CN104250022B - A kind of mixed valence vanadium oxide nano material and preparation method thereof - Google Patents
A kind of mixed valence vanadium oxide nano material and preparation method thereof Download PDFInfo
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Abstract
The preparation method that the present invention relates to a kind of mixed valence vanadium oxide nano material, will containing VO2+Compound dispersing and dissolving in deionized water, form A liquid, will containing VO3 -Compound dispersing and dissolving in deionized water, form B liquid, according to VO2+With VO3 -For the molar ratio of 1:1.4-1:2.4, under different concentration, at 10-160 DEG C by two kinds of solution mixing of above-mentioned AB, it is placed in synthesis reactor, airtight, then rise to 60-200 DEG C with the heating rate of 1-20 DEG C/min, stand 2-180h. Precipitate is separated after terminating, washs, dries this mixed valence vanadium oxide nano material prepared by crystallization. It is big that this material has Heat stability is good, water-fast, specific surface area, and crystal structure has layer structure, the bar-shaped structure of 1-dimention nano, in catalysis, electrode, sensor, electric capacity, the field such as lithium battery cathode and anode has potential application.
Description
Technical field
The invention belongs to field of material synthesis technology, the preparation method being specifically related to a kind 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, at catalysis, electrode, sensor, has important purposes in electrode material of lithium battery. Compound common for vanadium oxide material is the compound of homogeneous valence state, such as V2O3, VO2, V2O5, 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 catalyst, 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: A.M.Chippindal et al. (J.Mater.Chem.1992,2,601-608.) adopts the method for two kinds of unit price state vanadium oxide solid phase high?temperature nuclei of mixing, and reaction equation is: 5V2O5+V2O3→4V3O7, synthesized V3O7Material. The method needs experience high temperature reduction, the complicated programs such as fine vacuum mixes, high?temperature nuclei in building-up process. H.Qiao et al. (Electrochem.Commun.2006,8,21-26.) is by long-time at high temperature hydrothermal treatment consists V2O5Obtain the barium oxide of a kind of mixed valence, but find composing from XRD figure or have a lot of assorted peaks. Y.F.Zhang, et al. (Ceram.Int.2013,39,129-141.) by long-time at high temperature hydrothermal treatment consists V2O5With the barium oxide that hydrogen peroxide obtains a kind of mixed valence. G.Wang et al. (AcsNano2012,6,10296-10302.) is by long-time at high temperature hydrothermal treatment consists V2O5With the H that HCl obtains a kind of mixed valence2V3O8Material. K.H.Chang et al. (Acta.Mater.2007,55,6192-6197.) is by using H2O2Partial oxidation VO2+Method Hydrothermal Synthesis V3O7·H2O。
Correlational study finds that mixed valence oxyvanadium compound material is as catalysis, electrode material aspect has good advantage, but mostly the method for synthesis is solid phase pyroreaction, or at high temperature hydro-thermal Some redox or partial reduction vanadium species, because being generally not capable of controlling well the hydrolysis speed with crystal nucleation growth, the material obtained is mostly less pure, and the irregular heterogeneity of shape, is mostly more difficult to get nanometer materials.
Material structure determines the performance of material, and therefore, exploitation is a kind of reliably, and the synthetic method of the mixed valence vanadium oxide material of structure-controllable has great importance.This type of material is because of the performance of its uniqueness, it is possible to as catalysis, 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 big, and crystal structure on there is layer structure, the features such as the bar-shaped structure of 1-dimention nano, it is applicable to catalysis, electrode, photosensitive, electric capacity, the material such as lithium battery cathode and anode.
The technical scheme is that will containing VO2+(VOSO4, VOC2O4, VOCl2, vanadyl acetylacetonate etc.) and compound dispersing and dissolving forms A liquid in deionized water, by the compound (NaVO containing metavanadic acid root3,NH4VO3,KVO3) dispersing and dissolving forms B liquid in deionized water water, according to V4+With V5+The ratio of molar ratio 1:1.4:2-1:2.4, under different concentration, at 10-160 DEG C, above two solution is mixed, then again through the speed of different programming rate 1-10 DEG C/min, mixed liquor is risen to the crystallization temperature of 80-200 DEG C, in synthesis reactor, stand 2-180h. Precipitate is separated, wash, dry this mixed valence vanadium oxide material prepared. 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, by controlling variations in temperature and crystallization temperature, controlling nucleation and crystallization speed and hydrolysis rate, the control time is thus obtaining a nano bar-shape material.
