CN104250022A - Mixed valence vanadium oxide nano material and preparation method thereof - Google Patents

Mixed valence vanadium oxide nano material and preparation method thereof Download PDF

Info

Publication number
CN104250022A
CN104250022A CN201310268704.2A CN201310268704A CN104250022A CN 104250022 A CN104250022 A CN 104250022A CN 201310268704 A CN201310268704 A CN 201310268704A CN 104250022 A CN104250022 A CN 104250022A
Authority
CN
China
Prior art keywords
mixed
solution
vanadium oxide
temperature
oxide nano
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
Application number
CN201310268704.2A
Other languages
Chinese (zh)
Other versions
CN104250022B (en
Inventor
王峰
张超锋
徐杰
张晓辰
王业红
张哲�
王敏
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dalian Institute of Chemical Physics of CAS
Original Assignee
Dalian Institute of Chemical Physics of CAS
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Dalian Institute of Chemical Physics of CAS filed Critical Dalian Institute of Chemical Physics of CAS
Priority to CN201310268704.2A priority Critical patent/CN104250022B/en
Publication of CN104250022A publication Critical patent/CN104250022A/en
Application granted granted Critical
Publication of CN104250022B publication Critical patent/CN104250022B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Landscapes

  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

The invention relates to a preparation method of a mixed valence vanadium oxide nano material, and the method is as follows: a compound containing VO<2 +> is dispersed and dissolved in deionized water to form an A liquid, a compound containing VO<3-> is dispersed and dissolved in the deionized water to form a B liquid, according to the molar ratio of VO<2 +> and VO<3-> of 1:1.4-1:2.4, in different concentration, the A liquid and the B liquid are mixed at 10 to 160 DEG C, and added into a synthesis reactor, closed, then heated to 60-200 DEG C in the heating rate of 1 to 20 DEG C / min, and stood for 2-180h. After the crystallization is completed, the precipitate is separated, washed and dried to obtain the mixed valence vanadium oxide nano material. The mixed valence vanadium oxide nano material has good thermal stability, water resistance and large specific surface area, has a layered structure in the crystal structure, namely a one-dimensional nano rod structure, and has potential application in areas such as catalysis, electrodes, sensors, capacitors, lithium battery negative and positive poles, and the like.

