CN105685099A - Method for producing BiVO4-carried titanium oxide and antiviral composition - Google Patents
Method for producing BiVO4-carried titanium oxide and antiviral composition Download PDFInfo
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Abstract
The present invention provides a method for producing BiVO4-carried titanium oxide capable of presenting extremely excellent antiviral activity in light without ultraviolet light. According to the method for producing the BiVO4-carried titanium oxide, acidic suspension liquid including titanium oxide, bismuth ion, vanadate ion and solvent is processed by using a pulverizer to produce the BiVO4-carried titanium oxide. An antiviral composition of the present invention includes the BiVO4-carried titanium oxide produced by the method of the present invention and a cupric compound with the mass converted according to copper element of 0.1-20 parts by weight relative to the BiVO4-carried titanium oxide of 100 parts by weight.
Description
Technical field
The present invention relates to and be supported with BiVO4Titanium oxide manufacture method and containing being supported with BiVO4Titanium oxide and the antiviral property compositions of cupric compound。
Background technology
Having been found that in recent years and health is brought dysgenic new virus, the expansion of its infection is very troubling。As the material of the expansion preventing such viral infection disease, photocatalyst receives publicity (referring for example to patent documentation 1 and 2)。
Pucherite (is designated as " BiVO below4") it is widely known by the people (referring for example to non-patent literature 1) as excellent visible-light response type water decomposition photocatalyst。Its band gap is about 2.3eV, less than 3.0～3.2eV band gap of titanium oxide。It is to say, with compared with the well-known titanium oxide of photocatalyst material, it is possible to effectively utilize the light (visible ray) of longer wavelength side。
The more big activity of the general BET specific surface area of known photocatalyst is more high, once have studied the various BiVO adopting hydrothermal synthesis method4Manufacture method。But, due to the BiVO adopting hydrothermal synthesis method to produce4Utilization on cost height and industry is more difficult, the method therefore just manufactured in an atmosphere in recent studies on。
Such as, patent documentation 3 describes a kind of BiVO manufacturing visible light-responded property4The method of micropowder, it is characterised in that include under air, make NH under the existence of carbamide4VO3With Bi (NO3)3The operation of reaction。It addition, patent documentation 4 describes by the bismuth compound of solid and the vfanadium compound of solid being mixed, and carry out mechanical alloying (mechanicalalloying) process at 0 DEG C～100 DEG C, manufacture the BiVO that primary particle size is less than 10 μm4The method of microgranule。Furthermore, mechanical alloying method is that several above pressed powders are carried out ball milling (milling) process by the ball utilizing hard, carries out the manufacture method (non-patent literature 2) of Composite and alloying。
Titanium oxide is also widely known by the people (such as non-patent literature 3) as excellent carrier。Moreover it is known that containing being supported with BiVO4Inorganic compound and the compositions of cupric compound present extremely excellent antiviral activity in the daylight not having ultraviolet light。
At first technical literature
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2006-232729 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2011-136984 publication
Patent documentation 3: Japanese Unexamined Patent Publication 2004-024936 publication
Patent documentation 4: Japanese Unexamined Patent Publication 2005-035853 publication
Non-patent literature
Non-patent literature 1:J.Am.Chem.Soc.1999,121, pp11459-11467
Non-patent literature 2: Japanese welding society magazine the 59th volume (1990) the 2nd
Non-patent literature 3: a middle pool justice man of virtue and ability, (2008) catalyst brief guide, talk society of Co., Ltd.
Summary of the invention
Patent documentation 3 describes employing ureal antigen and can manufacture BiVO4Content。But it does not have about antiviral activity and support the record in titanium oxide。It addition, as described in the embodiment 1 of patent documentation 3, adopt the BiVO that this synthetic method is produced under air4BET specific surface area be 0.3m2About/g, is several μm as average primary particle diameter。Even if it addition, at the BiVO adopting the method for patent documentation 3 to produce4In containing cupric compound, antiviral activity is also and less high (comparative example 3 with reference to this specification)。
Patent documentation 4 describes the description below: the vfanadium compound mixing of the bismuth compound by solid and solid can be passed through, and carry out mechanical alloying at 0 DEG C～100 DEG C, manufacture the BiVO that primary particle size is less than 10 μm4Microgranule。But it does not have about antiviral activity and support the record in titanium oxide。Even if it addition, at the BiVO adopting the method for patent documentation 4 to produce4In containing cupric compound, antiviral activity is also and less high (comparative example 1 with reference to this specification)。
Titanium oxide is also widely known by the people (such as non-patent literature 3) as excellent carrier。Known to being supported with BiVO in recent years4Inorganic compound and the compositions of cupric compound present extremely excellent antiviral activity under visible light illumination。Although can envision by by BiVO4Loading method optimization improve the antiviral activity under visible ray further, but not about the opinion of this manufacture method。
The present invention provide do not have as under white LED illumination the daylight of ultraviolet light can present extremely excellent antiviral activity, be supported with BiVO4Titanium oxide manufacture method and containing being supported with BiVO4Titanium oxide and the antiviral composition of cupric compound。
The present invention completes for solving above-mentioned problem, is supported with BiVO in manufacture4Titanium oxide time, the acidic suspension that can comprise titanium oxide, bismuth ion, vanadic acid radical ion and solvent by utilizing pulverizer to process makes and is supported with BiVO4Titanium oxide。And then find, by the compositions that said method will be adopted to obtain and cupric compound combination, do not have ultraviolet light daylight antiviral property with adopt ureal antigen and mechanical alloying method produce compared with improve more than at least 10 times, thus completing the present invention。
That is, the present invention provides below scheme。
[1] one is supported with BiVO4The manufacture method of titanium oxide, the acidic suspension comprising titanium oxide, bismuth ion, vanadic acid radical ion and solvent by utilizing pulverizer to process manufactures。
[2] according to above-mentioned [1], it is supported with BiVO4The manufacture method of titanium oxide, pulverizer is the pulverizer using medium。
[3] according to above-mentioned [2], it is supported with BiVO4The manufacture method of titanium oxide, described pulverizer is ball mill or ball mill。