The selection of pentavalent vanadium acid group compound has important impact for synthetic material. Different vanadic acid roots under different concentration, different pH value, have different forms at temperature, the crystal structure pattern of material for synthesis has critically important impact. Such vanadic acid radical compound, it is possible to for sodium metavanadate, ammonium metavanadate, potassium metavanadate, sodium orthovanadate, ortho-vanadic acid potassium, sodium pyrovanadate, one or more in pyrovanadic acid ammonium, it is advantageous to vanadic acid compound be: sodium metavanadate, potassium metavanadate, ammonium metavanadate, one or more in sodium orthovanadate, best pentavalent vanadium acid group compound is: sodium metavanadate, one or more in ammonium metavanadate.
Synthetic material is had important impact by the selection of the oxygen ionized compound of tetravalence vanadium. The acid difference of the different oxygen ionized compounds of tetravalence vanadium, the stability of ion is different, and the form existed is also different, can have influence on crystal growth and the morphology control of mixed valence vanadium oxide material in certain degree. This tetravalence vanadium oxonium ion can be vanadium oxysulfate, divanadyl tetrachloride, vanadyl oxalate, vanadyl acetylacetonate, one or more in ethylenediaminetetraacetic acid vanadyl, it is advantageous to the oxygen ionized compound of tetravalence vanadium be: vanadium oxysulfate, vanadyl acetylacetonate, one or more in ethylenediaminetetraacetic acid vanadyl, the best oxygen ionized compound of tetravalence vanadium is: vanadium oxysulfate, 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 also resides in reasonable adjusting synthesis temperature, the concentration of mother solution, pentavalent vanadium acid group compound and the molar ratio of the oxygen ionized compound of tetravalence vanadium, response time, dwell temperature and time etc. The mixing temperature being suitable for is 0 DEG C-160 DEG C, it is advantageous to mixing temperature be 10 DEG C-80 DEG C, best mixing temperature is 20 DEG C-30 DEG C.
The concentration of the mother solution being suitable for is: VO2+: 0.008-1.0mol/L, VO3 -For 0.014-2.4mol/L. Preferably mother liquid concentration is: VO2+: 0.008-0.5mol/L, VO3 -For 0.014-0.24mol/L. Best mother liquid concentration is: VO2+: 0.008-0.1mol/L, VO3 -For 0.018-0.24mol/L. The VO being suitable for2+/VO3 -Molar ratio be 1:1.4-1:2.4, it is advantageous to VO2+/VO3 -Molar ratio be: 1:1.6-1:2.4, best VO2+/VO3 -Molar ratio be: 1:1.8-1:2.4. The response time being suitable for is: 0.1h-2h, it is advantageous to response time be: 0.1h-0.5h, the best response time is: 0.1h-0.3h. The dwell temperature being suitable for is: 0 DEG C-200 DEG C, it is advantageous to dwell temperature be: 20 DEG C-160 DEG C, best dwell temperature is: 80 DEG C-160 DEG C. The time of repose being suitable for is: 2h-360h, it is advantageous to time of repose be: 2h-240h, best time of repose is: 8h-72h.
The preparation method that the present invention relates to a kind of mixed valence vanadium oxide material, advantage is in that this material of synthesis has Heat stability is good, water-fast, specific surface area is big, and crystal structure on there is layer 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. Obtained material can be used as catalysis, electrode, sensor, electric capacity, the aspect such as lithium battery cathode and anode.
Detailed description of the invention:
In order to the present invention is further elaborated, several be embodied as case is given below, but the invention is not restricted to these embodiments.
