CN102602999B - Synthesis method for peroxide complex of vanadium and application of peroxide complex of vanadium - Google Patents
Synthesis method for peroxide complex of vanadium and application of peroxide complex of vanadium Download PDFInfo
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- CN102602999B CN102602999B CN201110027264.2A CN201110027264A CN102602999B CN 102602999 B CN102602999 B CN 102602999B CN 201110027264 A CN201110027264 A CN 201110027264A CN 102602999 B CN102602999 B CN 102602999B
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Abstract
The invention discloses a peroxide complex of vanadium, a preparation method and application of the peroxide complex of vanadium. The peroxide complex of vanadium is prepared by the following steps: dissolving carboxylic acid with hydroxyl in hydrogen peroxide, regulating the pH value of the solution by ammonia water to be larger than 7; adding vanadyl sulfate in the solution to obtain the reaction solution; after reaction, adding an organic solvent; standing to generate precipitate; and separating the precipitate from the solution to obtain the peroxide complex of vanadium. The novel synthesis method for the peroxide complex of vanadium provided by the invention is cheap in price of raw materials, low in toxicity, simple in preparation process and short in time consumption. The obtained peroxide complex of vanadium can be used for preparing vanadium dioxide powder and vanadium dioxide film, so that the selective range of raw materials for preparing the vanadium dioxide powder and the vanadium dioxide film is extended, and vanadium dioxide powder containing phase A is further obtained.
Description
Technical field
The synthetic method of crossing oxygen complex that the present invention relates to a kind of vanadium, belongs to title complex synthetic chemistry field.
Background technology
The oxygen complex of crossing of vanadium refers to a class vanadium compound that includes peroxy-radical part.This compounds is everlasting in organic synthesis and is used as catalyzer and oxygenant, so that reaction can be under mild conditions fast, optionally carry out [(1) Tao Chunyuan, Zhao Xinping, Wang Chuanwang. cross vanadyl organic coordination compound and the application in organic synthesis thereof. chemical reagent, 2005,27 (12), 726-728].This class title complex can also swash intravital insulin receptor enzyme simultaneously, can play and fall hypoglycemic effect, is expected to medicine [(1) the Shaver A. as treatment diabetes; Ng J.B.; Hall D.A.; Lum B.S.; Posner B.I., InorganicChemistry 1993,32 (14), 3109-3113. (2) Posner, B.I.; Faure, R.; Burgess, J.W., et al.Journal of Biological Chemistry, 1994,269 (6), 4596-4604.].
Except above application, the oxygen complex of crossing of vanadium also can be used as a kind of precursor, is used for synthesizing the oxide compound of vanadium.The oxide compound of vanadium serves many purposes, as vanadium dioxide (VO
2) can near 68 ℃, undergo phase transition, in phase transformation, VO
2the physicals such as optical transmittance, resistivity, susceptibility also can undergo mutation, therefore, VO
2can be used as [(1) Parkin, the I.P. such as temperature control smart window, sensor, storage media; Manning, T.D., Journal of Chemical Education2006,83 (3), 393-400. (2) Cao C.X.; Gao Y.F.; Luo H.J., Journal of Physical ChemistryC 2008,112,18810-18814. (3) Kang L.T., Gao Y.F., Luo H.J., Acs Applied Materials & Interfaces 2009,1,2211-2218.].And the recently people's such as Li research shows, take vanadium to cross oxygen complex be precursor, can be to VO
2the pattern of powder, size etc. regulate and control [(1) Li, G.C.; Chao, K.; Zhang, C.Q.; Zhang, Q.S.; Peng, H.R.; Chen, K.Z., Inorganic Chemistry 2009,48 (3), 1168-1172. (2) Nguyen, T.D.; Do, T.O., Langmuir 2009,25 (9), 5322-5332.].
The diversity of crossing oxygen complex kind and purposes in view of vanadium, with cheap, hypotoxic raw material, through simple technique, synthesize the oxygen complex of crossing of new vanadium, and being used in some specific organic synthesis as catalyzer of take, or take as precursor, control the oxide compound of synthetic vanadium, possess certain theory and the exploration meaning in practical application.
