CN104923310A - Preparation method for soluble amino phthalocyanine-titanium dioxide near-infrared photocatalyst - Google Patents
Preparation method for soluble amino phthalocyanine-titanium dioxide near-infrared photocatalyst Download PDFInfo
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Abstract
The invention relates to a preparation method for a soluble amino phthalocyanine-titanium dioxide near-infrared photocatalyst. The method comprises the following steps: synthesis of amino phthalonitrile, synthesis of amino phthalocyanine and preparation of the amino phthalocyanine-TiO2 near-infrared photocatalyst by using a sol-gel method. The invention has the following beneficial effects: the synthesized soluble amino phthalocyanine with strong adsorption in a near-infrared region is soluble in an acid sol system of TiO2; since the amino phthalocyanine-TiO2 photocatalyst is prepared by using the sol-gel method, amino phthalocyanine can contact with TiO2 in a molecular morphology, so the combination of amino phthalocyanine and TiO2 is uniform and stable, and the wavelength response range of TiO2 can extend to the near-infrared region; and the photocatalytic degradation effect of the amino phthalocyanine-TiO2 near-infrared photocatalyst is superior to the photocatalytic degradation effect of TiO2, and compared with common phthalocyanine-TiO2 photocatalyst, the amino phthalocyanine-TiO2 near-infrared photocatalyst has higher catalytic efficiency; meanwhile, the amino phthalocyanine-TiO2 near-infrared photocatalyst has certain stability and can be recycled.
Description
Technical field
The present invention relates to the preparation method of a kind of solubility amido phthalocyanine-titanium dioxide near infrared light catalyst.
Background technology
Society, environmental pollution and energy crisis cause people to pay close attention to day by day.Environmental friendliness, economic energy-conservation technology become study hotspot.Conductor photocatalysis degradation technique is a kind of technology adapting to this idea just.In numerous semi-conducting material, TiO
2become a kind of photochemical catalyst that research is the most deep.TiO
2corrosion-resistant, good stability, nontoxic pollution-free, cheap, be easy to get, and there is higher photocatalytic activity.But it also has certain applied defect, its forbidden band is wider, about 3.2eV, and this just determines absorbing wavelength to be less than the ultraviolet light of 387nm, and arrives this part light in the sunray of the earth and only account for 3% ~ 5%, visible TiO
2extremely low to the utilization rate of sunshine, this also determines that it is low at visible-near-infrared lower catalytic efficiency.
Therefore, people expand TiO by methods such as doping and dye sensitizations
2wavelength response range, to improve its photocatalysis efficiency.Wherein, it is visible-near-infrared that selected dyestuff should be able to absorb wide spectrum effectively, and effective bonding can be formed between dyestuff and semiconductor, the electronics being beneficial to be excited is injected into the conduction band of semiconductor by dyestuff, realize light induced electron and be separated with the effective of hole.In these dyestuffs, phthalocyanine complex is the sensitizer that a class has good chemical, light and thermally stable, strong absorption is there is in common metal phthalocyanine (as phthalocyanine blue, phthalocyanine green) at the visible region of 600nm ~ 700nm, but its dissolubility is poor, be difficult to be dissolved in common solvent, limit its application in photocatalysis field.By carrying out chemical modification to metal phthalocyanine, after phthalocyanine ring is introduced the substituting group such as carboxyl, sulfonic group, its dissolubility and space steric effect can be increased, reducing the polymerization of phthalocyanine, and then improve sensitizer at matrix (TiO
2) surface uniformity, further increase electron injection efficiency and photocatalytic activity.Especially, when when the peripheral phenyl ring of phthalocyanine introduces stronger electron donating group (as amido), its absorption maximum band red shift can be made, have stronger absorption in near-infrared region.