Description

A kind of mixed valence vanadium oxide nano material and preparation method thereof
Technical field
The invention belongs to field of material synthesis technology, be specifically related to a kind of preparation method of mixed valence vanadium oxide nano material.
Background technology
Vanadium is the transition metal that in the earth's crust, content is more, and vanadium oxide material is in catalysis, and electrode, sensor, has important purposes in electrode material of lithium battery.Compound common for vanadium oxide material is the compound of homogeneous valence state, as V 2o 3, VO 2, V 2o 5, barium oxide is a very complicated system in fact, except the barium oxide of these homogeneous valence states, also has the barium oxide of a lot of mixed valences.As catalyzer, electrode material, sensor material aspect, the barium oxide of homogeneous valence state of comparing, mixed valence can show more excellent performance in some cases.
Synthesis about mixed valence vanadium oxide material: the people such as A.M.Chippindal (J.Mater.Chem.1992,2,601-608.) adopt the method for mixing two kinds of unit price state vanadium oxide solid phase high―temperature nuclei, and reaction formula is: 5V 2o 5+ V 2o 3→ 4V 3o 7, synthesized V 3o 7material.The method needs to experience high temperature reduction in building-up process, and high vacuum mixes, the program that high―temperature nuclei etc. are complicated.The people such as H.Qiao (Electrochem.Commun.2006,8,21-26.) are by long-time at high temperature hydrothermal treatment consists V 2o 5obtain a kind of barium oxide of mixed valence, but find from XRD figure spectrum or have a lot of assorted peaks.Y.F.Zhang, waits people (Ceram.Int.2013,39,129-141.) by long-time at high temperature hydrothermal treatment consists V 2o 5a kind of barium oxide of mixed valence is obtained with hydrogen peroxide.The people such as G.Wang (Acs Nano2012,6,10296-10302.) are by long-time at high temperature hydrothermal treatment consists V 2o 5a kind of H of mixed valence is obtained with HCl 2v 3o 8material.The people such as K.H.Chang (Acta.Mater.2007,55,6192-6197.) are by using H 2o 2partial oxidation VO 2+method Hydrothermal Synthesis V 3o 7h 2o.
Correlative study finds that mixed valence oxyvanadium compound material is as catalysis, there is good advantage electrode materials aspect, but mostly the method for synthesis is solid phase pyroreaction, or at high temperature hydro-thermal Some redox or partial reduction vanadium species, because the speed that hydrolysis of usually can not controlling well grows with crystal nucleation, the material obtained is mostly not too pure, and shape irregularity heterogeneity, be mostly more difficult to get nanometer materials.
Material structure determines the performance of material, and therefore, exploitation is reliably a kind of, and the synthetic method of the mixed valence vanadium oxide material of structure-controllable has great importance.This type of material, may as catalysis because the performance of its uniqueness, and electrode, electric capacity, sensor, photosensitive, temperature-sensitive, electrode material of lithium battery aspect has potential application.
Summary of the invention
The invention reside in the preparation method providing a kind of mixed valence vanadium oxide material, this material has Heat stability is good, water-fast, specific surface area is large, and crystalline structure has laminate structure, the features such as the bar-shaped structure of 1-dimention nano, be applicable to catalysis, electrode, photosensitive, electric capacity, the materials such as lithium cell cathode and anode.
Technical scheme of the present invention is: will containing VO 2+(VOSO 4, VOC 2o 4, VOCl 2, vanadyl acetylacetonate etc.) and compound dispersing and dissolving forms A liquid, by the compound (NaVO containing metavanadic acid root in deionized water 3, NH 4vO 3, KVO 3) dispersing and dissolving forms B liquid, according to V in deionized water water 4+with V 5+the ratio of molar ratio 1:1.4:2-1:2.4, under different concentration, at 10-160 DEG C by above-mentioned two kinds of solution mixing, and then by the speed of different heat-up rate 1-10 DEG C/min, mixed solution is risen to the crystallization temperature of 80-200 DEG C, standing 2-180h in synthesis reactor.By throw out separation, washing, dry this mixed valence vanadium oxide material obtained.This mixed valence vanadium oxide particle is better than bibliographical information dimensionally, and is a nano bar-shape material.The preparation principle of this material is: by controlling the pH value of metavanadic acid root solution, concentration, temperature controls vanadic acid root form in the solution, interact with vanadium oxygen quadrivalent ion again, changed and crystallization temperature by control temperature, be controlled to crystalline nucleation speed and hydrolysis rate, period thus obtain a nano bar-shape material.
The selection of pentavalent vanadium acid group compound has important impact for synthetic materials.Different vanadic acid roots is under different concentration, and different pH value, has different forms at temperature, and the crystalline structure pattern for the material of synthesis has very important impact.Such vanadic acid radical compound can be sodium metavanadate, ammonium meta-vanadate, potassium metavanadate, sodium orthovanadate, ortho-vanadic acid potassium, sodium pyrovanadate, one or more in pyrovanadic acid ammonium, preferably vanadic acid compound is: sodium metavanadate, potassium metavanadate, ammonium meta-vanadate, one or more in sodium orthovanadate, best pentavalent vanadium acid group compound is: sodium metavanadate, one or more in ammonium meta-vanadate.
The selection of the oxygen ionized compound of tetravalence vanadium has important impact to synthetic materials.The acidity of the different oxygen ionized compounds of tetravalence vanadium is different, and the stability of ion is different, and the form of existence is also different, and certain degree can have influence on crystal growth and the morphology control of mixed valence vanadium oxide material.This tetravalence vanadium oxonium ion can be vanadylic sulfate, vanadyl chloride, vanadyl oxalate, vanadyl acetylacetonate, one or more in ethylenediamine tetraacetic acid (EDTA) vanadyl, preferably the oxygen ionized compound of tetravalence vanadium is: vanadylic sulfate, vanadyl acetylacetonate, one or more in ethylenediamine tetraacetic acid (EDTA) vanadyl, the best oxygen ionized compound of tetravalence vanadium is: vanadylic sulfate, one or more in vanadyl acetylacetonate.
