CN102530946A - Preparation method of phosphosilicate solid with high coordination number silicon atom - Google Patents
Preparation method of phosphosilicate solid with high coordination number silicon atom Download PDFInfo
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- CN102530946A CN102530946A CN2011104451266A CN201110445126A CN102530946A CN 102530946 A CN102530946 A CN 102530946A CN 2011104451266 A CN2011104451266 A CN 2011104451266A CN 201110445126 A CN201110445126 A CN 201110445126A CN 102530946 A CN102530946 A CN 102530946A
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Abstract
The invention relates to a preparation method of a phosphosilicate solid with a high coordination number silicon atom, which is characterized in that the method comprises the following steps: mixing a phosphorus precursor, a silicon precursor and a calcium precursor together to prepare a gel precursor sol solution in the presence of solvents; standing the gel precursor sol solution at room temperature to gel, aging, sintering and calcining to obtain the phosphosilicate solid. Polyhydric-alcohol such as inositol is employed by the method of the invention, which is helpful for the formation of high coordination number silicon, so that the phosphosilicate solid with a high coordination number silicon atom can be obtained.
Description
Technical field
The invention belongs to field of materials, particularly contain the silicophosphate solid preparation method of high ligancy Siliciumatom.
Background technology
At occurring in nature, Siliciumatom generally is that the form with four-coordination silicon exists, and having only minority is that form with high ligancy silicon exists, for example the stishovite that forms down of high pressure.But, in synthetic materials research in recent years, find that 5,6 coordination silicon can form under normal pressure, find also that simultaneously high coordination silicon all has certain influence to the structure and the performance of material, can make ultraviolet absorption peak generation red shift like high coordination silicon.Therefore, new synthetic route and new high coordination silicon materials still need further to study.
For the synthetic materials in the solution, most high coordination silicon mainly is and N, F or Cl coordinate to have only only a few to be and the O coordination.Through changing external stimulus, can change the ligancy of Siliciumatom like temperature, solvent and irradiation intensity, elevated temperature can make 5 coordinate silicon increase, co-conversion mutually between 5 coordination silicon and the 6 coordination silicon under radiation parameter.In addition, if in system, introduce polyvalent alcohol then help improving the probability that high coordination silicon forms, this is because polyvalent alcohol can impel O and Siliciumatom coordination, thereby forms high coordination silicon.
Less about the research report of solid-state high coordination silicon materials at present, these solid-state materials are under high temperature or condition of high voltage, to form high coordination silicon mostly.Glass material can make the silicon ligancy in the material change 6 into by 4 under pyroprocessing, and mainly the form with Si-O-P or Si-O-Si exists, and along with the increase of P content, 6 coordination silicon increase, and after bakingout process, these glass materials can form crystallization.And occur as yet about the research of the solid material of the silicon that contains high ligancy Siliciumatom under middle low temperature, the normal pressure.
Based on above-mentioned research, polyvalent alcohol helps forming high coordinate silicon in the solution, in solid-state material, introduces the formation that polyvalent alcohol might influence high coordination silicon through sol-gel method.This patent has reported that a kind of Prepared by Sol Gel Method contains the silicophosphate solid method of high ligancy Siliciumatom, promptly in system, introduces a kind of presoma that contains multi-hydroxy.
Summary of the invention
The purpose of this invention is to provide a kind of silicophosphate solid method that adopts the cryosol gel method to synthesize to contain high ligancy Siliciumatom.Because need usually under high temperature or condition of high voltage, just can help forming high coordination silicon, but the present invention can provide the high coordination silicon of reaction formation under low temperature, the low pressure, this is its characteristic that is superior to additive method.
The present invention realizes through following technical scheme:
A kind of silicophosphate solid preparation method is characterized in that, in the presence of solvent, phosphorus presoma and silicon precursor is hybridly prepared into the Gel Precursor sol solution; The Gel Precursor sol solution of preparation is at room temperature placed up to gel, and obtained the silicophosphate solid through ageing, sintering, calcining.
Preferably,, presoma also adds basic metal presoma or earth alkali metal presoma when mixing, for example calcium presoma, sodium presoma, potassium presoma, magnesium presoma and zinc precursor body.More preferably, add the calcium presoma.Do not add this type presoma and do not influence the formation of high coordination silicon.But can be after adding so that material has different purposes, such as being used as the better optical material of performance, biomaterial etc.