Strong wait (Treatment of Industrial Water, 2011,31 (4): 37-38) of Bian war utilize PC copper (CuPcTs) to be sensitizer, adopt solvent-thermal method original position to prepare CuPcTs/TiO
2composite nano-catalyst, and show under visible light, to phthalic acid in water two (2-ethylhexyl) ester (DEHP), there is good catalytic degradation effect.Yang Hui etc. (catalysis journal, 2007,28 (12): 1072-1076) for sensitizer, adopt sol-gel process to prepare phthalocyanine-sensitized TiO with PC copper (CuPcTs)
2colloidal sol, through Best-Effort request film forming and room temperature dry, obtained CuPcTs-TiO
2film.This CuPcTs-TiO
2film has higher photocatalytic activity to rhodamine B degraded.Du Yijun etc. (environmental protection science and technology, 2013,4:21-24) adopt sol-gel process to prepare phthalocyanine-TiO
2photochemical catalyst, and difference doping iron, copper, cobalt, nickel element, and study phthalocyanine-TiO under visible light
2photochemical catalyst is to the degradation effect of 5 kinds of organic dyestuff (methyl orange, methyl red, cresol-purple, methylene blue and malachite green).Phthalocyanine-the TiO of usual preparation
2photochemical catalyst sensitizer phthalocyanine used has stronger absorption at visible region, therefore this kind of phthalocyanine-TiO
2photochemical catalyst can only make TiO
2wavelength response range be extended to visible region, cannot near infrared region be extended to, thus preparation phthalocyanine-TiO
2photochemical catalyst does not absorb in near-infrared region.
Summary of the invention
The technical problem to be solved in the present invention is: based on the problems referred to above, the invention provides the preparation method of a kind of solubility amido phthalocyanine-titanium dioxide near infrared light catalyst.
The present invention solves the technical scheme that its technical problem adopts: the preparation method of a kind of solubility amido phthalocyanine-titanium dioxide near infrared light catalyst, comprises the following steps:
(1) synthesis of amido phthalic nitrile:
Nitro phthalic nitrile, organic amine, weak base and solvent is added in reaction vessel, room temperature reaction 12 ~ 24h under stirring condition, reactant liquor is poured in the beaker filling appropriate amount of deionized water after reaction terminates and precipitate, sediment is washed to washing lotion in neutral, dry, with absolute ethyl alcohol recrystallization, recrystallized product is put into vacuum drying oven 40 ~ 50 DEG C of drying 12 ~ 24h, obtain amido phthalic nitrile;
(2) synthesis of amido phthalocyanine:
Amido phthalic nitrile, slaine, 1 that step (1) is obtained is added in reaction vessel, 8-diazabicylo 11 carbon-7-alkene (DBU) and solvent, 130 ~ 160 DEG C of reaction 12 ~ 24h under nitrogen protection, be cooled to room temperature after reaction terminates, in reactant liquor, add ethyl acetate separating out to there being product, decompress filter, with ethyl acetate, methyl alcohol successively cyclic washing, dry, obtain black or blue solid powder, namely obtain amido phthalocyanine;
(3) sol-gel process is adopted to prepare amido phthalocyanine-TiO
2near infrared light catalyst:
In reaction vessel, add absolute ethyl alcohol, slowly drip TiO wherein under agitation
2precursor solution, stir and obtain solution A; In another reaction vessel, add deionized water, concentrated hydrochloric acid and glacial acetic acid, stir to obtain solution B; B solution at the uniform velocity stirred at 30 ~ 40 DEG C, solution A be slowly added drop-wise in B solution subsequently, 1 ~ 2h drips, and fully stirs and obtains TiO
2colloidal sol;
To TiO
2add the amido phthalocyanine of the obtained difference amount of step (2) in colloidal sol, be stirred to amido phthalocyanine and dissolve, obtain the amido phthalocyanine-TiO of clear
2colloidal sol, by amido phthalocyanine-TiO
2colloidal sol sealing, ageing 2 ~ 4d at 60 ~ 70 DEG C, uncovered oven dry is to powder afterwards, with absolute ethanol washing for several times, dry, obtain the amido phthalocyanine-TiO of different content
2near infrared light catalyst.