Summary of the invention
The object of the present invention is to provide a kind of oxygen complex and synthetic method thereof excessively of new vanadium, to expand the material choice scope of preparing hypovanadic oxide powder and vanadium dioxide film, and further obtain the hypovanadic oxide powder with new feature (containing A phase).
The technical solution used in the present invention is: a kind of preparation method who crosses oxygen complex of vanadium, comprises step: hydroxyl carboxylic acid is dissolved in hydrogen peroxide, and is greater than 7 by the pH value of ammoniacal liquor regulator solution; Then add vanadylic sulfate, obtain reaction soln, after react, add organic solvent, standing, generate precipitation, precipitation separation, obtains the mistake oxygen complex of vanadium.
Preferably, the mass concentration of described hydrogen peroxide is 6-30%.
Preferably, described hydroxyl carboxylic acid than for 0.01-3mol/L, is preferably 0.05-0.4mol/L with the molecular volume of described hydrogen peroxide.
Preferably, described hydroxyl carboxylic acid is selected from citric acid, tartrate and oxysuccinic acid.
Preferably, with ammoniacal liquor, regulating the pH value of described solution is 10-14.
The mass concentration of described ammoniacal liquor is 25%-30%.
Preferably, described vanadylic sulfate than for 0.01-2mol/L, is preferably 0.02-0.2mol/L with the molecular volume of described hydrogen peroxide.
Preferably, the temperature of described reaction is no more than 20 ℃, more preferably 0-15 ℃.
Preferably, the time of described reaction is more than 30 minutes, more preferably 2-4 hour.
Preferably, described organism is water soluble organic substance, and more preferably alcohol or ketone, as ethanol, Virahol, acetone etc.The consumption of described organic solvent is 0.5-5 times of reaction soln volume.
Described time of repose is no less than 1 hour, more preferably 4-20 hour, more preferably 4-8 hour.
The present invention also further discloses the oxygen complex of crossing that adopts vanadium that aforesaid method obtains, in a preferred embodiment disclosed by the invention, products therefrom detects its composition and content with ultimate analysis and inductively coupled plasma emmission spectrum, utilize the functional group comprising in Raman, Infrared spectroscopy product, can infer that the molecular formula that products therefrom is V
2n
3 ± xh
14 ± yo
4 ± z(span of z is 0 to 1 for x, y), and include peroxy-radical in its structural formula.Therefore, determine the oxygen complex of crossing that adopts product that aforesaid method of the present invention obtains to be vanadium.
The synthetic method of crossing oxygen complex of above-mentioned a kind of new vanadium provided by the present invention, cost of material used is cheap, toxicity is low, and its preparation technology is simple, consuming time few.The oxygen complex excessively of the vanadium that in addition, the present invention obtains is at VO
2the preparation aspect of powder and film, has following advantages:
1) can be applied to prepare VO simultaneously
2powder and VO
2film; At present simultaneously for the preparation of VO
2the conventional raw material of the vanadium of powder and film is V
2o
5, and other raw materials (as alkoxide of vanadium etc.), be just used for separately preparing VO
2powder or VO
2film;
2) price comparison is cheap, and toxicity is relatively little; Generally speaking, containing the raw material of vanadium, all price comparison is expensive, and toxicity is larger, and the present invention used be all low price, raw material that toxicity is low;
3) oxygen complex excessively of the vanadium that the present invention obtains is water miscible, is easy to use, and is particularly suitable for preparing VO in liquid-phase system
2powder and film; And V
2o
5solubleness in water is low, at preparation VO
2during film, often to after making it to melt, high temperature (approaching 1000 degree) become the liquid follow-up processing of carrying out again.And the oxygen complex of crossing of vanadium of the present invention does not need pyroprocessing, can carry out easily follow-up processing after water-soluble.Therefore, the invention also discloses a kind of purposes of oxygen complex excessively of above-mentioned vanadium, i.e. the application of oxygen complex excessively in preparing hypovanadic oxide powder or vanadium dioxide film of described vanadium.Further, the thing of described hypovanadic oxide powder is that M phase coexists mutually with A when lower than 68 ℃.