Except selecting the pentavalent vanadium acid group compound of proper fit, the oxygen ionized compound of tetravalence vanadium, the key of materials synthesis is also the molar ratio of the concentration of reasonable adjusting synthesis temperature, mother liquor, pentavalent vanadium acid group compound and the oxygen ionized compound of tetravalence vanadium, reaction times, dwell temperature and time etc.The mixing temperature be applicable to is 0 DEG C-160 DEG C, and preferably mixing temperature is 10 DEG C-80 DEG C, and best mixing temperature is 20 DEG C-30 DEG C.
The concentration of the mother liquor be applicable to is: VO 2+: 0.008-1.0mol/L, VO 3 -for 0.014-2.4mol/L.Preferably mother liquid concentration is: VO 2+: 0.008-0.5mol/L, VO 3 -for 0.014-0.24mol/L.Best mother liquid concentration is: VO 2+: 0.008-0.1mol/L, VO 3 -for 0.018-0.24mol/L.The VO be applicable to 2+/ VO 3 -molar ratio be 1:1.4-1:2.4, preferably VO 2+/ VO 3 -molar ratio be: 1:1.6-1:2.4, best VO 2+/ VO 3 -molar ratio be: 1:1.8-1:2.4.The reaction times be applicable to is: 0.1h-2h, and preferably the reaction times is: 0.1h-0.5h, and the best reaction times is: 0.1h-0.3h.The dwell temperature be applicable to is: 0 DEG C-200 DEG C, preferably dwell temperature is: 20 DEG C-160 DEG C, and best dwell temperature is: 80 DEG C-160 DEG C.The time of repose be applicable to is: 2h-360h, and preferably time of repose is: 2h-240h, and best time of repose is: 8h-72h.
The present invention relates to a kind of preparation method of mixed valence vanadium oxide material, advantage be synthesize this material has Heat stability is good, water-fast, specific surface area is large, and crystalline structure has laminate structure, the bar-shaped structure of 1-dimention nano, size can be controlled in length 600-1600nm, width is at 80-100nm, and thickness is at 20nm, and this preparation method is simple, synthesis controls easily.The aspects such as the material that obtains can be used as catalysis, electrode, sensor, electric capacity, lithium cell cathode and anode.
Embodiment:
In order to be further elaborated to the present invention, provide several concrete case study on implementation below, but the invention is not restricted to these embodiments.
Embodiment 1:
The VOSO of configuration 0.12mol/L 4the NaVO of solution and 0.20mol/L 3two kinds of solution, by two constant-flux pumps, are mixed with the mixed pipe line of the speed of 10mL/min at 25 DEG C by each 125mL of solution, mixed solution proceeds in the synthesis reactor of 350mL, put into the baking oven that initial temperature is 25 DEG C, rise to static temperature 160 DEG C with the heat-up rate of 10 DEG C/min, leave standstill 72h.After having synthesized, through filtering, deionized water wash vacuum-drying obtains the vanadium oxide nano-particle material of mixed valence.Adopt TG-DTA means to characterize to learn: under nitrogen atmosphere, this material can be stablized to 380 DEG C; Nitrogen adsorption detachment assays shows that this material specific surface is 80m 2/ g.
Embodiment 2:
The VOSO of configuration 0.01mol/L 4the NaVO of solution and 0.02mol/L 3two kinds of solution, by two constant-flux pumps, are mixed with the mixed pipe line of the speed of 10mL/min at 25 DEG C by each 125mL of solution, mixed solution proceeds in the synthesis reactor of 350mL, put into the baking oven that initial temperature is 25 DEG C, rise to static temperature 160 DEG C with the heat-up rate of 10 DEG C/min, leave standstill 48h.After having synthesized, through filtering, deionized water wash vacuum-drying obtains mixed valence vanadium oxide nano-particle material.Adopt TG-DTA means to characterize to learn: under nitrogen atmosphere, this material can be stablized to 380 DEG C; Nitrogen adsorption detachment assays shows that this material specific surface is 56m 2/ g.
Embodiment 3:
The VOSO of configuration 0.009mol/L 4the NaVO of solution and 0.02mol/L 3the each 125mL of solution, by two constant-flux pumps, mixed by two kinds of solution with the mixed pipe line of the speed of 10mL/min at 80 DEG C, mixed solution proceeds in the synthesis reactor of 350mL, puts into the baking oven that initial temperature is 80 DEG C, leaves standstill 72h.After having synthesized, through filtering, deionized water wash vacuum-drying obtains mixed valence vanadium oxide nano-particle material.Adopt TG-DTA means to characterize to learn: under nitrogen atmosphere, this material can be stablized to 350 DEG C; Nitrogen adsorption detachment assays shows that this material specific surface is 90m 2/ g.
Embodiment 4:
The VOSO of configuration 0.12mol/L 4the NaVO of solution and 0.02mol/L 3two kinds of solution, by two constant-flux pumps, are mixed with the mixed pipe line of the speed of 10mL/min at 80 DEG C by each 125mL of solution, mixed solution proceeds in the synthesis reactor of 350mL, put into the baking oven that initial temperature is 80 DEG C, rise to static temperature 160 DEG C with the heat-up rate of 10 DEG C/min, leave standstill 24h.After having synthesized, through filtering, deionized water wash vacuum-drying obtains mixed valence vanadium oxide nano-particle material.Adopt TG-DTA means to characterize to learn: under nitrogen atmosphere, this material can be stablized to 380 DEG C; Nitrogen adsorption detachment assays shows that this material specific surface is 40m 2/ g.
Embodiment 5:
The VOSO of configuration 0.014mol/L 4the NaVO of solution and 0.02mol/L 3two kinds of solution, by two constant-flux pumps, are mixed with the mixed pipe line of the speed of 10mL/min at 25 DEG C by each 125mL of solution, mixed solution proceeds in the synthesis reactor of 350mL, put into the baking oven that initial temperature is 25 DEG C, rise to static temperature 160 DEG C with the heat-up rate of 10 DEG C/min, leave standstill 72h.After having synthesized, through filtering, deionized water wash vacuum-drying obtains the barium oxide nano-particle material of mixed valence.Adopt TG-DTA means to characterize to learn: under nitrogen atmosphere, this material can be stablized to 350 DEG C; Nitrogen adsorption detachment assays shows that this material specific surface is 79m 2/ g.
Embodiment 6:
The VOSO of configuration 0.011mol/L 4the NaVO of solution and 0.02mol/L 3two kinds of solution, by two constant-flux pumps, are mixed with the mixed pipe line of the speed of 10mL/min at 10 DEG C by each 125mL of solution, mixed solution proceeds in the synthesis reactor of 350mL, put into the baking oven that initial temperature is 25 DEG C, rise to static temperature 120 DEG C with the heat-up rate of 10 DEG C/min, leave standstill 72h.After having synthesized, through filtering, deionized water wash vacuum-drying obtains mixed valence vanadium oxide nano-particle material.Adopt TG-DTA means to characterize to learn: under nitrogen atmosphere, this material can be stablized to 380 DEG C; Nitrogen adsorption detachment assays shows that this material specific surface is 70m 2/ g.
Embodiment 7:
The VOSO of configuration 0.010mol/L 4the NaVO of solution and 0.020mol/L 3two kinds of solution, by two constant-flux pumps, are mixed with the mixed pipe line of the speed of 10mL/min at 25 DEG C by each 125mL of solution, mixed solution proceeds in the synthesis reactor of 350mL, put into the baking oven that initial temperature is 25 DEG C, rise to static temperature 140 DEG C with the heat-up rate of 10 DEG C/min, leave standstill 48h.After having synthesized, through filtering, deionized water wash vacuum-drying obtains mixed valence vanadium oxide nano-particle material.Adopt TG-DTA means to characterize to learn: under nitrogen atmosphere, this material can be stablized to 370 DEG C; Nitrogen adsorption detachment assays shows that this material specific surface is 50m 2/ g.
Embodiment 8:
The VOSO of configuration 0.11mol/L 4the NaVO of solution and 0.20mol/L 3the each 125mL of solution, by two constant-flux pumps, with the speed of 10mL/min DEG C mixed pipe line two kinds of solution are mixed, mixed solution proceeds in the synthesis reactor of 350mL, put into the baking oven that initial temperature is 25 DEG C, rise to static temperature 100 DEG C with the heat-up rate of 10 DEG C/min, leave standstill 72h.After having synthesized, through filtering, deionized water wash vacuum-drying obtains mixed valence vanadium oxide nano-particle material.Adopt TG-DTA means to characterize to learn: under nitrogen atmosphere, this material can be stablized to 400 DEG C; Nitrogen adsorption detachment assays shows that this material specific surface is 36m 2/ g.
Embodiment 9:
The VOSO of configuration 0.011mol/L 4the NaVO of solution and 0.02mol/L 3two kinds of solution, by two constant-flux pumps, are mixed with the mixed pipe line of the speed of 10mL/min at 25 DEG C by each 125mL of solution, mixed solution proceeds in the synthesis reactor of 350mL, put into the baking oven that initial temperature is 25 DEG C, rise to static temperature 140 DEG C with the heat-up rate of 10 DEG C/min, leave standstill 48h.After having synthesized, through filtering, deionized water wash vacuum-drying obtains mixed valence vanadium oxide nano-particle material.Adopt TG-DTA means to characterize to learn: under nitrogen atmosphere, this material can be stablized to 420 DEG C; Nitrogen adsorption detachment assays shows that this material specific surface is 36m 2/ g.
Embodiment 10:
The VOSO of configuration 0.090mol/L 4the NaVO of solution 0.20mol/L 3two kinds of solution, by two constant-flux pumps, are mixed with the mixed pipe line of the speed of 10mL/min at 25 DEG C by each 125mL of solution, mixed solution proceeds in the synthesis reactor of 350mL, put into the baking oven that initial temperature is 25 DEG C, rise to static temperature 160 DEG C with the heat-up rate of 10 DEG C/min, leave standstill 48h.After having synthesized, through filtering, deionized water wash vacuum-drying obtains mixed valence vanadium oxide nano-particle material.Adopt TG-DTA means to characterize to learn: under nitrogen atmosphere, this material can be stablized to 390 DEG C; Nitrogen adsorption detachment assays shows that this material specific surface is 46m 2/ g.
Embodiment 11:
The VOSO of configuration 0.095mol/L 4the NH of solution and 0.20mol/L 4vO 3two kinds of solution, by two constant-flux pumps, are mixed with the mixed pipe line of the speed of 10mL/min at 25 DEG C by each 125mL of solution, mixed solution proceeds in the synthesis reactor of 350mL, put into the baking oven that initial temperature is 25 DEG C, rise to static temperature 160 DEG C with the heat-up rate of 10 DEG C/min, leave standstill 48h.After having synthesized, through filtering, deionized water wash vacuum-drying obtains mixed valence vanadium oxide nano-particle material.Adopt TG-DTA means to characterize to learn: under nitrogen atmosphere, this material can be stablized to 380 DEG C; Nitrogen adsorption detachment assays shows that this material specific surface is 60m 2/ g.
Embodiment 12:
The VOSO of configuration 0.011mol/L 4the NH of solution and 0.02mol/L 4vO 3the each 125mL of solution, by two constant-flux pumps, mixed by two kinds of solution with the mixed pipe line of the speed of 10mL/min at 80 DEG C, mixed solution proceeds in the synthesis reactor of 350mL, puts into the baking oven that initial temperature is 80 DEG C, leaves standstill 72h.After having synthesized, through filtering, deionized water wash vacuum-drying obtains the barium oxide nano-particle material of mixed valence.Adopt TG-DTA means to characterize to learn: under nitrogen atmosphere, this material can be stablized to 370 DEG C; Nitrogen adsorption detachment assays shows that this material specific surface is 66m 2/ g.
Embodiment 13:
The VOSO of configuration 0.012mol/L 4the NH of solution and 0.02mol/L 4vO 3two kinds of solution, by two constant-flux pumps, are mixed with the mixed pipe line of the speed of 10mL/min at 25 DEG C by each 125mL of solution, mixed solution proceeds in the synthesis reactor of 350mL, put into the baking oven that initial temperature is 25 DEG C, rise to static temperature 140 DEG C with the heat-up rate of 10 DEG C/min, leave standstill 48h.After having synthesized, through filtering, deionized water wash vacuum-drying obtains mixed valence vanadium oxide nano-particle material.Adopt TG-DTA means to characterize to learn: under nitrogen atmosphere, this material can be stablized to 400 DEG C; Nitrogen adsorption detachment assays shows that this material specific surface is 66m 2/ g.
Embodiment 14:
The VOSO of configuration 0.10mol/L 4the NH of solution and 0.20mol/L 4vO 3two kinds of solution, by two constant-flux pumps, are mixed with the mixed pipe line of the speed of 10mL/min at 25 DEG C by each 125mL of solution, mixed solution proceeds in the synthesis reactor of 350mL, put into the baking oven that initial temperature is 25 DEG C, rise to static temperature 160 DEG C with the heat-up rate of 10 DEG C/min, leave standstill 24h.After having synthesized, through filtering, deionized water wash vacuum-drying obtains mixed valence vanadium oxide nano-particle material.Adopt TG-DTA means to characterize to learn: under nitrogen atmosphere, this material can be stablized to 420 DEG C; Nitrogen adsorption detachment assays shows that this material specific surface is 26m 2/ g.