Further, in step (1), nitro phthalic nitrile is 3-nitro phthalic nitrile or 4-nitro phthalic nitrile, organic amine is n-butylamine, n-octyl amine or dimethylamine agueous solution, and weak base is triethylamine, potash or potassium acetate, and solvent is DMSO, DMF or DMAC.
Further, phthalic nitrile, organic amine, weak base rate of charge are mol ratio=1:(0.11 ~ 0.15 in step (1)): (0.2 ~ 0.25), the consumption of solvent is make to feed intake the molar concentration of total amount at 8 ~ 9mol/L.
Further, obtaining amido phthalic nitrile in step (1) is 3-n-butylamine-based phthalic nitrile (α-nBAPn), 3-dimethylamino phthalic nitrile (α-DMAPn), 4-n-butylamine-based phthalic nitrile (β-nBAPn) or 3-n-octyl amine base phthalic nitrile (α-nOAPn).
Further, in step (2), slaine is MnCl
24H
2o or CuCl
22H
2o, solvent is n-hexyl alcohol, n-amyl alcohol or n-heptanol, and phthalocyanine that need not be metal-doped is without the need to adding slaine.
Further, amido phthalic nitrile, slaine, DBU rate of charge are mol ratio=1:(0.25 ~ 0.3 in step (2)): (0.25 ~ 0.3), the consumption of solvent is make to feed intake the molar concentration of total amount at 0.55 ~ 0.85mol/L.
Further, obtaining amido phthalocyanine in step (2) is 3,3 ', 3 ", 3 " '-four n-butylamine-based manganese phthalocyanines (α-TnBAMnPc), 3,3 ', 3 ", 3 " '-four n-butylamine-based copper phthalocyanines (α-TnBACuPc), 3,3 ', 3 ", 3 " '-four n-butylamine-based phthalocyanine (α-TnBAH
2pc), 4,4 ', 4 "; 4 " '-four n-butylamine-based manganese phthalocyanines (β-TnBAMnPc), 3,3 ', 3 ", 3 " '-four dimethylamino manganese phthalocyanines (α-TDMAMnPc), 3,3 ', 3 ", 3 " '-four dimethylamino copper phthalocyanines (α-TDMACuPc) or 3,3 ', 3 ", 3 " '-four n-octyl amine base manganese phthalocyanines (α-TnOAMnPc).
Further, TiO in step (3)
2precursor solution be butyl titanate, TiCl
4, isopropyl titanate or metatitanic acid n-propyl.
Further, TiO in step (3)
2the concentration of precursor solution be 0.5 ~ 10g/mL, in solution B, the content of hydrochloric acid is 5 ~ 20wt%, and the content of acetic acid is 10 ~ 40wt%, and the volume ratio of solution A and solution B is 1:2 ~ 5, and the addition of amido phthalocyanine is relative to TiO
2be 0.5 ~ 8wt%.
The invention has the beneficial effects as follows: synthesize solvable and have the comparatively strong amido phthalocyanine absorbed near infrared region, this amido phthalocyanine dissolves in TiO
2acidic sol system, adopt sol-gel process prepare amido phthalocyanine-TiO
2photochemical catalyst, can make amido phthalocyanine with molecular conformation fully and TiO
2contact, thus and TiO
2in conjunction with even, stable, and TiO can be made
2wavelength response range be extended near infrared region; Amido phthalocyanine-TiO
2the photocatalytic degradation effect of near infrared light catalyst is better than TiO
2, with common phthalocyanine-TiO
2photochemical catalyst is compared higher catalytic efficiency, and has certain stability, can be recycled.
Accompanying drawing explanation
Below in conjunction with accompanying drawing, the present invention is further described.