[4] according to any one of above-mentioned [1]～[3], it is supported with BiVO4The manufacture method of titanium oxide, the pH value of acidic suspension is lower than 7。
[5] according to above-mentioned [4], it is supported with BiVO4The manufacture method of titanium oxide, the pH value of acidic suspension is 0.1～4.0。
[6] according to above-mentioned [5], it is supported with BiVO4The manufacture method of titanium oxide, the pH value of acidic suspension is 0.1～3.0。
[7] according to any one of above-mentioned [1]～[6], it is supported with BiVO4The manufacture method of titanium oxide, the BET specific surface area of titanium oxide is 25m2/ more than g。
[8] according to above-mentioned [7], it is supported with BiVO4The manufacture method of titanium oxide, the BET specific surface area of titanium oxide is 30～500m2/g。
[9] according to any one of above-mentioned [1]～[8], it is supported with BiVO4The manufacture method of titanium oxide, described suspension also comprises acid, and described acid is chosen from least one in mineral acid, sulfonic acid and carboxylic acid。
[10] according to above-mentioned [9], it is supported with BiVO4The manufacture method of titanium oxide, described acid comprises described mineral acid, and described mineral acid is chosen from least one in hydrochloric acid, hydrobromic acid, hydroiodic acid, hypochlorous acid, sulphuric acid, nitric acid, phosphoric acid, boric acid, hexafluoro-antimonic acid, Tetrafluoroboric acid and hexafluorophosphoric acid。
[11] according to above-mentioned [10], it is supported with BiVO4The manufacture method of titanium oxide, described mineral acid is nitric acid。
[12] a kind of antiviral property compositions, containing adopt above-mentioned [1]～[11] the manufacture method manufacture described in any one be supported with BiVO4Titanium oxide and cupric compound, described in 100 mass parts, be supported with BiVO4Titanium oxide, described cupric compound by copper conversion quality be 0.1～20 mass parts。
[13] the antiviral property compositions according to above-mentioned [12], titanium oxide is the titanium oxide being coated with silicon dioxide。
[14] the antiviral property compositions according to above-mentioned [12] or [13], in the titanium oxide being coated with silicon dioxide, the quality of silicon dioxide is 1～30 mass %。
[15] the antiviral property compositions according to any one of above-mentioned [12]～[14], supports the BiVO on described titanium oxide4Mean diameter be 5～800nm。
According to the present invention, it is possible to provide can present in the daylight not having ultraviolet light extremely excellent antiviral activity, be supported with BiVO4The manufacture method of titanium oxide, and containing being supported with BiVO4Titanium oxide and the antiviral property compositions of cupric compound。
Accompanying drawing explanation
Fig. 1 is that the reflection electronic adopting scanning electron microscope to obtain of the sample of embodiment 2 is as photo。Furthermore, multiplying power is 200000 times。
Fig. 2 is that the reflection electronic adopting scanning electron microscope to obtain of the sample of comparative example 2 is as photo。Furthermore, multiplying power is 50000 times。
Detailed description of the invention
Hereinafter, the present invention is described in detail, but the present invention is not limited to embodiment disclosed below。Furthermore, in this manual, " not having the daylight of ultraviolet light " (sometimes also referred to as " daylight ") refers to the visible ray that wavelength is more than 400nm, but is created substantially absent the place of the wavelength light lower than 400nm。
[it is supported with BiVO4The manufacture method of titanium oxide]
Hereinafter, the present invention is supported with BiVO4The manufacture method of titanium oxide illustrate。
The present invention is supported with BiVO4The manufacture method of titanium oxide, be adopt pulverizer to process the manufacture method comprising titanium oxide, bismuth ion, vanadic acid radical ion and the acidic suspension by the solvent of described each ion-solubility。In mechanical alloying method, the bismuth compound of use solid and the vfanadium compound of solid are as raw material, on the other hand, in the manufacture method of the present invention, use bismuth ion and vanadic acid radical ion as raw material。It is as a result, it is possible to titania surface supports finer BiVO4As a result, antiviral activity when containing cupric compound increases substantially。
< raw material titanium oxide >
Support BiVO4Titanium oxide before, it is possible to be common titanium oxide, the titanium oxide that has been coated to by silicon dioxide etc.。They are called in the lump raw material titanium oxide。
Titanium oxide is preferably used TiO2。It addition, as the crystal structure of titanium oxide, it is preferred to anatase-type titanium oxide, Titanium Dioxide Rutile Top grade and brookite type titanium oxide, more preferably anatase-type titanium oxide, Titanium Dioxide Rutile Top grade。
The BET specific surface area of the titanium oxide used in the present invention (supports BiVO4Value before) it is preferably 25m2/ more than g, more preferably 25m2/ g～1500m2/ g, more preferably 25～1000m2/ g, is further preferably 30～500m2/ g, it is particularly preferred to be 40～300m2/ g。If the BET specific surface area of titanium oxide is 25m2/ more than g, then dispersibility time slurried and transparency when coating material become good。If the BET specific surface area of titanium oxide is 1000m2/ below g, then, when the application of the antiviral property compositions of the coating etc. of antiviral property compositions, become easy to the operation of antiviral property compositions。At this, BET specific surface area is the BET specific surface area adopting N2 adsorption BET line-of-sight course to determine。
< is coated with the titanium oxide > of silicon dioxide
Raw material titanium oxide can also be the titanium oxide being coated with silicon dioxide。(the SiO of the silicon dioxide of the titanium oxide being coated with silicon dioxide used in the present invention2) ratio, in the titanium oxide be coated with silicon dioxide be preferably 1～30 mass %, more preferably 2～25 mass %, more preferably 3～25 mass %。If silica volume is more than 1 mass %, then support BiVO4Reaction carry out well。If silica volume is below 30 mass %, then can suppress the consumption that makes of more expensive silica material, both economical。
Furthermore, the titanium oxide being coated with silicon dioxide means the titanium oxide at the coating silicon dioxide of titania surface。
The suitable BET specific surface area of the titanium oxide being coated with silicon dioxide is same with above-mentioned titanium oxide, it addition, the suitable crystal structure of the titanium oxide for being coated with in the titanium oxide of silicon dioxide, is also same with above-mentioned titanium oxide。
< bismuth ion >