More preferably, the present invention provides a kind of silicophosphate solid preparation method, it is characterized in that, in the presence of solvent, with the phosphorus presoma, silicon precursor and calcium presoma are hybridly prepared into the Gel Precursor sol solution; The Gel Precursor sol solution of preparation is at room temperature placed up to gel, and obtained the silicophosphate solid through ageing, sintering, calcining.
Based on the present invention, the time that forms gel needs 1～10 day usually, and preferred 2-8 days, more preferably 3-5 days.
According to the present invention, said aging step comprises at a certain temperature, preferred 30-100 ℃, and more preferably under 40-60 ℃, ageing for some time, preferably more than 1 day, more preferably 3-10 days, also more preferably 5-7 days.
According to the present invention, said sintering step comprises, the gel after the ageing is put into baking oven carry out sintering; Preferably toast for some time in the baking oven about 120 ℃, preferred 10 minutes-20 days, more preferably 2-14 days; Also more preferably 7-14 days, solvent is wherein all volatilized.
The sample that the sol-gel method that the present invention adopted obtains is 300～700 ℃ of calcinings down.
According to the present invention, said calcining step comprises, the gel behind the sintering is reduced to room temperature, and then to be warming up to temperature by room temperature be 300～700 ℃, calcines for preferred 300-400 ℃, obtains xerogel.
According to the present invention, said calcining step also further comprises, is 300～700 ℃ with above-mentioned xerogel in temperature; Under preferred 300-400 ℃, calcined 10 minutes preferred 1-5 hour at least like constant temperature in tube furnace; More preferably naturally cooling after 2-3 hour, thus the silicophosphate solid obtained.
According to the present invention, preferably before each presoma mixes, earlier the phosphorus presoma is mixed with polyvalent alcohol.
According to the present invention; Preferred phosphorus presoma can be phosphoric acid; Butyl phosphate, triethyl phosphate, Vanadium Pentoxide in FLAKES, phytic acid etc., wherein phytic acid is that six hydroxyls on a kind of inositol are replaced the material that obtains by six phosphate groups, also is a kind of phosphorous presoma; It can obtain through inositol and Vanadium Pentoxide in FLAKES reaction, and both press the equivalent mol ratio and obtain at 1: 3.
According to the present invention; The phosphorus presoma can be by also can be at phosphoric acid; Introduce multiple polyvalent alcohol in the materials such as butyl phosphate, triethyl phosphate, Vanadium Pentoxide in FLAKES or phytic acid; Like inositol, melampyrum, N.F,USP MANNITOL, sorbyl alcohol, arabitol, Xylitol, pentitol, erythritol or threitol, thus with the reactant of its formation as the phosphorus presoma.More preferably the phosphorus presoma is selected from phosphoric acid, the reactant of the reactant of phytic acid, phosphoric acid and inositol or Vanadium Pentoxide in FLAKES and inositol.This system can promote the formation of high coordination silicon.Above-mentioned following assisting of polyhydroxy-alcohol, can prepare the silicophosphate solid that contains high ligancy Siliciumatom at a lower temperature.The phosphorus presoma that for example forms after the reaction of phosphoric acid and inositol, this is because phosphoric acid and inositol reaction make that the hydroxyl on the inositol is replaced by phosphate, thereby more help the formation of high coordination silicon.
According to the present invention, the presoma of preferred silicon is selected from this area silicon precursor commonly used, more preferably tetraethoxy (TEOS), methyl silicate etc.
According to the present invention, preferably with four water-calcium nitrate (Ca (NO
3)
24H
2O), nitrocalcite or calcium chloride are as the precursor of calcium.Oxide compound is Na in sodium presoma, potassium presoma, magnesium presoma and the zinc precursor body
2O, K
2The corresponding compounds of MOX such as O, MgO and ZnO, for example Repone K, sodium methoxide, zinc nitrate and magnesium nitrate etc.
Said reaction solvent is a reaction medium water, ethanol, or the mixture of second alcohol and water.
According to optimal technical scheme of the present invention, wherein: the phosphorus presoma, silicon precursor, the add-on of calcium presoma is through the P in the silicophosphate solid
2O
5, SiO
2Embody the P in the gained silicophosphate solid with the molar content of CaO
2O
5Molar content be 15%～90%, preferred 25%-70%, more preferably 30-60%.SiO
2Molar content be 10%～60%, preferred 15%-55%, more preferably 20-50%.The molar content of CaO is 0～55%, preferred 0%-45%, more preferably 0-35%.