Fig. 1 is the uv-visible absorption spectra figure of seven kinds of solubility amido phthalocyanines;
Fig. 2 is three kinds of amido phthalocyanine-TiO
2the uv-visible absorption spectra figure of near infrared light catalyst;
Fig. 3 is 1wt% α-TDMACuPc-TiO
2near infrared light catalyst and TiO
2the degradation curve figure of photocatalytic degradation crystal violet.
Detailed description of the invention
The invention will be further described in conjunction with specific embodiments now, and following examples are intended to the present invention instead of limitation of the invention further are described.
Embodiment 1
The solubility amido phthalocyanine that the present embodiment is selected is 3,3 ', 3 ", 3 " '-four n-octyl amine base manganese phthalocyanines (α-TnOAMnPc), concrete structure formula is as follows, and synthetic method is as follows:
(1) synthesis of 3-n-octyl amine base phthalic nitrile (α-nOAPn):
Thermometer is being housed, is adding 17.30g 3-nitro phthalic nitrile, 14.19g n-octyl amine, 20.24g triethylamine and 50mL DMAC in the there-necked flask of the 250mL of magnetic stirring successively, room temperature reaction 12h under stirring condition.Reaction terminates, and is poured in the beaker filling 500mL deionized water by reactant liquor and precipitates, and sediment is washed to washing lotion in neutral, dry, with absolute ethyl alcohol recrystallization, obtain orange/yellow solid, 50 DEG C of dry 24h in vacuum drying oven, obtain orange/yellow solid crystallization 25.4g, productive rate 84%.
(2) 3,3 ', 3 ", the 3 " synthesis of '-four n-octyl amine base manganese phthalocyanines (α-TnOAMnPc):
Thermometer is being housed, in the there-necked flask of the 100mL of magnetic stirring, is adding 4g α-nOAPn, 0.772g MnCl successively
24H
2o, 0.596g DBU and 40mL n-hexyl alcohol, under nitrogen protection in 155 DEG C of heating stirring reaction 16h.Be cooled to room temperature after reaction terminates, add ethyl acetate to reactant liquor and separate out black precipitate, decompress filter, with ethyl acetate, methyl alcohol successively cyclic washing, dry, obtain pressed powder 3.8g, productive rate 80%.
(3) the amido phthalocyanine-TiO selected
2near infrared light catalyst is 8wt% α-TnOAMnPc-TiO
2near infrared light catalyst, preparation method is as follows:
In constant pressure funnel, add 20mL butyl titanate, separately get 25mL absolute ethyl alcohol in 100mL beaker, under the condition of low rate mixing, butyl titanate in constant pressure funnel is slowly joined in beaker, control rate of addition, complete in 30min, obtain solution A.In 250mL there-necked flask, add 100mL deionized water, 25mL concentrated hydrochloric acid, 25mL glacial acetic acid, be uniformly mixed, obtain solution B.The there-necked flask that B solution is housed is moved in 30 DEG C of thermostatical oil baths the stirring that remains a constant speed, solution A is loaded in constant pressure funnel, be slowly added drop-wise in B solution, be added dropwise to complete in 1h, obtain TiO
2colloidal sol.Then take 400mg α-TnOAMnPc and join TiO
2in colloidal sol, be stirred to α-TnOAMnPc and dissolve, obtain the α-TnOAMnPc-TiO of clear
2photocatalyst sol.Ageing 3d at the photocatalyst sol prepared is sealed in 70 DEG C, rear uncovered oven dry, to powder, with absolute ethanol washing several, is dried, is obtained relative to TiO
2α-the TnOAMnPc-TiO of 8wt%
2photochemical catalyst.