Embodiment 15:
The VOSO of configuration 0.011mol/L 4the NH of solution and 0.02mol/L 4vO 3two kinds of solution, by two constant-flux pumps, are mixed with the mixed pipe line of the speed of 10mL/min at 25 DEG C by each 125mL of solution, mixed solution proceeds in the synthesis reactor of 350mL, put into the baking oven that initial temperature is 25 DEG C, rise to static temperature 160 DEG C with the heat-up rate of 10 DEG C/min, leave standstill 48h.After having synthesized, through filtering, deionized water wash vacuum-drying obtains mixed valence vanadium oxide nano-particle material.Adopt TG-DTA means to characterize to learn: under nitrogen atmosphere, this material can be stablized to 390 DEG C; Nitrogen adsorption detachment assays shows that this material specific surface is 66m 2/ g.
Embodiment 16:
The VOSO of configuration 0.0090mol/L 4the NH of solution and 0.02mol/L 4vO 3two kinds of solution, by two constant-flux pumps, are mixed with the mixed pipe line of the speed of 10mL/min at 25 DEG C by each 125mL of solution, mixed solution proceeds in the synthesis reactor of 350mL, put into the baking oven that initial temperature is 25 DEG C, rise to static temperature 160 DEG C with the heat-up rate of 5 DEG C/min, leave standstill 48h.After having synthesized, through filtering, deionized water wash vacuum-drying obtains the barium oxide nano-particle material of mixed valence.Adopt TG-DTA means to characterize to learn: under nitrogen atmosphere, this material can be stablized to 360 DEG C; Nitrogen adsorption detachment assays shows that this material specific surface is 91m 2/ g.
Embodiment 17:
The VOSO of configuration 0.012mol/L 4the NH of solution and 0.02mol/L 4vO 3two kinds of solution, by two constant-flux pumps, are mixed with the mixed pipe line of the speed of 10mL/min at 25 DEG C by each 125mL of solution, mixed solution proceeds in the synthesis reactor of 350mL, put into the baking oven that initial temperature is 25 DEG C, rise to static temperature 120 DEG C with the heat-up rate of 10 DEG C/min, leave standstill 48h.After having synthesized, through filtering, deionized water wash vacuum-drying obtains mixed valence vanadium oxide nano-particle material.Adopt TG-DTA means to characterize to learn: under nitrogen atmosphere, this material can be stablized to 380 DEG C; Nitrogen adsorption detachment assays shows that this material specific surface is 66m 2/ g.
Embodiment 18:
The VOSO of configuration 0.011mol/L 4the NH of solution and 0.02mol/L 4vO 3the each 125mL of solution, by two constant-flux pumps, mixed by two kinds of solution with the mixed pipe line of the speed of 10mL/min at 120 DEG C, mixed solution proceeds in the synthesis reactor of 350mL, puts into the baking oven that initial temperature is 120 DEG C, static temperature 120 DEG C, leaves standstill 24h.After having synthesized, through filtering, deionized water wash vacuum-drying obtains the barium oxide nano-particle material of mixed valence.Adopt TG-DTA means to characterize to learn: under nitrogen atmosphere, this material can be stablized to 380 DEG C; Nitrogen adsorption detachment assays shows that this material specific surface is 66m 2/ g.
Embodiment 19:
The VOSO of configuration 0.011mol/L 4the NH of solution and 0.02mol/L 4vO 3the each 125mL of solution, by two constant-flux pumps, mixed by two kinds of solution with the mixed pipe line of the speed of 10mL/min at 160 DEG C, mixed solution proceeds in the synthesis reactor of 350mL, puts into the baking oven that initial temperature is 160 DEG C, leaves standstill 24h.After having synthesized, through filtering, deionized water wash vacuum-drying obtains mixed valence vanadium oxide nano-particle material.Adopt TG-DTA means to characterize to learn: under nitrogen atmosphere, this material can be stablized to 370 DEG C; Nitrogen adsorption detachment assays shows that this material specific surface is 59m 2/ g.
Embodiment 20:
The VOSO of configuration 0.011mol/L 4the NH of solution and 0.02mol/L 4vO 3two kinds of solution, by two constant-flux pumps, are mixed with the mixed pipe line of the speed of 10mL/min at 25 DEG C by each 125mL of solution, mixed solution proceeds in the synthesis reactor of 350mL, put into the baking oven that initial temperature is 25 DEG C, rise to static temperature 120 DEG C with the heat-up rate of 10 DEG C/min, leave standstill 48h.After having synthesized, through filtering, deionized water wash vacuum-drying obtains mixed valence vanadium oxide nano-particle material.Adopt TG-DTA means to characterize to learn: under nitrogen atmosphere, this material can be stablized to 390 DEG C; Nitrogen adsorption detachment assays shows that this material specific surface is 46m 2/ g.
Embodiment 21:
The configuration vanadyl acetylacetonate solution of 0.011mol/L and the NaVO of 0.02mol/L 3two kinds of solution, by two constant-flux pumps, are mixed with the mixed pipe line of the speed of 10mL/min at 10 DEG C by each 125mL of solution, mixed solution proceeds in the synthesis reactor of 350mL, put into the baking oven that initial temperature is 25 DEG C, rise to static temperature 160 DEG C with the heat-up rate of 10 DEG C/min, leave standstill 48h.After having synthesized, through filtering, deionized water wash vacuum-drying obtains mixed valence vanadium oxide nano-particle material.Adopt TG-DTA means to characterize to learn: under nitrogen atmosphere, this material can be stablized to 380 DEG C; Nitrogen adsorption detachment assays shows that this material specific surface is 66m 2/ g.
Embodiment 22:
The configuration vanadyl acetylacetonate solution of 0.013mol/L and the NaVO of 0.02mol/L 3two kinds of solution, by two constant-flux pumps, are mixed with the mixed pipe line of the speed of 10mL/min at 25 DEG C by each 125mL of solution, mixed solution proceeds in the synthesis reactor of 350mL, put into the baking oven that initial temperature is 25 DEG C, rise to static temperature 120 DEG C with the heat-up rate of 10 DEG C/min, leave standstill 72h.After having synthesized, through filtering, deionized water wash vacuum-drying obtains mixed valence vanadium oxide nano-particle material.Adopt TG-DTA means to characterize to learn: under nitrogen atmosphere, this material can be stablized to 390 DEG C; Nitrogen adsorption detachment assays shows that this material specific surface is 46m 2/ g.