When adopting the peroxide complex preparation hypovanadic oxide powder of vanadium of the present invention, the described method of preparing hypovanadic oxide powder, comprises the steps: oxygen complex excessively and the reductive agent of above-mentioned vanadium to be added to the water the formation aqueous solution, obtains VO after hydrothermal treatment consists
2powder.
Preferably, the mass volume ratio of crossing oxygen complex and water of described vanadium is 1g/L-7g/L.
Preferably, described reductive agent is selected from oxalic acid, citric acid or ethanol.
Preferably, the consumption of described reductive agent is the 0.3-2.0 that crosses oxygen complex times (weight ratio) of vanadium.
Preferably, during described hydrothermal treatment consists, in reactor, the filling proportion of the aqueous solution is 50%-90%, more preferably 70%-85%.
Preferably, the temperature of described hydrothermal treatment consists is higher than 160 ℃, more preferably 180-260 ℃; The hydro-thermal reaction time is more than 10 hours, more preferably 24-72 hour.
The present invention also further discloses the hypovanadic oxide powder that adopts aforesaid method to obtain, and the thing of this hypovanadic oxide powder is that M phase coexists mutually with A when lower than 68 ℃.
Adopt the superoxide of above-mentioned vanadium provided by the present invention to prepare VO
2powder, related technique is simple, and the thing of product can be regulated and controled mutually, and can obtain reporting in document less A phase VO
2powder; Due at present to A phase VO
2performance solve seldom, and adopt the present invention can prepare A phase VO
2, can be just research A phase VO
2starting material are provided, possess potential scientific research meaning.In addition the precursor that oxygen complex can be used as the vanadium that a class is new of crossing that, also further illustrates vanadium is prepared VO
2powder.
When adopting the peroxide complex preparation vanadium dioxide film of vanadium of the present invention, the described method of preparing vanadium dioxide film, comprise the steps: above-mentioned vanadium to cross oxygen complex and the additive formation aqueous solution that is dissolved in the water, described aqueous solution plated film, on substrate, is then after heat treatment obtained to vanadium dioxide film in inert atmosphere.
Preferably, the mass volume ratio of crossing oxygen complex and water of described vanadium is 10g/L-100g/L, more preferably 20-100g/L.
Preferably, described additive is water soluble organic substance, more preferably polyvinylpyrrolidone or cetyl trimethylammonium bromide.
Preferably, the mass volume ratio of described additive and water is 20g/L-120g/L, more preferably 20-100g/L.
Conventional film coating method in this areas such as the described method on substrate by aqueous solution plated film comprises spin-coating, lifts, spray pyrolysis, more preferably spin-coating.
Described substrate is that ability is higher than the substrate of 350 ℃ of temperature, more preferably silica glass.
Described thermal treatment temp is higher than 350 ℃, 450-600 ℃ more preferably, and heat treatment time surpasses 20 minutes, more preferably 20-240 minute, more preferably 20-180 minute.
Described inert atmosphere is preferably nitrogen or argon gas etc.
The vanadium dioxide film that adopts above-mentioned preparation method to obtain, utilizes the analysis means such as XRD, Raman to characterize mutually its thing in room temperature, be at room temperature mainly M phase VO2; Utilize ultraviolet-visible-infrared spectrophotometer to test the optical transmittance of this film at 240-2600nm wave band, wherein visible ray (500-800nm wave band) transmitance surpasses 35%, in 2000nm place infrared light adjusting function, surpasses 25%.
Adopt the superoxide of above-mentioned vanadium provided by the present invention to prepare vanadium dioxide film, related technique is simple, and gained Film Optics performance of control is good.Meanwhile, the present invention has also illustrated that the precursor that oxygen complex can be used as the vanadium that a class is new of crossing of vanadium provided by the present invention prepares vanadium dioxide film.
To sum up, the invention has the beneficial effects as follows: the synthetic method of crossing oxygen complex of a kind of new vanadium provided by the present invention, cost of material used is cheap, toxicity is low, and its preparation technology is simple, consuming time few.The oxygen complex of crossing of the vanadium obtaining can be expanded and prepare the material choice scope of hypovanadic oxide powder and vanadium dioxide film simultaneously for the preparation of hypovanadic oxide powder and film, and has further obtained the hypovanadic oxide powder containing A phase.