The bismuth ion used in the present invention, makes by the bismuth compound becoming raw material is dissolved in solvent。As this bismuth compound, bismuth nitrate, bismuth oxide, bismuth bromide, bismuth sulfate, bismuth acetate, bismuth chloride, bismuth sulfide, bismuth iodide, fluoride bismuth, Bismugel (Biothrax)., bismuth citrate, bismuth oxychloride, bismuth and ammonium citrate, bismuth subcarbonate, bismuth neodecanoate, bismuth subsalicylate, novismuth (nitric acid oxidation bismuth: BiO (NO can be enumerated3)), Bismuth hydrate., isopropanol bismuth, acetic acid oxygen bismuth (acetic acid oxidation bismuth: BiOCH3And basic bismuth nitrate (BiNO COO)3(OH)2) etc.。It is preferably bismuth nitrate, bismuth sulfate, bismuth chloride, more preferably bismuth nitrate。Bismuth compound can be anhydride can also be hydrate。These materials, it is possible to be used singly or in combination of two or more kinds to use。
In order to be made the solution containing bismuth ion by the bismuth compound as raw material, described bismuth compound can be made to dissolve by adding acid in solvent, form stable bismuth ion。As such acid, the carboxylic acid etc. such as the sulfonic acid such as the mineral acids such as hydrochloric acid, hydrobromic acid, hydroiodic acid, hypochlorous acid, sulphuric acid, nitric acid, phosphoric acid, boric acid, hexafluoro-antimonic acid, Tetrafluoroboric acid and hexafluorophosphoric acid, methanesulfonic acid, ethyl sulfonic acid, benzenesulfonic acid, p-methyl benzenesulfonic acid, trifluoromethanesulfonic acid, polystyrolsulfon acid, kayexalate and acetic acid, citric acid, formic acid, gluconic acid, lactic acid, oxalic acid and tartaric acid can be enumerated。As above-mentioned acid, it is preferred to comprise the mineral acid of at least one in above-mentioned cited mineral acid, more preferably nitric acid。These materials, it is possible to be used singly or in combination of two or more kinds to use。
< vanadic acid radical ion >
The vanadic acid radical ion used in the present invention, makes by the vfanadium compound becoming raw material is dissolved in solvent。As this vfanadium compound, ammonium vanadate, vanadium oxide, bromination vanadium, triethoxy vanadium oxide, vanadium fluoride, stearic acid vanadium oxide, three isopropoxy vanadium oxides, vanadium oxytrifluoride and vanadium oxytrichloride can be enumerated, it is preferred to ammonium vanadate。Vfanadium compound can be anhydride can also be hydrate。These materials, it is possible to be used singly or in combination of two or more kinds to use。
In order to be made the solvent containing vanadic acid radical ion by the vfanadium compound as raw material, described vfanadium compound can be made to dissolve by adding acid in solvent, form stable vanadic acid radical ion。As such acid, it is same with the acid being used for making bismuth ion。
< solvent >
As the solvent that bismuth ion and vanadic acid radical ion are dissolved, it is preferred to use water but it also may comprise solvent in addition to water further。As solvent in addition to water, as long as raw material bismuth ion, vanadic acid radical ion and water can be dissolved。The content of the water in the total amount of solvent is preferably more than 80 mass %, more preferably more than 90 mass %, more preferably more than 95 mass %, is further preferably more than 99 mass %。
< suspension >
Suspension comprises above-mentioned titanium oxide, bismuth ion, vanadic acid radical ion and above-mentioned solvent。
This suspension is acid (at 25 DEG C, pH value is less than 7)。The pH value of suspension is preferably 0.1～4.0, more preferably 0.1～3.0, and more preferably 0.3～2.5, further it is preferably 0.5～2.0, much further preferably from 0.5～1.5, is more further preferably 0.7～1.5。If pH value is more than 0.1, then can suppress the consumption that makes of acid, both economical。If pH value is less than 7, then bismuth ion and vanadic acid radical ion can keep the state of ion and stable existence in a solvent, by utilizing pulverizer to process, it is possible to support fine BiVO on titanium oxide4。
As being used for adjusting the acid of the pH value of suspension, it is same with the acid being used for making bismuth ion。
It is supported with BiVO from manufacturing expeditiously4Titanium oxide viewpoint and make uniform suspension viewpoint set out, in suspension, be preferably 0.1～50g relative to the content of the raw material titanium oxide (when being coated with the titanium oxide of silicon dioxide for its total amount) of 100mL solvent, it is more preferably 1.0～20g, more preferably 2.0～10g, is further preferably 3.0～8.0g。
Furthermore, bismuth ion in suspension and the content of vanadic acid radical ion, it is preferred to: it is supported with BiVO described later4Titanium oxide in, obtained BiVO4It is the amount in OK range described later relative to the ratio of the titanium oxide (being its total amount when being coated with the titanium oxide of silicon dioxide) of 100 mass parts。
The manufacture method of this suspension is not particularly limited。
Such as, can in advance above-mentioned bismuth compound be dissolved in solvent and be added as needed on acid and manufacture the solution containing bismuth ion, above-mentioned vfanadium compound is dissolved in solvent and is added as needed on acid and manufacture the solution containing vanadic acid radical ion, make raw material titanium oxide be scattered in solvent in advance and be added as needed on acid to manufacture the titanium oxide suspension that have adjusted pH value, these liquid are mixed together with solvent as required, thus obtaining suspension。
Alternatively, it is also possible to the solution containing bismuth ion, solution containing vanadic acid radical ion and raw material titanium oxide are added in solvent, and it is added as needed on acid, thus obtaining suspension。
Additionally, can also bismuth compound and vfanadium compound be added in solvent and be added as needed on acid and obtain the solution containing bismuth ion and vanadic acid radical ion, in this solution, add raw material titanium oxide or its suspension and be added as needed on acid and/or solvent, thus obtaining suspension。
Alternatively, it is also possible to bismuth compound, vfanadium compound and raw material titanium oxide are added in solvent, and it is added as needed on acid, thus obtaining suspension。
< pulverizer >
In the present invention, by utilizing pulverizer to process suspension, collision energy is utilized to make reaction carry out, it is possible to make titanium oxide support BiVO4。Even if as long as pulverizer comprise solution also be able to use pulverizer be just not particularly limited, it is preferable to use the pulverizer of medium, more preferably ball mill or ball mill。
Composition as the medium used in pulverizer, as long as have the medium of suitable hardness and proportion just without particular limitation of, zirconium oxide, Achates, aluminium oxide, steel, glass, tungsten carbide, chromium steel and silicon nitride etc. can be used, as the medium used in pulverizer, the resin balls including iron core can be used。Composition as the medium used in pulverizer, it is preferred to zirconium oxide, Achates, aluminium oxide and glass, more preferably zirconium oxide and aluminium oxide, more preferably zirconium oxide。
When using ball mill as pulverizer, the rotating speed of the feed bin (bin) having received medium is preferably 10～1000rpm, more preferably 50～500rpm, more preferably 100～300rpm。