According to the present invention, for obtaining containing the silicophosphate solid of high ligancy Siliciumatom, wherein P
2O
5And SiO
2The molar content of mol ratio and CaO the formation of high coordination silicon is had very big influence.More preferably P
2O
5/ SiO
2Molar ratio be 0.2-15, preferred 0.5～9.
The silicophosphate solid that contains high coordination Siliciumatom number of the present invention's preparation is along with the increase of phosphorus content, and the high coordination silicon of formation increases.
Of the present invention temperature is warming up to temperature by room temperature is 300～700 ℃, is in air, to carry out.
The characteristics that contain the silicophosphate solid preparation method of high ligancy Siliciumatom provided by the invention are:
1) the phosphorous presoma that the present invention selected for use itself just can the catalysis solgel reaction, does not need the extra catalyzer that adds again.
2) the present invention is following assisting of polyhydroxy-alcohol, can prepare the silicophosphate solid that contains high ligancy Siliciumatom at a lower temperature.
3) the resulting silicophosphate solid material that contains high ligancy Siliciumatom of the present invention is the adjustable amorphous material of multi-component composition, also can be crystal.
Description of drawings
Fig. 1 and Fig. 2 are the XRD diffractogram of the silicophosphate solid sample that obtains among the embodiment of the invention 1-3.
Fig. 3 and 4 NMR figure for the silicophosphate solid sample that obtains among the embodiment of the invention 1-3.
Fig. 5 is the NMR figure of the silicophosphate solid sample that obtains in the embodiment of the invention 4.
In the XRD diffracting spectrum and NMR collection of illustrative plates among the accompanying drawing 1-5, through the XRD diffracting spectrum can test material whether crystallization, through NMR can test material in the coordination situation of silicon, as-106ppm--120ppm is a four-coordination silicon, and-be hexa-coordinate silicon about 213ppm.
Embodiment
Protection scope of the present invention is not limited only to above embodiment.According to content disclosed by the invention, those skilled in the art will recognize that under the situation that does not break away from given technical characterictic of technical scheme of the present invention and scope, the above embodiment is made many variations and revises all belong to protection scope of the present invention.
Embodiment 1: the preparation of silicophosphate solid
According to the P in the preparation table 1 silicophosphate solid sample
2O
5, SiO
2With the CaO molar content, the presoma (phosphoric acid, tetraethoxy and four water-calcium nitrate) of corresponding content is mixed with Gel Precursor solution (changing four water-calcium nitrate into calcium chloride or nitrocalcite does not all influence the result).At first, get presoma phosphoric acid in the sample bottle of 10ml, add tetraethoxy (TEOS) then successively, second alcohol and water (volume ratio is about 1: 1, and add-on gets final product can dissolve aforementioned presoma) stirs 30min, in whipping process, adds Ca (NO
3)
24H
2O is (because calcium chloride or nitrocalcite can carry out according to identical reaction conditions; And final through all existing after the calcining with the form of oxide compound, thereby content can not change, therefore; The four water-calcium nitrate here can also be calcium chloride or nitrocalcite), obtain the Gel Precursor sol solution.The Gel Precursor sol solution of preparation at room temperature placed up to gel (needs 2～10 days usually; Depend on the ratio between each presoma); Gel was put into 60 ℃ of baking oven ageings more than 1 day; And then put into the baking of 120 ℃ of baking ovens solvent is wherein all volatilized, be cooled to room temperature.In air, the temperature of tube furnace is warmed up to 300～700 ℃ by room temperature with the heat-up rate of 5 ℃/min, constant temperature in the tube furnace of gel under 300 ℃～700 ℃ of doing is carried out sintering naturally cooling after at least 10 minutes, obtain the silicophosphate solid sample.