Embodiment 1:
The VOSO of configuration 0.12mol/L4The NaVO of solution and 0.20mol/L3Two kinds of solution, by two constant-flux pumps, are mixed at the mixed pipe line of 25 DEG C by each 125mL of solution with the speed of 10mL/min, mixed liquor 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 programming rate of 10 DEG C/min, stand 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 stably to 380 DEG C; Nitrogen adsorption detachment assays shows that this material specific surface is 80m2/g。
Embodiment 2:
The VOSO of configuration 0.01mol/L4The NaVO of solution and 0.02mol/L3Two kinds of solution, by two constant-flux pumps, are mixed at the mixed pipe line of 25 DEG C by each 125mL of solution with the speed of 10mL/min, mixed liquor 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 programming rate of 10 DEG C/min, stand 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 stably to 380 DEG C; Nitrogen adsorption detachment assays shows that this material specific surface is 56m2/g。
Embodiment 3:
The VOSO of configuration 0.009mol/L4The NaVO of solution and 0.02mol/L3Two kinds of solution, by two constant-flux pumps, are mixed at the mixed pipe line of 80 DEG C by each 125mL of solution with the speed of 10mL/min, and mixed liquor proceeds in the synthesis reactor of 350mL, put into the baking oven that initial temperature is 80 DEG C, stand 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 stably to 350 DEG C; Nitrogen adsorption detachment assays shows that this material specific surface is 90m2/g。
Embodiment 4:
The VOSO of configuration 0.12mol/L4The NaVO of solution and 0.02mol/L3Two kinds of solution, by two constant-flux pumps, are mixed at the mixed pipe line of 80 DEG C by each 125mL of solution with the speed of 10mL/min, mixed liquor 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 programming rate of 10 DEG C/min, stand 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 stably to 380 DEG C; Nitrogen adsorption detachment assays shows that this material specific surface is 40m2/g。
Embodiment 5:
The VOSO of configuration 0.014mol/L4The NaVO of solution and 0.02mol/L3Two kinds of solution, by two constant-flux pumps, are mixed at the mixed pipe line of 25 DEG C by each 125mL of solution with the speed of 10mL/min, mixed liquor 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 programming rate of 10 DEG C/min, stand 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 stably to 350 DEG C; Nitrogen adsorption detachment assays shows that this material specific surface is 79m2/g。
Embodiment 6:
The VOSO of configuration 0.011mol/L4The NaVO of solution and 0.02mol/L3Two kinds of solution, by two constant-flux pumps, are mixed at the mixed pipe line of 10 DEG C by each 125mL of solution with the speed of 10mL/min, mixed liquor 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 programming rate of 10 DEG C/min, stand 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 stably to 380 DEG C; Nitrogen adsorption detachment assays shows that this material specific surface is 70m2/g。
Embodiment 7:
The VOSO of configuration 0.010mol/L4The NaVO of solution and 0.020mol/L3Two kinds of solution, by two constant-flux pumps, are mixed at the mixed pipe line of 25 DEG C by each 125mL of solution with the speed of 10mL/min, mixed liquor 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 programming rate of 10 DEG C/min, stand 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 stably to 370 DEG C; Nitrogen adsorption detachment assays shows that this material specific surface is 50m2/g。
Embodiment 8:
The VOSO of configuration 0.11mol/L4The NaVO of solution and 0.20mol/L3The 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 liquor 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 programming rate of 10 DEG C/min, stand 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 stably to 400 DEG C; Nitrogen adsorption detachment assays shows that this material specific surface is 36m2/g。
Embodiment 9:
The VOSO of configuration 0.011mol/L4The NaVO of solution and 0.02mol/L3Two kinds of solution, by two constant-flux pumps, are mixed at the mixed pipe line of 25 DEG C by each 125mL of solution with the speed of 10mL/min, mixed liquor 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 programming rate of 10 DEG C/min, stand 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 stably to 420 DEG C; Nitrogen adsorption detachment assays shows that this material specific surface is 36m2/g。
Embodiment 10:
The VOSO of configuration 0.090mol/L4The NaVO of solution 0.20mol/L3Two kinds of solution, by two constant-flux pumps, are mixed at the mixed pipe line of 25 DEG C by each 125mL of solution with the speed of 10mL/min, mixed liquor 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 programming rate of 10 DEG C/min, stand 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 stably to 390 DEG C; Nitrogen adsorption detachment assays shows that this material specific surface is 46m2/g。
Embodiment 11:
The VOSO of configuration 0.095mol/L4The NH of solution and 0.20mol/L4VO3Two kinds of solution, by two constant-flux pumps, are mixed at the mixed pipe line of 25 DEG C by each 125mL of solution with the speed of 10mL/min, mixed liquor 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 programming rate of 10 DEG C/min, stand 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 stably to 380 DEG C; Nitrogen adsorption detachment assays shows that this material specific surface is 60m2/g。
Embodiment 12:
The VOSO of configuration 0.011mol/L4The NH of solution and 0.02mol/L4VO3Two kinds of solution, by two constant-flux pumps, are mixed at the mixed pipe line of 80 DEG C by each 125mL of solution with the speed of 10mL/min, and mixed liquor proceeds in the synthesis reactor of 350mL, put into the baking oven that initial temperature is 80 DEG C, stand 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 stably to 370 DEG C; Nitrogen adsorption detachment assays shows that this material specific surface is 66m2/g。
Embodiment 13:
The VOSO of configuration 0.012mol/L4The NH of solution and 0.02mol/L4VO3Two kinds of solution, by two constant-flux pumps, are mixed at the mixed pipe line of 25 DEG C by each 125mL of solution with the speed of 10mL/min, mixed liquor 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 programming rate of 10 DEG C/min, stand 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 stably to 400 DEG C; Nitrogen adsorption detachment assays shows that this material specific surface is 66m2/g。
Embodiment 14:
The VOSO of configuration 0.10mol/L4The NH of solution and 0.20mol/L4VO3Two kinds of solution, by two constant-flux pumps, are mixed at the mixed pipe line of 25 DEG C by each 125mL of solution with the speed of 10mL/min, mixed liquor 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 programming rate of 10 DEG C/min, stand 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 stably to 420 DEG C; Nitrogen adsorption detachment assays shows that this material specific surface is 26m2/g。
Embodiment 15:
The VOSO of configuration 0.011mol/L4The NH of solution and 0.02mol/L4VO3Two kinds of solution, by two constant-flux pumps, are mixed at the mixed pipe line of 25 DEG C by each 125mL of solution with the speed of 10mL/min, mixed liquor 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 programming rate of 10 DEG C/min, stand 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 stably to 390 DEG C; Nitrogen adsorption detachment assays shows that this material specific surface is 66m2/g。
Embodiment 16:
The VOSO of configuration 0.0090mol/L4The NH of solution and 0.02mol/L4VO3Two kinds of solution, by two constant-flux pumps, are mixed at the mixed pipe line of 25 DEG C by each 125mL of solution with the speed of 10mL/min, mixed liquor 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 programming rate of 5 DEG C/min, stand 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 stably to 360 DEG C; Nitrogen adsorption detachment assays shows that this material specific surface is 91m2/g。
Embodiment 17:
The VOSO of configuration 0.012mol/L4The NH of solution and 0.02mol/L4VO3Two kinds of solution, by two constant-flux pumps, are mixed at the mixed pipe line of 25 DEG C by each 125mL of solution with the speed of 10mL/min, mixed liquor 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 programming rate of 10 DEG C/min, stand 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 stably to 380 DEG C; Nitrogen adsorption detachment assays shows that this material specific surface is 66m2/g。
Embodiment 18:
The VOSO of configuration 0.011mol/L4The NH of solution and 0.02mol/L4VO3Two kinds of solution, by two constant-flux pumps, are mixed at the mixed pipe line of 120 DEG C by each 125mL of solution with the speed of 10mL/min, and mixed liquor proceeds in the synthesis reactor of 350mL, put into the baking oven that initial temperature is 120 DEG C, static temperature 120 DEG C, stand 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 stably to 380 DEG C; Nitrogen adsorption detachment assays shows that this material specific surface is 66m2/g。
Embodiment 19:
The VOSO of configuration 0.011mol/L4The NH of solution and 0.02mol/L4VO3Two kinds of solution, by two constant-flux pumps, are mixed at the mixed pipe line of 160 DEG C by each 125mL of solution with the speed of 10mL/min, and mixed liquor proceeds in the synthesis reactor of 350mL, put into the baking oven that initial temperature is 160 DEG C, stand 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 stably to 370 DEG C; Nitrogen adsorption detachment assays shows that this material specific surface is 59m2/g。
Embodiment 20:
The VOSO of configuration 0.011mol/L4The NH of solution and 0.02mol/L4VO3Two kinds of solution, by two constant-flux pumps, are mixed at the mixed pipe line of 25 DEG C by each 125mL of solution with the speed of 10mL/min, mixed liquor 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 programming rate of 10 DEG C/min, stand 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 stably to 390 DEG C; Nitrogen adsorption detachment assays shows that this material specific surface is 46m2/g。
Embodiment 21:
The vanadyl acetylacetonate solution of configuration 0.011mol/L and the NaVO of 0.02mol/L3Two kinds of solution, by two constant-flux pumps, are mixed at the mixed pipe line of 10 DEG C by each 125mL of solution with the speed of 10mL/min, mixed liquor 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 programming rate of 10 DEG C/min, stand 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 stably to 380 DEG C; Nitrogen adsorption detachment assays shows that this material specific surface is 66m2/g。
Embodiment 22:
The vanadyl acetylacetonate solution of configuration 0.013mol/L and the NaVO of 0.02mol/L3Two kinds of solution, by two constant-flux pumps, are mixed at the mixed pipe line of 25 DEG C by each 125mL of solution with the speed of 10mL/min, mixed liquor 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 programming rate of 10 DEG C/min, stand 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 stably to 390 DEG C; Nitrogen adsorption detachment assays shows that this material specific surface is 46m2/g。
Embodiment 23:
The vanadyl acetylacetonate solution of configuration 0.013mol/L and the NaVO of 0.02mol/L3Two kinds of solution, by two constant-flux pumps, are mixed at the mixed pipe line of 25 DEG C by each 125mL of solution with the speed of 10mL/min, mixed liquor 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 programming rate of 5 DEG C/min, stand 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 stably to 380 DEG C; Nitrogen adsorption detachment assays shows that this material specific surface is 44m2/g。
Embodiment 24:
The vanadyl acetylacetonate solution of configuration 0.010mol/L and the NaVO of 0.02mol/L3Two kinds of solution, by two constant-flux pumps, are mixed at the mixed pipe line of 25 DEG C by each 125mL of solution with the speed of 10mL/min, mixed liquor 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 programming rate of 10 DEG C/min, stand 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 stably to 380 DEG C; Nitrogen adsorption detachment assays shows that this material specific surface is 66m2/g。
Embodiment 25:
The vanadyl acetylacetonate solution of configuration 0.012mol/L and the NaVO of 0.02mol/L3Two kinds of solution, by two constant-flux pumps, are mixed at the mixed pipe line of 25 DEG C by each 125mL of solution with the speed of 10mL/min, mixed liquor 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 programming rate of 10 DEG C/min, stand 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 stably to 380 DEG C; Nitrogen adsorption detachment assays shows that this material specific surface is 63m2/g。
Embodiment 26:
The vanadyl acetylacetonate solution of configuration 0.12mol/L and the NaVO of 0.20mol/L3Two kinds of solution, by two constant-flux pumps, are mixed at the mixed pipe line of 80 DEG C by each 125mL of solution with the speed of 10mL/min, and mixed liquor proceeds in the synthesis reactor of 350mL, put into the baking oven that initial temperature is 80 DEG C, stand 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 stably to 390 DEG C; Nitrogen adsorption detachment assays shows that this material specific surface is 36m2/g。
Embodiment 27:
The vanadyl acetylacetonate solution of configuration 0.10mol/L and the NaVO of 0.20mol/L3Two kinds of solution, by two constant-flux pumps, are mixed at the mixed pipe line of 25 DEG C by each 125mL of solution with the speed of 10mL/min, mixed liquor 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 programming rate of 10 DEG C/min, stand 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 stably to 390 DEG C; Nitrogen adsorption detachment assays shows that this material specific surface is 45m2/g。