Embodiment 2
The solubility amido phthalocyanine that the present embodiment is selected is 4,4 ', 4 ", 4 " '-four n-butylamine-based manganese phthalocyanines (β-TnBAMnPc), concrete structure formula is as follows, and synthetic method is as follows:
(1) synthesis of 4-n-butylamine-based phthalic nitrile (β-nBAPn):
Thermometer is being housed, is adding 17.30g 4-nitro phthalic nitrile, 8.03g n-butylamine, 20.24g triethylamine and 50mL DMAC in the there-necked flask of the 250mL of magnetic stirring successively, room temperature reaction 12h under stirring condition.Reaction terminates, and is poured in the beaker filling 500mL deionized water by reactant liquor and precipitates, and sediment is washed to washing lotion in neutral, dry, with absolute ethyl alcohol recrystallization, obtain orange/yellow solid, 50 DEG C of dry 24h in vacuum drying oven, obtain orange/yellow solid crystallization 22.9g, productive rate 93%.
(2) 4,4 ', 4 ", the 4 " synthesis of '-four n-butylamine-based manganese phthalocyanines (β-TnBAMnPc):
Thermometer is being housed, in the there-necked flask of the 100mL of magnetic stirring, is adding 4g β-nBAPn, 0.985g MnCl successively
24H
2o, 0.76g DBU and 40mL n-hexyl alcohol, under nitrogen protection in 155 DEG C of heating stirring reaction 16h.Be cooled to room temperature after reaction terminates, add ethyl acetate to reactant liquor and separate out black precipitate, decompress filter, with ethyl acetate, methyl alcohol successively cyclic washing, dry, obtain pressed powder 3.7g, productive rate 74%.
(3) the amido phthalocyanine-TiO selected
2near infrared light catalyst is 1wt% β-TnBAMnPc-TiO
2near infrared light catalyst, preparation method is as follows:
In constant pressure funnel, add 20mL butyl titanate, separately get 25mL absolute ethyl alcohol in 100mL beaker, under the condition of low rate mixing, butyl titanate in constant pressure funnel is slowly joined in beaker, control rate of addition, complete in 30min, obtain solution A.In 250mL there-necked flask, add 100mL deionized water, 25mL concentrated hydrochloric acid, 25mL glacial acetic acid, be uniformly mixed, obtain solution B.The there-necked flask that B solution is housed is moved in 30 DEG C of thermostatical oil baths the stirring that remains a constant speed, solution A is loaded in constant pressure funnel, be slowly added drop-wise in B solution, be added dropwise to complete in 1h, obtain TiO
2colloidal sol.Then take 50mg β-TnBAMnPc and join TiO
2in colloidal sol, be stirred to β-TnBAMnPc and dissolve, obtain the β-TnBAMnPc-TiO of clear
2photocatalyst sol.Ageing 3d at the photocatalyst sol prepared is sealed in 70 DEG C, rear uncovered oven dry, to powder, with absolute ethanol washing several, is dried, is obtained relative to TiO
2β-the TnBAMnPc-TiO of 1wt%
2photochemical catalyst.
Embodiment 3
The solubility amido phthalocyanine that the present embodiment is selected is 3,3 ', 3 ", 3 " '-four dimethylamino copper phthalocyanines (α-TDMACuPc), concrete structure formula is as follows, and synthetic method is as follows:
(1) synthesis of 3-dimethylamino phthalic nitrile (α-DMAPn):
Thermometer is being housed, is adding 17.30g 3-nitro phthalic nitrile, 20.45g dimethylamine agueous solution (33wt%), 20.24g triethylamine and 50mL DMAC in the there-necked flask of the 250mL of magnetic stirring successively, room temperature reaction 12h under stirring condition.Reaction terminates, and is poured in the beaker filling 500mL deionized water by reactant liquor and precipitates, and sediment is washed to washing lotion in neutral, dry, with absolute ethyl alcohol recrystallization, obtain orange/yellow solid, put it into 50 DEG C of dry 24h in vacuum drying oven, obtain orange/yellow solid crystallization 18.5g, productive rate 85%.