Embodiment 23:
The configuration vanadyl acetylacetonate solution of 0.013mol/L and the NaVO of 0.02mol/L 3two kinds of solution, by two constant-flux pumps, are mixed with the mixed pipe line of the speed of 10mL/min at 25 DEG C by each 125mL of solution, mixed solution proceeds in the synthesis reactor of 350mL, put into the baking oven that initial temperature is 25 DEG C, rise to static temperature 100 DEG C with the heat-up rate of 5 DEG C/min, leave standstill 72h.After having synthesized, through filtering, deionized water wash vacuum-drying obtains mixed valence vanadium oxide nano-particle material.Adopt TG-DTA means to characterize to learn: under nitrogen atmosphere, this material can be stablized to 380 DEG C; Nitrogen adsorption detachment assays shows that this material specific surface is 44m 2/ g.
Embodiment 24:
The configuration vanadyl acetylacetonate solution of 0.010mol/L and the NaVO of 0.02mol/L 3two kinds of solution, by two constant-flux pumps, are mixed with the mixed pipe line of the speed of 10mL/min at 25 DEG C by each 125mL of solution, mixed solution proceeds in the synthesis reactor of 350mL, put into the baking oven that initial temperature is 160 DEG C, rise to static temperature 160 DEG C with the heat-up rate of 10 DEG C/min, leave standstill 48h.After having synthesized, through filtering, deionized water wash vacuum-drying obtains mixed valence vanadium oxide nano-particle material.Adopt TG-DTA means to characterize to learn: under nitrogen atmosphere, this material can be stablized to 380 DEG C; Nitrogen adsorption detachment assays shows that this material specific surface is 66m 2/ g.
Embodiment 25:
The configuration vanadyl acetylacetonate solution of 0.012mol/L and the NaVO of 0.02mol/L 3two kinds of solution, by two constant-flux pumps, are mixed with the mixed pipe line of the speed of 10mL/min at 25 DEG C by each 125mL of solution, mixed solution proceeds in the synthesis reactor of 350mL, put into the baking oven that initial temperature is 25 DEG C, rise to static temperature 200 DEG C with the heat-up rate of 10 DEG C/min, leave standstill 24h.After having synthesized, through filtering, deionized water wash vacuum-drying obtains mixed valence vanadium oxide nano-particle material.Adopt TG-DTA means to characterize to learn: under nitrogen atmosphere, this material can be stablized to 380 DEG C; Nitrogen adsorption detachment assays shows that this material specific surface is 63m 2/ g.
Embodiment 26:
The configuration vanadyl acetylacetonate solution of 0.12mol/L and the NaVO of 0.20mol/L 3the each 125mL of solution, by two constant-flux pumps, mixed by two kinds of solution with the mixed pipe line of the speed of 10mL/min at 80 DEG C, mixed solution proceeds in the synthesis reactor of 350mL, puts into the baking oven that initial temperature is 80 DEG C, leaves standstill 72h.After having synthesized, through filtering, deionized water wash vacuum-drying obtains mixed valence vanadium oxide nano-particle material.Adopt TG-DTA means to characterize to learn: under nitrogen atmosphere, this material can be stablized to 390 DEG C; Nitrogen adsorption detachment assays shows that this material specific surface is 36m 2/ g.
Embodiment 27:
The configuration vanadyl acetylacetonate solution of 0.10mol/L and the NaVO of 0.20mol/L 3two kinds of solution, by two constant-flux pumps, are mixed with the mixed pipe line of the speed of 10mL/min at 25 DEG C by each 125mL of solution, mixed solution proceeds in the synthesis reactor of 350mL, put into the baking oven that initial temperature is 25 DEG C, rise to static temperature 100 DEG C with the heat-up rate of 10 DEG C/min, leave standstill 72h.After having synthesized, through filtering, deionized water wash vacuum-drying obtains mixed valence vanadium oxide nano-particle material.Adopt TG-DTA means to characterize to learn: under nitrogen atmosphere, this material can be stablized to 390 DEG C; Nitrogen adsorption detachment assays shows that this material specific surface is 45m 2/ g.
Embodiment 28:
The configuration vanadyl acetylacetonate solution of 0.010mol/L and the NH of 0.02mol/L 4vO 3two kinds of solution, by two constant-flux pumps, are mixed with the mixed pipe line of the speed of 10mL/min at 25 DEG C by each 125mL of solution, mixed solution proceeds in the synthesis reactor of 350mL, put into the baking oven that initial temperature is 25 DEG C, rise to static temperature 160 DEG C with the heat-up rate of 10 DEG C/min, leave standstill 72h.After having synthesized, through filtering, deionized water wash vacuum-drying obtains mixed valence vanadium oxide nano-particle material.Adopt TG-DTA means to characterize to learn: under nitrogen atmosphere, this material can be stablized to 390 DEG C; Nitrogen adsorption detachment assays shows that this material specific surface is 76m 2/ g.
Embodiment 29:
The configuration vanadyl acetylacetonate solution of 0.012mol/L and the NH of 0.02mol/L 4vO 3two kinds of solution, by two constant-flux pumps, are mixed with the mixed pipe line of the speed of 10mL/min at 25 DEG C by each 125mL of solution, mixed solution proceeds in the synthesis reactor of 350mL, put into the baking oven that initial temperature is 25 DEG C, rise to static temperature 120 DEG C with the heat-up rate of 10 DEG C/min, leave standstill 48h.After having synthesized, through filtering, deionized water wash vacuum-drying obtains mixed valence vanadium oxide nano-particle material.Adopt TG-DTA means to characterize to learn: under nitrogen atmosphere, this material can be stablized to 370 DEG C; Nitrogen adsorption detachment assays shows that this material specific surface is 62m 2/ g.
Embodiment 30:
The configuration vanadyl acetylacetonate solution of 0.009mol/L and the NH of 0.02mol/L 4vO 3the each 125mL of solution, by two constant-flux pumps, mixed by two kinds of solution with the mixed pipe line of the speed of 10mL/min at 80 DEG C, mixed solution proceeds in the synthesis reactor of 350mL, puts into the baking oven that initial temperature is 80 DEG C, leaves standstill 72h.After having synthesized, through filtering, deionized water wash vacuum-drying obtains mixed valence vanadium oxide nano-particle material.Adopt TG-DTA means to characterize to learn: under nitrogen atmosphere, this material can be stablized to 380 DEG C; Nitrogen adsorption detachment assays shows that this material specific surface is 86m 2/ g.