Medium is preferably dimensioned to be Φ 0.05～50mm, more preferably Φ 0.1～75mm, more preferably Φ 0.2～50mm。If medium is of a size of more than Φ 0.05mm, then easy recovering medium from serosity, if medium is of a size of below Φ 100mm, then can shorten the response time。
< reaction condition >
Grinding time, i.e. response time are preferably more than 1 hour, more preferably more than 3 hours, more preferably more than 5 hours。By processing more than 1 hour, reaction carries out equably。It addition, from the view point of shorten manufacturing time, it is preferred to less than 50 hours, more preferably less than 20 hours, more preferably less than 10 hours。
From the view point of uniformly and be sufficiently carried out reaction, pulverize temperature, i.e. reaction temperature and be preferably more than 5 DEG C, more preferably more than 10 DEG C, more preferably more than 25 DEG C, it addition, from the view point of reduce the energy expenditure of heat tracing, it is preferably less than 50 DEG C, more preferably less than 40 DEG C。Generally if room temperature, even if then not heating especially, reaction is also sufficiently carried out。
The separation of reacted medium can utilize sieve to carry out。From the view point of chemical proofing and cost, the material of sieve is preferably rustless steel, fluororesin, polyethylene, vinyl chloride or nylon, more preferably fluororesin, polyethylene, vinyl chloride or nylon, more preferably fluororesin。
Remove medium and obtain containing being supported with BiVO4The suspension of titanium oxide, can separate as solid constituent from mixed liquor。This separation method without particular limitation of, it is solid etc. to enumerate filtration, settlement separate, centrifugation, evaporation, but preferred isolated by filtration。
Isolated it is supported with BiVO4Titanium oxide, carry out as required washing, dry, pulverize, classification etc.。
< is supported with BiVO4Titanium oxide >
Obtain be supported with BiVO by above-mentioned process4Titanium oxide in, BiVO4Quality be preferably 0.1～20 mass parts relative to the raw material titanium oxide (be coated with the titanium oxide of silicon dioxide when for its total amount) of 100 mass parts, more preferably 0.5～15 mass parts, more preferably 1～10 mass parts。If BiVO4Quality be 0.1～20 mass parts relative to the titanium oxide (or being coated with the titanium oxide of silicon dioxide) of 100 mass parts, then the ntiviral characteristic of antiviral property compositions becomes good, and the ratio of the vanadium in compositions, bismuth element can be reduced, both economical。
Not hindering in the scope of effect of the present invention, BiVO can also be supported with4Titanium oxide in comprise except BiVO4With the composition beyond titanium oxide (or being coated with the titanium oxide of silicon dioxide), but preferably do not comprise this composition。It is supported with BiVO4Titanium oxide in, BiVO4It is preferably more than 80 mass % with the content of titanium oxide (or being coated with the titanium oxide of silicon dioxide), more preferably more than 90 mass %, more preferably more than 95 mass %, is further preferably more than 99 mass %。
It is being supported with BiVO4Titanium oxide in, from the view point of antiviral property and operability have both, BiVO4Mean diameter be preferably 5～800nm, more preferably 10～500nm, more preferably 10～200nm, further be preferably 10～100nm, more further be preferably 10～50nm。
BiVO4Mean diameter can be observed by reflection electronic picture and obtain。Specifically, BiVO4Mean diameter the method recorded in an embodiment can be adopted to measure。
[antiviral property compositions]
The antiviral property compositions of the present invention, is supported with BiVO containing what the above-mentioned manufacture method of employing produced4Titanium oxide and cupric compound, described in 100 mass parts, be supported with BiVO4Titanium oxide, described cupric compound by copper conversion quality be 0.1～20 mass parts。
Furthermore, " it is supported with BiVO4Titanium oxide ", when use as titanium oxide be coated with the titanium oxide of silicon dioxide, refer to and " be supported with BiVO4The titanium oxide being coated with silicon dioxide "。
Adopt what this manufacture method produced to be supported with BiVO4Titanium oxide, by containing cupric compound, even if also present the antiviral activity of excellence in the daylight not having ultraviolet light。
< cupric compound >
The cupric compound of the present invention, is the copper compound that valence mumber is divalent of copper。Cupric compound does not show ntiviral characteristic when independent。But, by be supported with BiVO4Titanium oxide combination, present ntiviral characteristic。As long as the copper compound that the valence mumber of cupric compound copper is divalent just without particular limitation of。It is one kind or two or more that such as cupric compound is chosen from hydroxyl cupric compound, (b) cupric halogenide, (c) cupric inorganic acid salt, (d) cupric acylate, (e) copper oxide, (f) copper sulfide, (g) copper azide and (h) cupric silicate that (a) is represented by following formula (1)。
Cu2(OH)3X(1)
(in formula, X represents anion)
X in formula (1) is more preferably selected from the halogens such as Cl, Br and I, CH3The carboxylic acid conjugate base of COO etc., NO3(SO4)1/2Deng mineral acid conjugate base and OH in any one。X in formula (1) is more preferably selected from Cl, CH3COO、NO3、(SO4)1/2With a kind in OH。
Preferred (b) cupric halogenide is one kind or two or more in copper chloride, copper fluoride and copper bromide。More preferably copper chloride。
Preferred (c) cupric inorganic acid salt is one kind or two or more in copper sulfate, copper nitrate, Copper diiodate(Cu(IO3)2), cupric perchlorate, cupric oxalate, tetraboric acid copper, Tetraamminecopper Sulfate, sulfamic acid copper, ammonium chloride copper, Copper pyrophosphate. and curpic carbonate。More preferably copper sulfate。
Preferred (d) cupric acylate is cupric carboxylate。As preferred cupric carboxylate, can enumerate selected from Tubercuprose., copper acetate, propanoic acid copper, copper butyrate, valeric acid copper, caproic acid copper, enanthic acid copper, cupric octoate, n-nonanoic acid copper, capric acid copper, myristic acid copper, copper palmitate, heptadecanoic acid copper, copper stearate, copper oleate, Cupric Lactate., malic acid copper, copper citrate, copper benzoate, phthalic acid copper, M-phthalic acid copper, p-phthalic acid copper, copper salicylate, mellic acid. copper, cupric oxalate, malonic acid copper, succinic acid copper, 1,3-propanedicarboxylic acid copper, adipic acid copper, fumaric acid copper, glycolic copper, glyceric acid copper, copper gluconate, cupric tartrate, acetylacetone copper, oacetic acid copper, isovaleric acid copper, β-resorcylic acid copper, diacetic acid copper, formyl succinic acid copper, bigcatkin willow amino acid copper, double, two (2 ethyl hexanoic acid) copper, one kind or two or more in decanedioic acid copper and copper naphthenate。More preferably copper acetate。
As other preferred cupric compound, that can enumerate in oxine copper (oxinecopper), acetylacetone copper, oacetic acid copper, copper trifluoromethanesulfcomposite, CuPc, ethanol copper, isopropanol copper, methanol copper and cupric dimethyldithio carbamate is one kind or two or more。