Wherein, contain pairing P in the silicophosphate solid sample of high ligancy Siliciumatom
2O
5, SiO
2As shown in table 1 with the molar content of CaO;
Table 1: the P in the different samples
2O
5, SiO
2With the CaO molar content
| Sample | P 2O 5 | SiO 2 | CaO | P 2O 5∶SiO 2Mol ratio |
| 1 | 53.4％ | 24.4％ | 22.2％ | 2.2 |
| 2 | 35.9％ | 49.4％ | 14.7％ | 0.7 |
Embodiment 2: the preparation of silicophosphate solid
According to the method among the embodiment 1, phosphorous presoma phosphoric acid is replaced with triethyl phosphate, butyl phosphate, phytic acid respectively, the P that it has identical mol ratio with phosphoric acid
2O
5, other process is identical, obtains silicophosphate solid sample 1 and sample 2 respectively.
Embodiment 3: the preparation of silicophosphate solid
According to the method in embodiment 1 and 2, in triethyl phosphate, butyl phosphate, phytic acid and phosphoric acid, add inositol (IS) respectively, P in itself and the phosphorous presoma
2O
5Mol ratio be 1/3, other process is identical, obtains silicophosphate solid sample 1 and sample 2.Wherein introduce inositol in phosphoric acid and the triethyl phosphate in the sample 1, introduced inositol in phytic acid, butyl phosphate and the triethyl phosphate in the sample 2.
Embodiment 4: the preparation of silicophosphate solid
According to the method among the embodiment 1, phosphorous presoma phosphoric acid is replaced with the substituent (reactant of inositol and Vanadium Pentoxide in FLAKES) of inositol and inositol respectively, be respectively and 2 replace, 4 replace and 6 replace, other process is identical, obtains silicophosphate solid sample 1.
Experimental example 1: the silicophosphate solid form detects (XRD)
With the silicophosphate solid sample grinding powder that obtains in embodiment 1,2 and 3, with the whether crystallization of XRD test material, its detected result is as depicted in figs. 1 and 2.Be crystalline as the silicophosphate solid of the presoma formation of phosphorus wherein with phosphoric acid, butyl phosphate; Still is crystalline introducing inositol (IS) back phosphoric acid as the phosphorus silicic acid solid that presoma obtains, and the silicophosphate solid that butyl phosphate obtains as presoma is unbodied.And phytic acid, triethyl phosphate be as the presoma of phosphorus, and the silicophosphate solid of sample 1 and 2 two components of sample is unbodied.
Experimental example 2: the silicon ligancy detects (NMR) in the silicophosphate solid
With the silicophosphate solid sample grinding powder that obtains in embodiment 1,2,3 and 4, with the coordination situation of solid NMR test material, its detected result such as Fig. 3, Fig. 4, shown in Figure 5.As can be seen from Figure 3, with the presoma of phosphoric acid, during forming, sample 1 do not have the formation of 6 coordination silicon as phosphorus.After in system, introducing inositol (IS), find to have the formation of 6 coordination silicon, explain that the introducing of inositol in phosphoric acid helps forming 6 coordination silicon, this possibly be to have formed phytic acid owing to react between the two.From Fig. 3, Fig. 4, can find out, adopt the presoma of phytic acid as phosphorus, the formation of 6 coordination silicon is all arranged during sample 1 is formed with sample 2, and the 6 coordination silicon that form in the sample 1 be many, this possibly cause than higher owing to its phosphorus content.Butyl phosphate has the formation of a small amount of 6 coordination silicon as the presoma of phosphorus in sample 2 is formed, and adopts triethyl phosphate not have the formation of 6 coordination silicon.After in system, introducing inositol (IS), butyl phosphate and triethyl phosphate all do not form hexa-coordinate silicon with inositol (IS) blend as the presoma of phosphorus respectively.Through relatively finding with Fig. 1 and Fig. 2; It is crystalline that butyl phosphate and phosphoric acid and inositol blend form high coordination silicophosphate solid sample as the presoma of phosphorus respectively, and phytic acid is unbodied as the high coordination silicophosphate solid that the presoma of phosphorus forms.
As can be seen from Figure 5, the increase along with inositol (IS) is gone up phosphoric acid replacement amount forms 6 coordinate silicon more easily.
Claims (10)
1. a silicophosphate solid preparation method is characterized in that, in the presence of solvent, phosphorus presoma and silicon precursor is hybridly prepared into the Gel Precursor sol solution; The Gel Precursor sol solution of preparation is at room temperature placed up to gel, and obtained the silicophosphate solid through ageing, sintering, calcining.Preferably,, presoma also adds basic metal presoma or earth alkali metal presoma when mixing, for example calcium presoma, sodium presoma, potassium presoma, magnesium presoma and zinc precursor body etc.
2. according to the preparation method of claim 1, it is characterized in that in the presence of solvent, with the phosphorus presoma, silicon precursor and calcium presoma are hybridly prepared into the Gel Precursor sol solution; The Gel Precursor sol solution of preparation is at room temperature placed up to gel, and obtained the silicophosphate solid through ageing, sintering, calcining.
3. according to the method for claim 1 or 2, it is characterized in that said aging step comprises at a certain temperature, preferred 30-100 ℃, more preferably under 40-60 ℃, ageing for some time, preferably more than 1 day, more preferably 3-10 days, also more preferably 5-7 days.
4. according to each method of claim 1-3, it is characterized in that said sintering step comprises; Gel after the ageing is put into baking oven carry out sintering; Preferably toast for some time in the baking oven about 120 ℃, preferred 10 minutes-20 days, more preferably 2-14 days; Also more preferably 7-14 days, solvent is wherein all volatilized.
5. according to each method of claim 1-4, it is characterized in that the sample that the sol-gel method that is adopted obtains is 300～700 ℃ of calcinings down.Preferred calcining step comprises, the gel behind the sintering is reduced to room temperature, and then to be warming up to temperature by room temperature be 300～700 ℃, calcines for preferred 300-400 ℃, obtains xerogel.Optional said calcining step also further comprises, is 300～700 ℃ with above-mentioned xerogel in temperature, under preferred 300-400 ℃; Calcined at least 10 minutes like constant temperature in tube furnace; Preferred 1-5 hour, more preferably naturally cooling after 2-3 hour, thus obtain the silicophosphate solid.
6. according to each method of claim 1-5, it is characterized in that said phosphorus presoma is selected from phosphoric acid, butyl phosphate, triethyl phosphate, Vanadium Pentoxide in FLAKES, phytic acid.Preferably; Said phosphorus presoma can also be in phosphoric acid, butyl phosphate, triethyl phosphate, Vanadium Pentoxide in FLAKES or phytic acid separately or mix and introduce polyvalent alcohol; Like inositol, melampyrum, N.F,USP MANNITOL, sorbyl alcohol, arabitol, Xylitol, pentitol, erythritol or threitol, thus with the reactant of its formation as the phosphorus presoma.More preferably the phosphorus presoma is selected from phosphoric acid, the reactant of the reactant of phytic acid, phosphoric acid and inositol or Vanadium Pentoxide in FLAKES and inositol.
7. according to each method of claim 1-6, it is characterized in that said silicon precursor is selected from tetraethoxy (TEOS) or methyl silicate.
8. according to each method of claim 1-7, it is characterized in that said calcium presoma is selected from four water-calcium nitrate, nitrocalcite, calcium chloride.
9. according to each method of claim 1-8, it is characterized in that said reaction solvent is a water, ethanol, or the mixture of second alcohol and water.
10. according to each method of claim 1-9, it is characterized in that, with the P in the silicophosphate solid
2O
5, SiO
2With the molar content of CaO be benchmark, the P in the resulting silicophosphate solid
2O
5Molar content be 15%～90%, preferred 25%-70%, more preferably 30-60%.SiO
2Molar content be 10%～60%, preferred 15%-55%, more preferably 20-50%.The molar content of CaO is 0～55%, preferred 0%-45%, more preferably 0-35%.More preferably P
2O
5/ SiO
2Molar ratio be 0.2-15, preferred 0.5～9.
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| CN101921061A (en) * | 2010-08-06 | 2010-12-22 | 中国科学院化学研究所 | Method for preparing phosphosilicate based glass |
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| CN101921061A (en) * | 2010-08-06 | 2010-12-22 | 中国科学院化学研究所 | Method for preparing phosphosilicate based glass |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106362214A (en) * | 2016-08-24 | 2017-02-01 | 北京幸福益生高新技术有限公司 | Regenerated silicon material as well as preparation method and application thereof |
| KR20190067775A (en) * | 2016-08-24 | 2019-06-17 | 팡 후 | Regenerative Medicine Materials and Methods of Making and Application |
| KR102258806B1 (en) | 2016-08-24 | 2021-06-01 | 팡 후 | Regenerative medicine material and its manufacturing method and application |
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