(2) 3,3 ', 3 ", the 3 " synthesis of '-four dimethylamino copper phthalocyanines (α-TDMACuPc):
Thermometer is being housed, in the there-necked flask of the 100mL of magnetic stirring, is adding 4g α-DMAPn, 0.997g CuCl successively
22H
2o, 0.889g DBU and 40mL n-hexyl alcohol, under nitrogen protection in 155 DEG C of heating stirring reaction 16h.Be cooled to room temperature after reaction terminates, add ethyl acetate to reactant liquor and separate out dark blue precipitate, decompress filter, with ethyl acetate, methyl alcohol successively cyclic washing, dry, obtain pressed powder 3.9g, productive rate 78%.
(3) the amido phthalocyanine-TiO selected
2near infrared light catalyst is 0.5wt% α-TDMACuPc-TiO
2near infrared light catalyst, preparation method is as follows:
In constant pressure funnel, add 20mL butyl titanate, separately get 25mL absolute ethyl alcohol in 100mL beaker, under the condition of low rate mixing, butyl titanate in constant pressure funnel is slowly joined in beaker, control rate of addition, complete in 30min, obtain solution A.In 250mL there-necked flask, add 100mL deionized water, 25mL concentrated hydrochloric acid, 25mL glacial acetic acid, be uniformly mixed, obtain solution B.The there-necked flask that B solution is housed is moved in 30 DEG C of thermostatical oil baths the stirring that remains a constant speed, solution A is loaded in constant pressure funnel, be slowly added drop-wise in B solution, be added dropwise to complete in 1h, obtain TiO
2colloidal sol.Then take 25mg α-TDMACuPc and join TiO
2in colloidal sol, be stirred to α-TDMACuPc and dissolve, obtain the blue α-TDMACuPc-TiO of clear
2photocatalyst sol.Ageing 3d at the photocatalyst sol prepared is sealed in 70 DEG C, rear uncovered oven dry, to powder, with absolute ethanol washing several, is dried, is obtained relative to TiO
2α-the TDMACuPc-TiO of 0.5wt%
2photochemical catalyst.
Embodiment 4
The solubility amido phthalocyanine that the present embodiment is selected is 3,3 ', 3 ", 3 " '-four n-butylamine-based phthalocyanine (α-TnBAH
2pc), concrete structure formula is as follows, and synthetic method is as follows:
(1) synthesis of 3-n-butylamine-based phthalic nitrile (α-nBAPn):
Thermometer is being housed, is adding 17.30g 3-nitro phthalic nitrile, 8.03g n-butylamine, 20.24g triethylamine and 50mL DMAC in the there-necked flask of the 250mL of magnetic stirring successively, room temperature reaction 12h under stirring condition.Reaction terminates, and is poured in the beaker filling 500mL deionized water by reactant liquor and precipitates, and sediment is washed to washing lotion in neutral, dry, with absolute ethyl alcohol recrystallization, obtain orange/yellow solid, 50 DEG C of dry 24h in vacuum drying oven, obtain orange/yellow solid crystallization 21.9g, productive rate 89%.
(2) 3,3 ', 3 ", 3 " '-four n-butylamine-based phthalocyanine (α-TnBAH
2pc) synthesis:
Thermometer is being housed, in the there-necked flask of the 100mL of magnetic stirring, is adding 4g α-nBAPn, 0.76g DBU and 40mL n-hexyl alcohol successively, under nitrogen protection in 155 DEG C of heating stirring reaction 16h.Be cooled to room temperature after reaction terminates, add ethyl acetate to reactant liquor and separate out black precipitate, decompress filter, with ethyl acetate, methyl alcohol successively cyclic washing, dry, obtain pressed powder 3.4g, productive rate 84%.