The cupric compound of the present invention is above-mentioned (a) hydroxyl cupric compound, (b) cupric halogenide, (c) cupric inorganic acid salt and (d) cupric acylate (b) represented by formula (1) preferably。It addition, aspect that is few from impurity and that do not consume cost, the cupric compound of the present invention is the above-mentioned hydroxyl cupric compound represented by formula (1) more preferably。Furthermore, the hydroxyl cupric compound that above-mentioned (a) is represented by formula (1) can be anhydride can also be hydrate。
The copper quality (quality of Cu) in cupric compound contained in the antiviral property compositions of the present invention, is supported with BiVO relative to 100 mass parts4Titanium oxide, it is preferred to 0.1～20 mass parts, more preferably 0.2～17.5 mass parts, more preferably 0.3～15 mass parts, further be preferably 0.3～10 mass parts, more further be preferably 0.3～5 mass parts, it is particularly preferred to be 0.4～1 mass parts。If the copper quality in cupric compound is supported with BiVO relative to 100 mass parts4Titanium oxide be more than 0.1 mass parts, then ntiviral characteristic and antibiotic property become good。If it addition, the copper quality in cupric compound is supported with BiVO relative to 100 mass parts4Titanium oxide be below 20 mass parts, then be prevented from being supported with BiVO4Titania surface be coated to by cupric compound, it is possible to increase the photocatalytic activity of antiviral property compositions, and inactivation of virus can be made with a small amount of antiviral property compositions, therefore both economical。
At this, it is supported with BiVO relative to 100 mass parts4Titanium oxide, copper quality in cupric compound, can by the raw material of cupric compound, titanium oxide (or being coated with the titanium oxide of silicon dioxide) and BiVO4Input amount calculate。Additionally, also the antiviral property compositions of the present invention can be heated in a solution of hydrofluoric acid, its CL is made to make lysate, use ICP emission spectrographic analysis device ((strain) Shimadzu Seisakusho Ltd. system, model ICPS-7500) analyze the extracting solution extracted from lysate, adopt ICP method analysis thus obtaining copper amount。
In antiviral property compositions, cupric compound can support in titanium oxide and/or BiVO4On。The method supported, can adopt and cupric compound is made aqueous solution, with titanium oxide and/or BiVO4The commonly known methods such as mixing carry out。It addition, in antiviral property compositions, cupric compound can not also support in titanium oxide and/or BiVO4Above it is scattered in titanium oxide and BiVO4Between。
The antiviral property compositions of the present invention, as it has been described above, as must containing and be supported with BiVO by composition4Titanium oxide and cupric compound but it also may be contained within other any composition in the scope not interfering with the purpose of the present invention。But, from the view point of improve ntiviral characteristic, in antiviral property compositions, be supported with BiVO4Titanium oxide and the total content of cupric compound, relative to the quality of antiviral property compositions, it is preferred to more than 90 mass %, more preferably more than 95 mass %, more preferably more than 99 mass %, it is particularly preferred to be 100 mass %。
In the antiviral property compositions of the present invention, from the view point of antiviral property and operability have both, BiVO4Mean diameter be preferably 5～800nm, more preferably 10～500nm, more preferably 10～200nm, further be preferably 10～100nm, more further be preferably 10～50nm。
BiVO4Mean diameter can be observed by reflection electronic picture and obtain。Specifically, BiVO4Mean diameter the method recorded in an embodiment can be adopted to be measured。
Embodiment
Hereinafter, by embodiment, the present invention is described in detail, but the present invention is not limited to following embodiment。
< raw material >
Titanium oxide (Showa electrician セ ラ ミ ッ Network ス (strain) system that will use in below example and comparative example, F-4, Detitanium-ore-type) and be coated with silicon dioxide titanium oxide (Showa electrician セ ラ ミ ッ Network ス (strain) make, F-4S20, Detitanium-ore-type) silica volume and BET specific surface area be shown in table 1。Furthermore, it is coated with the silica volume of the titanium oxide of silicon dioxide, is undertaken quantitatively by high-frequency induction coupled plasma optical emission spectrum analysis, be relative to the titanium oxide being coated with silicon dioxide, silicon dioxide (SiO2) quality %。BET specific surface area adopts N2 adsorption BET line-of-sight course described later to measure。The results are shown in table 1。
Table 1
< embodiment 1 >
The titanium oxide (Showa electrician セ ラ ミ ッ Network ス (strain) is made, F-4, Detitanium-ore-type) making 2.500g is suspended in 50mL ion exchange water and produces suspension, and utilizes the HNO of 5mol/L3The pH value of suspension is adjusted to 1.6 by aqueous solution。Then, prepared the Bi (NO of 0.188g3)3·5H2The NH of O (Northeast chemistry (strain) system) and 0.045g4VO3The HNO of (Northeast chemistry (strain) system) 5mol/L of lysed 0.75mL and 1.00mL respectively3Solution。Then, to be dissolved with Bi (NO3)3·5H2The HNO of O3Solution, it is dissolved with NH4VO3HNO3They are put in suspension by the order of solution, obtain the suspension that pH value is 1.3。This suspension is put in ア イ ボ イ (Aiboi) wide mouthed bottle of 100mL of the zirconia ball equipped with 50g Φ 3.0mm, close lid。It is disposed on desk-top pot grinding machine turntable (ア ズ ワ Application (strain) system), rotates 5 hours with the rotating speed of 150rpm, made and be supported with BiVO4The suspension of titanium oxide。By by obtained suspension filtered, dry, obtaining and be supported with BiVO4Titanium oxide (relative to the titanium oxide of 100 mass parts, as BiVO4Support 5 mass parts)。
Make 1.000g's to be supported with BiVO4Titanium dioxide powder be suspended in 100mL distilled water and produce suspension, 0.014g (is supported with BiVO relative to 100 mass parts4Titanium dioxide powder, be scaled 0.5 mass parts by copper) CuCl2·2H2O (Northeast chemistry (strain) system) adds in this suspension, has stirred 10 minutes。Adding sodium hydroxide (Northeast chemistry (strain) system) aqueous solution of 1.0mol/L so that the pH value of suspension becomes 10, carrying out stirring mixing in 30 minutes, thus obtaining serosity。
This serosity is filtered, with the obtained powder body of pure water, dries at 80 DEG C, and use blender size degradation。So, as the sample of embodiment 1, make antiviral property compositions, be namely supported with BiVO4And Cu2(OH)3The titanium oxide of Cl。Furthermore, CuCl2·2H2O is hydrolyzed, and becomes Cu2(OH)3Cl。PH meter uses (strain) hole field made D-51 of making to carry out。
(embodiment 2)
Except titanium oxide is set to be coated with beyond the titanium oxide (Showa electrician セ ラ ミ ッ Network ス (strain) is made, F-4S05, Detitanium-ore-type) of silicon dioxide, method similarly to Example 1 is adopted to make the sample of embodiment 2。
(embodiment 3)