Embodiment 28:
The vanadyl acetylacetonate solution of configuration 0.010mol/L and the NH of 0.02mol/L4VO3Two kinds of solution, by two constant-flux pumps, are mixed at the mixed pipe line of 25 DEG C by each 125mL of solution with the speed of 10mL/min, mixed liquor 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 programming rate of 10 DEG C/min, stand 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 stably to 390 DEG C; Nitrogen adsorption detachment assays shows that this material specific surface is 76m2/g。
Embodiment 29:
The vanadyl acetylacetonate solution of configuration 0.012mol/L and the NH of 0.02mol/L4VO3Two kinds of solution, by two constant-flux pumps, are mixed at the mixed pipe line of 25 DEG C by each 125mL of solution with the speed of 10mL/min, mixed liquor 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 programming rate of 10 DEG C/min, stand 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 stably to 370 DEG C; Nitrogen adsorption detachment assays shows that this material specific surface is 62m2/g。
Embodiment 30:
The vanadyl acetylacetonate solution of configuration 0.009mol/L and the NH of 0.02mol/L4VO3Two kinds of solution, by two constant-flux pumps, are mixed at the mixed pipe line of 80 DEG C by each 125mL of solution with the speed of 10mL/min, and mixed liquor proceeds in the synthesis reactor of 350mL, put into the baking oven that initial temperature is 80 DEG C, stand 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 stably to 380 DEG C; Nitrogen adsorption detachment assays shows that this material specific surface is 86m2/g。
Claims (8)
1. a mixed valence vanadium oxide nano material, it is characterised in that: will containing VO2+Compound and containing VO3 -Compound, make certain density A, B mother solution after being scattered in deionized water respectively;
VO in A mother solution2+Ion concentration is: 0.008～1.0mol/L;
VO in B mother solution3 -Ion concentration is: 0.02～2.2mol/L;
Under 10～160 DEG C of mixing temperatures, under certain mixing condition, by VO2+/VO3 -Molar ratio for 1:1.4～1:2.4 mixes, and is placed in synthesis reactor, airtight, then rises to 60～200 DEG C with the heating rate of 1～20 DEG C/min, stands 2～180h.
2. the preparation method of a kind of mixed valence vanadium oxide nano material described in a claim 1, it is characterised in that: will containing VO2+Compound and containing VO3 -Compound, make certain density mother solution after being scattered in deionized water respectively;
VO in A mother solution2+Ion concentration is: 0.008～1.0mol/L;
VO in B mother solution3 -Ion concentration is: 0.02～2.2mol/L;
Under 10～160 DEG C of mixing temperatures, under certain mixing condition, by VO2+/VO3 -Molar ratio for 1:1.4～1:2.4 mixes, and is placed in synthesis reactor, airtight, then rises to 60～200 DEG C with the heating rate of 1～20 DEG C/min, stands 2～180h.
3. the preparation method described in claim 2, it is characterised in that: described containing VO2+Compound is one or more in vanadium oxysulfate, divanadyl tetrachloride, vanadyl oxalate, vanadyl acetylacetonate;
Described containing VO3 -Compound be NaVO3,NH4VO3,KVO3One or more.
4. the preparation method described in claim 2, it is characterised in that:
Described containing VO2+Compound is one or more in vanadium oxysulfate, vanadyl acetylacetonate;
Described containing VO3 -Compound be NH4VO3, NaVO3One or more.
5. the preparation method described in claim 2,3 or 4, it is characterised in that: mixing temperature is 10 DEG C～80 DEG C, and heating rate is 1～10 DEG C/min;
Dwell temperature is: 60 DEG C～180 DEG C, and time of repose is: 4h～180h.
6. the preparation method described in claim 5, it is characterised in that: mixing temperature is 25 DEG C～60 DEG C, and programming rate is 5～10 DEG C/min
Dwell temperature is: 80 DEG C～160 DEG C, and time of repose is: 8h～72h.
7. the preparation method described in claim 2,3 or 4, it is characterised in that:
VO in A mother solution2+Ion concentration is: 0.008～0.24mol/L;
VO in B mother solution3 -Ion concentration is: 0.02～0.5mol/L.
8. the preparation method described in claim 5, it is characterised in that:
VO in A mother solution2+Ion concentration is: 0.008～0.14mol/L;
VO in B mother solution3 -Ion concentration is: 0.02～0.2mol/L.
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| 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 |
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| 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 |
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