Accompanying drawing explanation
Fig. 1 is the Raman collection of illustrative plates of embodiment 1 products therefrom, at 885cm
-1, 608cm
-1, 526cm
-1the peak at the place characteristic peak that is peroxy-radical, shows to contain in product peroxy-radical.971cm
-1the peak at place is the characteristic peak of V=O key.
Fig. 2 is the infared spectrum of embodiment 1 products therefrom, at 870cm
-1, 610cm
-1, 523cm
-1the characteristic peak that the peak at place is peroxy-radical, 950cm
-1the peak at place is the characteristic peak of V=O key.
Fig. 3 is the TG-DSC curve of embodiment 1 products therefrom in nitrogen atmosphere.
Fig. 4 is embodiment 4 gained VO
2the XRD figure spectrum of powder, shows that product is A phase and M phase VO
2coexist.
Fig. 5 is embodiment 4 gained VO
2the TEM figure of powder, shows product nano bar-shape structure.
Fig. 6 is embodiment 4 gained VO
2dSC curve in the temperature-rise period of powder, shows to contain in product M phase VO
2, transformation temperature is near 66 ℃.
Fig. 7 is embodiment 7 gained VO
2the Raman collection of illustrative plates of film, shows that thing is M phase VO mutually
2.
Fig. 8 is embodiment 7 gained VO
2the SEM figure of film, shows that film is dense.
Fig. 9 is embodiment 7 gained VO
2film is crossed curve the optical lens of 30,90 ℃, and the infrared light regulation rate that the transmitance that shows visible ray (500-800nm wave band) surpasses 40%, 2000nm place is 38%.
Embodiment
Embodiment 1
In the hydrogen peroxide that is 30% in 50 milliliters of massfractions, add 2.10 grams of citric acids, with ammoniacal liquor, pH value is adjusted to 10, above-mentioned solution is placed in to ice-water bath, slowly add 1.63 grams of vanadylic sulfates, stir after 2 hours, add 50 milliliters of ethanol also standing 4 hours, will after the sedimentation and filtration separation of gained, obtain the oxygen complex of crossing of vanadium.
The Raman collection of illustrative plates of the present embodiment products therefrom is as shown in Figure 1: at 885cm
-1, 608cm
-1, 526cm
-1the peak at the place characteristic peak that is peroxy-radical, shows to contain in product peroxy-radical.971cm
-1the peak at place is the characteristic peak of V=O key.
The infared spectrum of the present embodiment products therefrom is as shown in Figure 2: at 870cm
-1, 610cm
-1, 523cm
-1the characteristic peak that the peak at place is peroxy-radical, 950cm
-1the peak at place is the characteristic peak of V=O key.
Above-mentioned analytical results shows, in the product that the present embodiment obtains, has peroxy-radical.
Composition analysis detected result is as follows:
With the quality percentage composition of the elements such as N, H, C in ultimate analysis instrument mensuration products therefrom, result is as follows: N 12.6%, and H 3.9%, and C, S do not detect.
The content that detects the V element in products therefrom with inductively coupled plasma transmitting emmission spectrum, result is: the quality percentage composition of V element is 30.6%.
Because the test of O element is more difficult, the element comprising according to starting material used only has C, H, O, N, S, V, the element in product also only has these, and the mass percent that therefore cuts N, H, V is the percentage composition 52.9% of O element afterwards.According to these results presumption molecular formula, some errors of introducing when considering instrument test and calculating, so infer that product consists of V
2n
3 ± xh
14 ± yo
11 ± z.
In addition, also product has been done in nitrogen atmosphere hot analysis (TG-DSC is shown in Fig. 3), according to TG-DSC curve, lost approximately 33% below 150 degree, this part is the water of physical adsorption and peroxide bridge fracture (near the exothermic peaks corresponding 129 degree); At 150-350 degree, lost approximately 18%, and the mass percent sum of N and H is 16.5%, this section be the release of corresponding N, H element probably; And loss approximately only has 2% more than 350 degree, illustrate that 350 degree have mainly been left V and O element later, i.e. the oxide compound of vanadium.Therefore, the result of TG-DSC tracing analysis also verifies that the elementary composition of product is V to a certain extent
2n
3 ± xh
14 ± yo
11 ± z(span of z is 0 to 1 for x, y).