Bi (NO will be dissolved with3)3·5H2The HNO of O3Solution, it is dissolved with NH4VO3HNO3Solution utilizes the HNO of 5mol/L after putting into3The pH value of suspension is adjusted to 0.5 by aqueous solution, adopts method similarly to Example 2 to obtain the sample of embodiment 3 in addition。
(embodiment 4)
The titanium oxide (Showa electrician セ ラ ミ ッ Network ス (strain) is made, F-4S05, Detitanium-ore-type) being coated with silicon dioxide making 2.500g is suspended in 50mL ion exchange water and produces suspension, utilizes the HNO of 5mol/L3The pH value of suspension is adjusted to 2.6 by aqueous solution。Then, prepare the Bi (NO of 0.188g3)3·5H2The NH of O (Northeast chemistry (strain) system) and 0.045g4VO3The HNO of (Northeast chemistry (strain) system) 5mol/L of lysed 0.75mL and 1.00mL respectively3Solution, to be dissolved with Bi (NO3)3·5H2The HNO of O3Solution, it is dissolved with NH4VO3HNO3They are put in suspension by the order of solution, obtain the suspension that pH value is 2.0。This suspension is put in the ア イ ボ イ wide mouthed bottle of 100mL of the zirconia ball equipped with 50g Φ 3.0mm, close lid。It is disposed on desk-top pot grinding machine turntable (ア ズ ワ Application (strain) system), rotates 5 hours with the rotating speed of 150rpm, made and be supported with BiVO4The suspension of the titanium oxide being coated with silicon dioxide。By by obtained suspension filtered, dry, obtaining and be supported with BiVO4Titanium oxide (relative to the titanium oxide being coated with silicon dioxide of 100 mass parts, as BiVO4Support 5 mass parts)。
Make 1.000g's to be supported with BiVO4The titanium dioxide powder being coated with silicon dioxide be suspended in 100mL distilled water and produce suspension, 0.014g (is supported with BiVO relative to 100 mass parts4The titanium dioxide powder being coated with silicon dioxide, be scaled 0.5 mass parts by copper) CuCl2·2H2O (Northeast chemistry (strain) system) adds in this suspension, has stirred 10 minutes。Adding sodium hydroxide (Northeast chemistry (strain) system) aqueous solution of 1.0mol/L so that the pH value of suspension becomes 10, carrying out stirring mixing in 30 minutes, thus obtaining serosity。
This serosity is filtered, with the obtained powder body of pure water, dries at 80 DEG C, and use blender size degradation。So, as the sample of embodiment 4, make antiviral property compositions, be namely supported with BiVO4And Cu2(OH)3The titanium oxide being coated with silicon dioxide of Cl。Furthermore, CuCl2·2H2O is hydrolyzed, and becomes Cu2(OH)3Cl。PH meter uses (strain) hole field made D-51 of making to carry out。
(embodiment 5)
Using the titanium oxide being coated with silicon dioxide relative to 100 mass parts, as BiVO4Support 5 mass parts, be changed to and be coated with the titanium oxide of silicon dioxide, BiVO relative to 100 mass parts4Loading be 2 mass parts, adopt method similarly to Example 2 to obtain the sample of embodiment 5 in addition。
(embodiment 6)
Except making ア イ ボ イ wide mouthed bottle rotate 2 hours with the rotating speed of 150rpm, method similarly to Example 2 is adopted to obtain the sample of embodiment 6。
(comparative example 1)
The titanium oxide (Showa electrician セ ラ ミ ッ Network ス (strain) is made, F-4, Detitanium-ore-type) making 2.500g is suspended in 50mL ion exchange water and produces suspension。Then, by the Bi (NO of 0.188g3)3·5H2The NH of O (Northeast chemistry (strain) system) and 0.045g4VO3(Northeast chemistry (strain) system) puts in suspension。Now the pH value of suspension is 4.2。Now Bi (NO in suspension3)3·5H2O and NH4VO3It it is solid almost without dissolving, it does not have ionizing。This suspension is put in the ア イ ボ イ wide mouthed bottle of 100mL of the zirconia ball equipped with 50g Φ 3.0mm, close lid。It is disposed on desk-top pot grinding machine turntable (ア ズ ワ Application (strain) system), rotates 5 hours with the rotating speed of 150rpm, made the suspension of the titanium oxide being supported with atypic Bi and V compound。By by obtained suspension filtered, dry, adopting mechanical alloying method to obtain the titanium oxide being supported with atypic Bi and V compound。
The titanium dioxide powder being supported with atypic Bi and V compound making 1.000g is suspended in 100mL distilled water produces suspension, CuCl by 0.014g (relative to the titanium dioxide powder being supported with atypic Bi and V compound of 100 mass parts, be scaled 0.5 mass parts by copper)2·2H2O (Northeast chemistry (strain) system) adds in this suspension, has stirred 10 minutes。Adding sodium hydroxide (Northeast chemistry (strain) system) aqueous solution of 1.0mol/L so that the pH value of suspension becomes 10, carrying out stirring mixing in 30 minutes, thus obtaining serosity。This serosity is filtered, with the obtained powder body of pure water, dries at 80 DEG C, and use blender size degradation。So, as the sample of comparative example 1, made and be supported with BiVO4And Cu2(OH)3The titanium oxide of Cl。Furthermore, CuCl2·2H2O is hydrolyzed, and becomes Cu2(OH)3Cl。PH meter uses (strain) hole field made D-51 of making to carry out。
(comparative example 2)
Except titanium oxide is set to be coated with the titanium oxide of silicon dioxide, the method same with comparative example 1 is adopted to obtain the sample of comparative example 2。Furthermore, the pH value of suspension is 4.4, for acidity。
(comparative example 3)
The titanium oxide (Showa electrician セ ラ ミ ッ Network ス (strain) is made, F-4, Detitanium-ore-type) making 10.000g is suspended in 300mL distilled water and produces suspension, utilizes the HNO of 5mol/L3The pH value of suspension is adjusted to 1.3 by aqueous solution。Then, prepare the Bi (NO of 0.752g3)3·5H2The NH of O (Northeast chemistry (strain) system) and 0.182g4VO3The HNO of (Northeast chemistry (strain) system) 5mol/L of lysed 3.0mL and 4.0mL respectively3Solution, to be dissolved with Bi (NO3)3·5H2The HNO of O3Solution, it is dissolved with NH4VO3HNO3They are put in suspension by the order of solution, obtain the suspension that pH value is 0.9。Then, the carbamide (Northeast chemistry (strain) system) of 10.000g is put in suspension, in the upper heating of hot type agitator (hotstirrer) to the temperature of 80 DEG C, at the temperature of 80 DEG C, maintains 8 hours。By by obtained suspension filtered, dry, obtaining the titanium oxide being supported with atypic Bi and V compound。
The titanium dioxide powder being supported with atypic Bi and V compound making 1.000g is suspended in 100mL distilled water produces suspension, CuCl by 0.014g (relative to the titanium dioxide powder being supported with atypic Bi and V compound of 100 mass parts, be scaled 0.5 mass parts by copper)2·2H2O (Northeast chemistry (strain) system) adds in this suspension, has stirred 10 minutes。Adding sodium hydroxide (Northeast chemistry (strain) system) aqueous solution of 1.0mol/L so that the pH value of suspension becomes 10, carrying out stirring mixing in 30 minutes, thus obtaining serosity。This serosity is filtered, with the obtained powder body of pure water, dries at 80 DEG C, and use blender size degradation。So, as the sample of comparative example 3, make and be supported with atypic Bi and V compound and Cu2(OH)3The titanium oxide of Cl。Furthermore, CuCl2·2H2O is hydrolyzed, and becomes Cu2(OH)3Cl。PH meter uses (strain) hole field made D-51 of making to carry out。
(comparative example 4)
Except titanium oxide is set to be coated with the titanium oxide of silicon dioxide, the method same with comparative example 3 is adopted to obtain the sample of comparative example 4。
(comparative example 5)
Except without putting into beyond the zirconia ball of Φ 3.0mm, method similarly to Example 1 is adopted to obtain the sample of comparative example 5。
(comparative example 6)
Except without putting into beyond the zirconia ball of Φ 3.0mm, method similarly to Example 2 is adopted to obtain the sample of comparative example 6。
(comparative example 7)
The titanium dioxide powder making 1.000g is suspended in 100mL distilled water and produces suspension, by the CuCl of 0.014g (relative to the titanium dioxide powder of 100 mass parts, be scaled 0.5 mass parts by copper)2·2H2O (Northeast chemistry (strain) system) adds in this suspension, has stirred 10 minutes。Adding sodium hydroxide (Northeast chemistry (strain) system) aqueous solution of 1mol/L so that the pH value of suspension becomes 10.0, carrying out stirring mixing in 30 minutes, thus obtaining serosity。This serosity is filtered, with the obtained powder body of pure water, dries at 80 DEG C, and utilize blender size degradation, made the sample of comparative example 7。
(comparative example 8)
Except titanium oxide is set to be coated with the titanium oxide of silicon dioxide, the method same with comparative example 7 is adopted to obtain the sample of comparative example 8。
(comparative example 9)
The titanium oxide (Showa electrician セ ラ ミ ッ Network ス (strain) is made, F-4S20, Detitanium-ore-type) being coated with silicon dioxide making 2.500g is suspended in 50mL ion exchange water and produces suspension。Then, prepare the Bi (NO of 0.188g3)3·5H2The NH of O (Northeast chemistry (strain) system) and 0.045g4VO3The HNO of (Northeast chemistry (strain) system) 5mol/L of lysed 0.75mL and 1.00mL respectively3Solution, to be dissolved with Bi (NO3)3·5H2The HNO of O3Solution, it is dissolved with NH4VO3HNO3They are put in suspension by the order of solution, then by the NaOH solution of 5mol/L, pH value are adjusted to 12.0。This suspension is put in the ア イ ボ イ wide mouthed bottle of 100mL of the zirconia ball equipped with 50g Φ 3.0mm, close lid。It is disposed on desk-top pot grinding machine turntable (ア ズ ワ Application (strain) system), rotates 5 hours with the rotating speed of 150rpm, made and be supported with BiVO4The suspension of the titanium oxide being coated with silicon dioxide。By by obtained suspension filtered, dry, obtaining the titanium oxide being coated with silicon dioxide being supported with atypic Bi and V compound。
The titanium dioxide powder being coated with silicon dioxide being supported with atypic Bi and V compound making 1.000g is suspended in 100mL distilled water produces suspension, CuCl by 0.014g (relative to the titanium dioxide powder being coated with silicon dioxide being supported with atypic Bi and V compound of 100 mass parts, be scaled 0.5 mass parts by copper)2·2H2O (Northeast chemistry (strain) system) adds in this suspension, has stirred 10 minutes。Adding sodium hydroxide (Northeast chemistry (strain) system) aqueous solution of 1.0mol/L so that the pH value of suspension becomes 10, carrying out stirring mixing in 30 minutes, thus obtaining serosity。This serosity is filtered, with the obtained powder body of pure water, dries at 80 DEG C, and use blender size degradation。So, as the sample of comparative example 9, make and be supported with atypic Bi and V compound and Cu2(OH)3The titanium oxide of Cl。Furthermore, CuCl2·2H2O is hydrolyzed, and becomes Cu2(OH)3Cl。PH meter uses (strain) hole field made D-51 of making to carry out。
< evaluates >
To the sample making embodiment 1～the 6 and comparative example 1～9 made as described above, carry out following evaluation。
(X-ray diffraction mensuration)
The sample of embodiment 1～6 and the sample of comparative example 1～6,9 are carried out X-ray diffraction mensuration, identifies the compound comprising Bi and V being present in sample。Determinator uses " X ' pertPRO " of PANalytical company, use copper target, use Cu-K α 1 ray, be 0.0167deg and scanning speed has carried out X-ray diffraction mensuration when being 3.3deg/min at tube voltage to be 45kV, tube current be 40mA, measurement range 2 θ=20～100deg, sampling width。
(BiVO4Mean diameter)
To the BiVO in the sample obtained in embodiment and comparative example4Mean diameter, by reflection electronic picture observe measured。At this, for instance " sample obtained in embodiment 1 " is meaned the end product obtained by embodiment 1, is namely supported with BiVO4And Cu2(OH)3The titanium oxide of Cl。Also it is same about other embodiments and comparative example。
As BiVO4The determinator of mean diameter, employ " very-high performance scanning electron microscope S-5500 " that Hitachi's (strain) makes。Reflection electronic picture is used to observe 100 BiVO4Particle, determines each BiVO4The particle diameter of particle。The meansigma methods of the particle diameter this determined is as mean diameter。Furthermore, BiVO4Particle diameter, at BiVO4For being BiVO when spherical4The diameter of particle, at BiVO4Particle have spherical beyond shape when, be will pass through BiVO4BiVO on the axis of the center of gravity of particle4The value that among the length of particle, maximum and minima obtain divided by 2 after being added。
(the evaluation of the ntiviral characteristic under radiation of visible light: LOG (N/N0) mensuration)
The ntiviral characteristic of the sample of embodiment 1～6 and comparative example 1～9, by using the model experiment of phage (bacteriophage) to adopt following methods to confirm。Furthermore, utilize relative to the inactivation capacity of phage as the method for the model of ntiviral characteristic, be recorded in such as Appl.MicrobiolBiotechnol., 79, in pp.127-133 (2008), it is known that adopt the method can obtain the result with reliability。It addition, this mensuration is based on JISR1706。
Being respectively coated the embodiment 1～6 of 2.5mg and the sample of comparative example 1～9 on glass plate (50mm × 50mm × 1mm), the coating weight having made per unit area is 1.0g/m2Evaluation sample。
In deep type culture dish, spread filter paper, add a small amount of aquesterilisa。Filter paper placed the evaluation sample of above-mentioned record。The use 1/500NB of 100 μ L is dripped so that phage-infect value becomes about 6.7 × 10 on it6～about 2.6 × 107Q phagus beta (NBRC20012) suspension that the mode of pfu/ml is modulated, covers PET (polyethylene terephthalate) thin film made to make specimen surface contact with phage。Glass plate is covered on this deep type culture dish, it can be used as mensuration assembly。Prepare multiple same mensuration assembly。
Additionally, employ in 15W white fluorescent lamp (パ Na ソ ニ ッ Network (strain) system as light source, complete white fluorescent lamp (fullwhitefluorescentlamp), FL15N) light source of ultraviolet cutoff light filter (day east Resin Industry (strain) makes, N-113) it is mounted with on。Multiple mensuration assembly has been stood in the position that illumination is 800 luxs (utilizing illumination meter: the IM-5 of (strain) ト プ U Application is measured)。Irradiating from light starting after 60 minutes, the phage concentration carrying out the sample on glass plate measures。It addition, the illumination in room when making mensuration is below 200 luxs。Furthermore, the stopwatch irradiating the use of the elapsed time starting commercially available from light measures。