Claims (8)

1. a mixed valence vanadium oxide nano material, is characterized in that: will containing VO 2+compound and containing VO 3 -compound, make certain density A, B mother liquor after being scattered in deionized water respectively;
VO in A mother liquor 2+ionic concn is: 0.008-1.0mol/L;
VO in B mother liquor 3 -ionic concn is: 0.02-2.2mol/L;
Under 10-160 DEG C of mixing temperature, under certain mixing condition, by VO 2+/ VO 3 -for the molar ratio of 1:1.4-1:2.4 mixes, be placed in synthesis reactor, airtight, then rise to 60-200 DEG C with the temperature rise rate of 1-20 DEG C/min, leave standstill 2-180h.
2. a preparation method for a kind of mixed valence vanadium oxide nano material described in claim 1, is characterized in that: will containing VO 2+compound and containing VO 3 -compound, make certain density mother liquor after being scattered in deionized water respectively;
VO in A mother liquor 2+ionic concn is: 0.008-1.0mol/L;
VO in B mother liquor 3 -ionic concn is: 0.02-2.2mol/L;
Under 10-160 DEG C of mixing temperature, under certain mixing condition, by VO 2+/ VO 3 -for the molar ratio of 1:1.4-1:2.4 mixes, be placed in synthesis reactor, airtight, then rise to 60-200 DEG C with the temperature rise rate of 1-20 DEG C/min, leave standstill 2-180h.
3. according to preparation method according to claim 2, it is characterized in that: described containing VO 2+compound is one or more in vanadylic sulfate, vanadyl chloride, vanadyl oxalate, vanadyl acetylacetonate;
Described containing VO 3 -compound be NaVO 3, NH 4vO 3, KVO 3one or more.
4., according to preparation method according to claim 2, it is characterized in that:
Described containing VO 2+compound is one or more in vanadylic sulfate, vanadyl acetylacetonate;
Described containing VO 3 -compound be NH 4vO 3, NaVO 3one or more.
5. according to the preparation method described in claim 2,3 or 4, it is characterized in that: mixing temperature is 10-80 DEG C, temperature rise rate is 1-10 DEG C/min;
Dwell temperature is: 60-180 DEG C, and time of repose is: 4h-180h.
6. according to preparation method according to claim 5, it is characterized in that: mixing temperature is 25 DEG C-60 DEG C, heat-up rate is 5-10 DEG C/min;
Dwell temperature is: 80 DEG C-160 DEG C, and time of repose is: 8h-72h.
7., according to the preparation method described in claim 2,3 or 4, it is characterized in that:
VO in A mother liquor 2+ionic concn is: 0.008-0.24mol/L;
VO in B mother liquor 3 -ionic concn is: 0.02-0.5mol/L.
8., according to preparation method according to claim 5, it is characterized in that:
VO in A mother liquor 2+ionic concn is: 0.008-0.14mol/L;
VO in B mother liquor 3 -ionic concn is: 0.02-0.2mol/L.
CN201310268704.2A 2013-06-27 2013-06-27 A kind of mixed valence vanadium oxide nano material and preparation method thereof Active CN104250022B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201310268704.2A CN104250022B (en) 2013-06-27 2013-06-27 A kind of mixed valence vanadium oxide nano material and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201310268704.2A CN104250022B (en) 2013-06-27 2013-06-27 A kind of mixed valence vanadium oxide nano material and preparation method thereof