Embodiment 2
The hydrogen peroxide that is 30% by 20 milliliters of massfractions is dissolved in 80 ml waters, add again 1.08 grams of tartrate, after pH value being adjusted to 12 with ammoniacal liquor, above-mentioned solution is placed in to ice-water bath, slowly add 0.78 gram of vanadylic sulfate, stir after 4 hours, add 120 milliliters of Virahols also standing 8 hours, will after the sedimentation and filtration separation of gained, obtain the oxygen complex of crossing of vanadium.
Utilize Raman, Infrared spectroscopy the present embodiment products therefrom, in infrared, Raman spectrum, all occurred the characteristic peak of peroxy-radical, so determine and wherein contain peroxy-radical.
Embodiment 3
In the hydrogen peroxide that is 30% in 50 milliliters of massfractions, add 2.40 grams of oxysuccinic acid, after pH value being adjusted to 14 with ammoniacal liquor, above-mentioned solution is placed in to ice-water bath, slowly add 1.96 grams of vanadylic sulfates, stir after 4 hours, add after 80 milliliters of acetone standing 6 hours, will after the sedimentation and filtration separation of gained, obtain the oxygen complex of crossing of vanadium.
Utilize the functional group comprising in Raman, Infrared spectroscopy the present embodiment products therefrom, in infrared, Raman spectrum, all occurred the characteristic peak of peroxy-radical, so determine and wherein contain peroxy-radical.
Embodiment 2 and 3 products therefroms are through ultimate analysis, and its products therefrom forms and meets general formula V
2n
3 ± xh
14 ± yo
11 ± z, wherein the value of x, y, z is all between 0-1.
Embodiment 4
Oxygen complex excessively and 0.03 gram of oxalic acid of 0.10 gram of embodiment, 1 gained vanadium are dissolved in 100 ml waters, then be placed in 120 milliliters of reactors, be incubated 24 hours after being warming up to 260 ℃, after naturally cooling, by after the black-and-blue sedimentation and filtration separation of gained, 80 ℃ of oven dry just obtain VO after 24 hours
2powder.
The present embodiment gained VO
2the XRD figure spectrum of powder as shown in Figure 4, shows that product is A phase and M phase VO
2coexist.
Embodiment 5
Oxygen complex excessively and 0.30 milliliter of ethanol of 0.30 gram of embodiment, 2 gained vanadium are dissolved in 90 ml waters, then be placed in 120 milliliters of reactors, be incubated 72 hours after being warming up to 180 ℃, after naturally cooling, by after the black-and-blue sedimentation and filtration separation of gained, 80 ℃ of oven dry just obtain VO after 24 hours
2powder.
The present embodiment gained VO
2powder is through the test of XRD diffraction analysis, and result shows that XRD figure spectrum is the characteristic peak of A phase and M phase, more approaching with the XRD figure spectrum in embodiment 4, shows that product is A phase and M phase VO
2coexist.
Embodiment 6
Oxygen complex excessively and 0.83 gram of citric acid of 0.66 gram of embodiment, 3 gained vanadium are dissolved in 100 ml waters, then be placed in 120 milliliters of reactors, be incubated 48 hours after being warming up to 230 ℃, after naturally cooling, by after the black-and-blue sedimentation and filtration separation of gained, 80 ℃ of oven dry just obtain VO after 24 hours
2powder.
The present embodiment gained VO
2powder is through the test of XRD diffraction analysis, and result shows that XRD figure spectrum is the characteristic peak of A phase and M phase, more approaching with the XRD figure spectrum in embodiment 4, shows that product is A phase and M phase VO
2coexist.
Embodiment 7
Oxygen complex excessively and 0.9 gram of polyvinylpyrrolidone (molecular-weight average is 1300000) of 0.3 gram of embodiment, 1 gained vanadium are dissolved in 15 ml waters, then by the method for spin-coating, above-mentioned solution is applied on silica glass substrate, this substrate is placed in to nitrogen atmosphere, heat-up rate with 15 ℃/min rises to 450 ℃ from room temperature, is incubated 180 minutes.Then naturally cooling, just obtains VO
2film.