Following method is adopted to carry out the mensuration of phage concentration。Make the sample that the phage recovered liquid (SCDLP culture medium) of 9.9ml permeates on glass plate, vibrate 10 minutes with vibrating machine。The normal saline added with peptone is used suitably to dilute this phage recovered liquid。To additionally cultivate 5.0 × 108～2.0 × 109In the liquid that coliform (NBRC106373) culture fluid of individual/ml and the LB soft agar medium being added with calcium mix, after adding the 1ml liquid just now diluted and mixing, by this liquid dissemination in the LB agar culture medium being added with calcium, after cultivating 15 hours at 37 DEG C, by visually measuring the plaque number of phage。The dilution ratio being multiplied by phage recovered liquid by obtained plaque number obtains phage concentration N。
By initial phage concentration N0Phage relative concentration (LOG (N/N is obtained with the phage concentration N after the stipulated time0))。Furthermore, LOG (N/N0) value more little (absolute value is more big), the ntiviral characteristic of sample is more excellent。
< result >
(observation of reflection electronic picture)
The photo of the reflection electronic picture of the sample of embodiment 2 is shown in Fig. 1, the photo of the reflection electronic picture of the sample of comparative example 2 is shown in Fig. 2。Fig. 1 is the photo of the reflection electronic picture of the sample of embodiment 2, and Fig. 2 is the photo of the reflection electronic picture of the sample of comparative example 2。Fig. 1 is the photo of the reflection electronic picture of the multiplying power of 200000 times, and Fig. 2 is the photo of the reflection electronic picture of the multiplying power of 50000 times。
In fig. 1 and 2, it is possible to be judged as: in reflection electronic picture, seem that the region become clear especially is the region that there is heavy element Bi。By this reflection electronic picture it can be seen that the BiVO of the sample obtained in example 24Primary particle size be tens of nm, and the BiVO of the sample obtained in comparative example 24Primary particle size be about 1 μm。
(the evaluation of the ntiviral characteristic under radiation of visible light: LOG (N/N0) mensuration)
The evaluation result of the ntiviral characteristic of (ultraviolet cutoff) under radiation of visible light is shown in table 2 below。
Contrast by embodiment 1 with comparative example 1,3 and embodiment 2 and comparative example 2,4, known manufacture method is compared with mechanical alloying method, ureal antigen etc., it is possible to make containing cupric compound time antiviral activity exceed more than at least 10 times be supported with BiVO4Titanium oxide。
Contrast by embodiment 1 with comparative example 5 and embodiment 2 and comparative example 6, it is known that it is important for utilizing collision energy to react。
Contrast by embodiment 1 with embodiment 2, it is known that the titanium oxide used in this manufacture method is preferably the titanium oxide being coated with silicon dioxide。
Contrast by embodiment 2,3,4 and comparative example 9, it is known that the pH value of suspension is acidity is important。
Claims (15)
1. one kind is supported with BiVO4The manufacture method of titanium oxide, the acidic suspension comprising titanium oxide, bismuth ion, vanadic acid radical ion and solvent by utilizing pulverizer to process manufactures。
2. according to claim 1 it is supported with BiVO4The manufacture method of titanium oxide, pulverizer is the pulverizer using medium。
3. according to claim 2 it is supported with BiVO4The manufacture method of titanium oxide, described pulverizer is ball mill or ball mill。
4. according to claim 1 and 2 it is supported with BiVO4The manufacture method of titanium oxide, the pH value of acidic suspension is lower than 7。
5. according to claim 4 it is supported with BiVO4The manufacture method of titanium oxide, the pH value of acidic suspension is 0.1～4.0。
6. according to claim 5 it is supported with BiVO4The manufacture method of titanium oxide, the pH value of acidic suspension is 0.1～3.0。
7. according to claim 1 and 2 it is supported with BiVO4The manufacture method of titanium oxide, the BET specific surface area of titanium oxide is 25m2/ more than g。
8. according to claim 7 it is supported with BiVO4The manufacture method of titanium oxide, the BET specific surface area of titanium oxide is 30～500m2/g。
9. according to claim 1 and 2 it is supported with BiVO4The manufacture method of titanium oxide,
Described suspension also comprises acid,
Described acid is chosen from least one in mineral acid, sulfonic acid and carboxylic acid。
10. according to claim 9 it is supported with BiVO4The manufacture method of titanium oxide,
Described acid comprises described mineral acid,
Described mineral acid is chosen from least one in hydrochloric acid, hydrobromic acid, hydroiodic acid, hypochlorous acid, sulphuric acid, nitric acid, phosphoric acid, boric acid, hexafluoro-antimonic acid, Tetrafluoroboric acid and hexafluorophosphoric acid。
It is supported with BiVO 11. according to claim 104The manufacture method of titanium oxide, described mineral acid is nitric acid。
12. an antiviral property compositions, containing adopt claim 1～11 the manufacture method manufacture described in any one be supported with BiVO4Titanium oxide and cupric compound,
It is supported with BiVO described in 100 mass parts4Titanium oxide, described cupric compound by copper conversion quality be 0.1～20 mass parts。
13. antiviral property compositions according to claim 12, titanium oxide is the titanium oxide being coated with silicon dioxide。
14. antiviral property compositions according to claim 13, in the titanium oxide being coated with silicon dioxide, the quality of silicon dioxide is 1～30 mass %。
15. the antiviral property compositions according to claim 12 or 13, support the BiVO on described titanium oxide4Mean diameter be 5～800nm。
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| JP2014254030A JP2016113331A (en) | 2014-12-16 | 2014-12-16 | MANUFACTURING METHOD OF TITANIUM OXIDE CARRYING BiVO4 AND ANTIVIRAL COMPOSITION |
| JP2014-254030 | 2014-12-16 |
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| CN109939744A (en) * | 2019-04-16 | 2019-06-28 | 黑龙江大学 | A kind of preparation method and application of ultra-thin two-dimension metal phthalocyanine/composite bismuth vanadium photocatalyst |
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| JP2016113417A (en) * | 2014-12-16 | 2016-06-23 | 昭和電工株式会社 | Antiviral composition, antiviral agent, photocatalyst and virus deactivation method |
| CN109046395B (en) * | 2018-08-30 | 2023-08-11 | 南通纺织丝绸产业技术研究院 | Bismuth tellurate/bismuth oxide heterojunction material, preparation method and application thereof |
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Also Published As
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| TW201632466A (en) | 2016-09-16 |
| KR20160073308A (en) | 2016-06-24 |
| JP2016113331A (en) | 2016-06-23 |
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