Publications (2)

Publication Number Publication Date
CN104250022A true CN104250022A (en) 2014-12-31
CN104250022B CN104250022B (en) 2016-06-15

Family

ID=52185312

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201310268704.2A Active CN104250022B (en) 2013-06-27 2013-06-27 A kind of mixed valence vanadium oxide nano material and preparation method thereof

Country Status (1)

Country Link
CN (1) CN104250022B (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101391814A (en) * 2008-10-31 2009-03-25 中国科学院上海硅酸盐研究所 Method for preparing rutile phase hypovanadic oxide powder
WO2012097687A1 (en) * 2011-01-21 2012-07-26 中国科学院上海硅酸盐研究所 Doped vanadium dioxide powder, dispersion, and preparation methods and applications therefor
CN102757094A (en) * 2011-04-28 2012-10-31 中国科学院上海硅酸盐研究所 Method for preparing steady phase-A vanadium dioxide nanorod

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101391814A (en) * 2008-10-31 2009-03-25 中国科学院上海硅酸盐研究所 Method for preparing rutile phase hypovanadic oxide powder
WO2012097687A1 (en) * 2011-01-21 2012-07-26 中国科学院上海硅酸盐研究所 Doped vanadium dioxide powder, dispersion, and preparation methods and applications therefor
CN102757094A (en) * 2011-04-28 2012-10-31 中国科学院上海硅酸盐研究所 Method for preparing steady phase-A vanadium dioxide nanorod

Also Published As

Publication number Publication date
CN104250022B (en) 2016-06-15

Similar Documents

Publication Publication Date Title
CN102531050B (en) Method for preparing TiO2 (B) nano wires and application of prepared TiO2 (B) nano wires
CN102963929B (en) Method for preparing lanthanum-doped bismuth titanate nano powder by sol-gel hydrothermal method
CN104667951B (en) A kind of preparation method of bromine oxygen bismuth thin film photochemical catalyst
CN103240073B (en) Zn&lt;2+&gt;-doped BiVO4 visible-light-driven photocatalyst and preparation method thereof
CN105289585B (en) A kind of preparation method of the rear-earth-doped oxidation manganese of support type for ozone catalyst
CN101597086A (en) Method for preparing nano manganese dioxide with different crystal forms in low-temperature acid solution
CN104393256B (en) The preparation method of LiFePO4 phosphoric acid vanadium lithium/carbon In-situ reaction positive electrode
CN103736480B (en) A kind of corner star pucherite as catalysis material and preparation method thereof
Li et al. Relationship between crystalline phases and photocatalytic activities of BiVO4
CN103708424A (en) Preparation method of {001} crystal surface-exposed BioBr square nanosheet
CN103372424B (en) A kind of synthetic method of high activity N-F codope pucherite visible-light photocatalysis material
CN101913651A (en) Hydrothermal method for preparing triclinic-phase FeVO4 micro particles
CN101791548A (en) Visible light catalyst BiVO4 and preparation method thereof
CN105195198A (en) Mpg-C3N4/Bi0.9Nd0.1VO4 composite photocatalyst and preparation method and application thereof
CN103904343B (en) The preparation method of all-vanadium redox flow battery electrolytic solution
CN104707635B (en) A kind of high activity phosphorus doping bismuth vanadate photocatalyst and preparation method and application
CN102602988B (en) Method for preparing lithium titanate (Li4Ti5O12) with large specific area
CN102995120B (en) Nanometer TiO2 monocrystalline material, preparation method and application thereof
CN102744086B (en) Preparation method of ZrO2-TiO2/SO42-solid acid catalyst
CN104445341B (en) A kind of preparation method of the nanometer yttrium aluminium garnet powder of pure YAG phase
Lin et al. Factors influencing the structure of electrochemically prepared α-MnO2 and γ-MnO2 phases
CN101342479A (en) Preparation method for three-dimensional ordered foramen magnum titanium oxygen &#39;lithium ion screen&#39;
CN104250022A (en) Mixed valence vanadium oxide nano material and preparation method thereof
CN104328479B (en) The method that the water-heat process utilizing glycerol to modulate synthesizes (010) preferred orientation bismuth vanadate powder
CN103351026B (en) Method for preparing rod-shaped NH4V3O8 nanocrystal

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant