under specified temp in an oven.After question response still naturally cooling, take out reaction product, 60 DEG C of dryings 24 ~ 48 hours, finally obtain the AgCrO of 10 ~ 20nm size through repeatedly eccentric cleaning process and in vacuum drying oven 2nanocrystalline material.
Below in conjunction with specific embodiment and accompanying drawing, the invention will be further described, but be not limited to described content below.
Embodiment 1:
At room temperature according to Ag:Cr mol ratio be 0.9 ~ 1.1:1 weigh AgNO 3with Cr (NO 3) 3after, add through magnetic stirrer about 10 ~ 15 minutes in deionized water, until completely dissolved, then added the NaOH of 4 times of molar weights of mineralizer effect, continuing stirring about 10 ~ 15 minutes to dissolving completely, forming hydro-thermal reaction presoma.Above-mentioned precursors is transferred in hydrothermal reaction kettle and (is generally tetrafluoroethylene), control reaction solution filling ratio about 65%.Sealing kettle is placed in temperature programmed control baking oven and carries out hydro-thermal reaction, and setting temperature of reaction is 230 DEG C, and the reaction times is 36 ~ 60 hours.
After reaction terminates, treat that kettle naturally cools to room temperature, open kettle and take out reaction product.Use deionized water, rare HNO successively 3, rare NH 3h 2for several times, finally 60 DEG C of insulations drying in 24 ~ 48 hours in vacuum drying oven, can obtain AgCrO to the eccentric cleaning such as O, deionized water, dehydrated alcohol 2nanocrystalline.
Embodiment 2:
At room temperature according to Ag:Cr mol ratio be 1:1 weigh AgNO 3with Cr (NO 3) 3after, add through magnetic stirrer about 10 ~ 15 minutes in deionized water, until completely dissolved, then added the NaOH of 4 times of molar weights of mineralizer effect, continuing stirring about 10 ~ 15 minutes to dissolving completely, forming hydro-thermal reaction presoma.
Above-mentioned precursors is transferred in hydrothermal reaction kettle and (is generally tetrafluoroethylene), control reaction solution filling ratio about 65 ~ 75%.Sealing kettle is placed in temperature programmed control baking oven and carries out hydro-thermal reaction, and setting temperature of reaction is 210 DEG C, and the reaction times is 36 ~ 60 hours.
After reaction terminates, treat that kettle naturally cools to room temperature, open kettle and take out reaction product.Use deionized water, rare HNO successively 3, rare NH 3h 2for several times, finally 60 DEG C of insulations drying in 24 ~ 48 hours in vacuum drying oven, can obtain AgCrO to the eccentric cleaning such as O, deionized water, dehydrated alcohol 2nanocrystalline.
Embodiment 3:
At room temperature according to Ag:Cr mol ratio be 1:1 weigh AgNO 3with Cr (NO 3) 3after, add through magnetic stirrer about 10 ~ 15 minutes in deionized water, until completely dissolved, then added the NaOH of 3 times of molar weights of mineralizer effect, continuing stirring about 10 ~ 15 minutes to dissolving completely, forming hydro-thermal reaction presoma.
Above-mentioned precursors is transferred in hydrothermal reaction kettle and (is generally tetrafluoroethylene), control reaction solution filling ratio about 70%.Sealing kettle is placed in temperature programmed control baking oven and carries out hydro-thermal reaction, and setting temperature of reaction is 190 DEG C, and the reaction times is 36 ~ 60 hours.
After reaction terminates, treat that kettle naturally cools to room temperature, open kettle and take out reaction product.Use deionized water, rare HNO successively 3, rare NH 3h 2for several times, finally 60 DEG C of insulations drying in 24 ~ 48 hours in vacuum drying oven, can obtain AgCrO to the eccentric cleaning such as O, deionized water, dehydrated alcohol 2nanocrystalline.
Embodiment 4:
At room temperature according to Ag:Cr mol ratio be 0.9:1 weigh AgNO 3with Cr (NO 3) 3after, add through magnetic stirrer about 10 ~ 15 minutes in deionized water, until completely dissolved, then added the NaOH of 5 times of molar weights of mineralizer effect, continuing stirring about 10 ~ 15 minutes to dissolving completely, forming hydro-thermal reaction presoma.
Above-mentioned precursors is transferred in hydrothermal reaction kettle and (is generally tetrafluoroethylene), control reaction solution filling ratio about 75%.Sealing kettle is placed in temperature programmed control baking oven and carries out hydro-thermal reaction, and setting temperature of reaction is 190 DEG C, and the reaction times is 36 ~ 60 hours.
After reaction terminates, treat that kettle naturally cools to room temperature, open kettle and take out reaction product.Use deionized water, rare HNO successively 3, rare NH 3h 2for several times, finally 60 DEG C of insulations drying in 24 ~ 48 hours in vacuum drying oven, can obtain AgCrO to the eccentric cleaning such as O, deionized water, dehydrated alcohol 2nanocrystalline.
Obviously, those skilled in the art can to the AgCrO of delafossite structure of the present invention 2the hydrothermal preparing process of nanocrystalline material and nanocrystalline material thereof carry out various change and modification and do not depart from the spirit and scope of the present invention.Like this, if belong within claim of the present invention and equivalent technical scope thereof to these amendments of the present invention and modification, then the present invention is also intended to comprise these change and modification.

Claims (2)

1. a delafossite structure AgCrO 2the preparation method of nanocrystalline material, is characterized in that one prepares delafossite structure AgCrO fast 2the low-temperature hydro-thermal synthesis of nanocrystalline material, it utilizes low-temperature hydrothermal to react, regulation and control comprise the filling ratio parameter of reaction solution in precursors component, temperature of reaction and hydrothermal reaction kettle, react at 190 ~ 230 DEG C after 36 ~ 60 hours, by reaction product through repeatedly eccentric cleaning process, obtain nano level AgCrO 2crystalline material; Described precursors is made up of following method: first at room temperature by AgNO 3with Cr (NO 3) 3add in deionized water according to mol ratio 0.9 ~ 1.1:1, after the abundant stirring and dissolving of magnetic stirring apparatus; The NaOH adding 3 ~ 5 times of molar weights is again as mineralizer, stand-by after being stirred well to dissolving completely; The filling ratio of adjusting hydrothermal reaction kettle for reaction liquid is 65 ~ 75%.
2. delafossite structure AgCrO according to claim 1 2the preparation method of nanocrystalline material, is characterized in that: adopt deionized water, rare HNO successively 3, rare NH 3h 2the secondary ordered pair reaction product of O, dehydrated alcohol carries out eccentric cleaning.
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* Cited by examiner, † Cited by third party
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CN104058461B (en) * 2014-07-04 2016-07-06 武汉理工大学 A kind of delafossite structure CuFeO2The low temperature preparation method of crystalline material
DE102015117277A1 (en) * 2015-10-09 2017-04-13 Soraya Heuss-Aßbichler Process for preparing an inorganic compound of the general formula AXO2
CN107098401B (en) * 2017-06-02 2018-11-30 武汉理工大学 A kind of delafossite structure CuCoO2Crystalline material and its low temperature preparation method
CN108680609B (en) * 2018-03-15 2021-02-09 中国科学院合肥物质科学研究院 Room-temperature ammonia gas sensor taking p-type delafossite structure oxide as sensitive material and preparation method thereof
CN110980791B (en) * 2019-12-05 2021-05-11 武汉理工大学 P type delafossite structure CuScO2Crystalline material, method for the production thereof and use thereof
CN114160065B (en) * 2021-11-17 2024-02-13 昆明理工大学 Preparation method of crystalline phase controllable delafossite AgFeO2 powder material

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Sanjay Kumar et al..Hydrothermal Synthesis of AgCrO2 Delafossite in Supercritical Water:A New Single-Step Process.《Chem. Mater.》.2013,第25卷第2083-2088页. *
Yu Liu et al..Microwave hydrothermal synthesis of Ag2CrO4 photocatalyst for fast degradation of PCP-Na under visible light irradiation.《Catalysis Communications》.2012,第26卷第63-67页. *

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