Embodiment 8
Oxygen complex excessively and 0.3 gram of polyvinylpyrrolidone (molecular-weight average is 1300000) of 1.5 grams of embodiment, 2 gained vanadium are dissolved in 15 ml waters, then by the method lifting, above-mentioned solution is applied on silica glass substrate, this substrate is placed in to argon gas atmosphere, with 20 ℃/min, from room temperature, rise to 600 ℃, be incubated 20 minutes.Then naturally cooling, just obtains VO
2film.
Embodiment 9
Oxygen complex excessively and 0.4 gram of cetyl trimethylammonium bromide of 0.6 gram of embodiment, 3 gained vanadium are dissolved in 15 ml waters, then by the method for spin-coating, above-mentioned solution is applied on silica glass substrate, this substrate is placed in to argon gas atmosphere, with 20 ℃/min, from room temperature, rise to 500 ℃, be incubated 60 minutes.Then naturally cooling, just obtains VO
2film.
Claims (3)
1. a preparation method who crosses oxygen complex for vanadium, comprises the following steps: hydroxyl carboxylic acid is dissolved in hydrogen peroxide, and is greater than 7 by the pH value of ammoniacal liquor regulator solution; Then add vanadylic sulfate, obtain reaction soln, after react, add organic solvent, standing, generate precipitation, precipitation separation, obtains the mistake oxygen complex of vanadium; The mass concentration of described hydrogen peroxide is 6-30%; Described hydroxyl carboxylic acid is 0.01mol/L-3mol/L with the molecular volume ratio of described hydrogen peroxide; Described hydroxyl carboxylic acid is selected from citric acid, tartrate and oxysuccinic acid; Described vanadylic sulfate is 0.01mol/L-2mol/L with the molecular volume ratio of described hydrogen peroxide; Described organic solvent is water-miscible organic solvent; The temperature of described reaction is no more than 20 ℃; The time of described reaction is more than 30 minutes.
2. the purposes of crossing oxygen complex of the vanadium that a kind of preparation method who crosses oxygen complex of vanadium prepares as claimed in claim 1, is characterized in that the application in preparing hypovanadic oxide powder or vanadium dioxide film.
3. purposes as claimed in claim 2, is characterized in that, the thing of described hypovanadic oxide powder is that M phase coexists mutually with A when lower than 68 ℃.
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| CN108217727A (en) * | 2018-04-12 | 2018-06-29 | 四川星明能源环保科技有限公司 | A phase hypovanadic oxides and preparation method thereof |
| CN112266018A (en) * | 2020-10-16 | 2021-01-26 | 成都先进金属材料产业技术研究院有限公司 | Method for preparing nano vanadium dioxide by reverse hydrolysis precipitation |
| CN114672668B (en) * | 2022-04-06 | 2023-09-08 | 中南大学 | Method for preparing vanadium pentoxide by reducing precipitated vanadium and vanadium pentoxide and application |
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Non-Patent Citations (4)
| Title |
|---|
| Guicun Li et al..Synthesis of Urchin-like VO2 Nanostructures Composed of Radially Aligned Nanobelts and Their Disassembly.《Inorg. Chem.》.2009,第48卷(第3期),1168-1172. |
| M. Kaliva et al..pH-Dependent Investigations of Vanadium(V)-Peroxo-Malate Complexes from Aqueous Solutions. In Search of Biologically Relevant Vanadium(V)-Peroxo Species.《Inorg. Chem.》.2001,第40卷(第15期),3711-3718. |
| pH-Dependent Investigations of Vanadium(V)-Peroxo-Malate Complexes from Aqueous Solutions. In Search of Biologically Relevant Vanadium(V)-Peroxo Species;M. Kaliva et al.;《Inorg. Chem.》;20010619;第40卷(第15期);3711-3718 * |
| Synthesis of Urchin-like VO2 Nanostructures Composed of Radially Aligned Nanobelts and Their Disassembly;Guicun Li et al.;《Inorg. Chem.》;20090106;第48卷(第3期);1168-1172 * |
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