(3) the amido phthalocyanine-TiO selected
2near infrared light catalyst is 2wt% α-TnBAH
2pc-TiO
2near infrared light catalyst, preparation method is as follows:
In constant pressure funnel, add 20mL butyl titanate, separately get 25mL absolute ethyl alcohol in 100mL beaker, under the condition of low rate mixing, butyl titanate in constant pressure funnel is slowly joined in beaker, control rate of addition, complete in 30min, obtain solution A.In 250mL there-necked flask, add 100mL deionized water, 25mL concentrated hydrochloric acid, 25mL glacial acetic acid, be uniformly mixed, obtain solution B.The there-necked flask that B solution is housed is moved in 30 DEG C of thermostatical oil baths the stirring that remains a constant speed, solution A is loaded in constant pressure funnel, be slowly added drop-wise in B solution, be added dropwise to complete in 1h, obtain TiO
2colloidal sol.Then 100mg α-TnBAH is taken
2pc joins TiO
2in colloidal sol, be stirred to α-TnBAH
2pc dissolves, and obtains the α-TnBAH of clear
2pc-TiO
2photocatalyst sol.Ageing 3d at the photocatalyst sol prepared is sealed in 70 DEG C, rear uncovered oven dry, to powder, with absolute ethanol washing several, is dried, is obtained relative to TiO
2α-the TnBAH of 2wt%
2pc-TiO
2photochemical catalyst.
The experiment of crystal violet in photocatalytic degradation water
Amido phthalocyanine-the TiO of different content, different structure
2the photocatalytic degradation experiment of near infrared light catalyst, its step is as follows:
In 100mL beaker, add 70mL methyl violet aqueous solution (concentration 10mg/L) successively, 70mg amido phthalocyanine-TiO
2near infrared light catalyst (concentration 1mg/mL), keeps the pH=7 of solution, and lucifuge stirs 10min, makes catalyst and crystal violet reach the attached balance of absorption-desorption.With halogen tungsten lamp simulated solar irradiation, irradiate under reaction system being placed in halogen tungsten lamp, 3mL solution is got every 30min, with 0.2 μm of micropore filter elimination catalyst granules, measure filtrate in the change of 580nm (crystal violet maximum absorption wavelength) place's absorbance with ultraviolet-visible spectrophotometer, measure crystal violet degradation rate by following formula:
A
0: initial absorbance, absorbance during At:t.
In order to contrast, adopt commodity TiO
2under identical experiment condition, the experiment of crystal violet in photocatalytic degradation water has been carried out as photochemical catalyst.
Fig. 1 is the absorption spectrogram of seven kinds of amido phthalocyanines, and visible amido phthalocyanine exists stronger absorption near infrared region.
Fig. 2 is wherein three kinds of amido phthalocyanine-TiO
2the absorption spectrogram of near infrared light catalyst, visible amido phthalocyanine-TiO
2stronger absorption is there is near infrared light catalyst near infrared region.
Fig. 3 is wherein a kind of amido phthalocyanine-TiO
2the catalytic degradation curve of near infrared light catalyst, contrasts known with TiO2, and catalyst is than simple TiO
2catalytic effect will be got well.
Following table is seven kinds of amido phthalocyanine-TiO
2near infrared light catalyst is to the catalysis degradation modulus of crystal violet:
Amido phthalocyanine-TiO as seen from the above table
2the catalytic effect of near infrared light catalyst is good.
Claims (9)
1. a preparation method for solubility amido phthalocyanine-titanium dioxide near infrared light catalyst, is characterized in that: comprise the following steps:
(1) synthesis of amido phthalic nitrile:
Nitro phthalic nitrile, organic amine, weak base and solvent is added in reaction vessel, room temperature reaction 12 ~ 24h under stirring condition, reactant liquor is poured in the beaker filling appropriate amount of deionized water after reaction terminates and precipitate, sediment is washed to washing lotion in neutral, dry, with absolute ethyl alcohol recrystallization, recrystallized product is put into vacuum drying oven 40 ~ 50 DEG C of drying 12 ~ 24h, obtain amido phthalic nitrile;
(2) synthesis of amido phthalocyanine:
Amido phthalic nitrile, slaine, 1 that step (1) is obtained is added in reaction vessel, 8-diazabicylo 11 carbon-7-alkene (DBU) and solvent, 130 ~ 160 DEG C of reaction 12 ~ 24h under nitrogen protection, be cooled to room temperature after reaction terminates, in reactant liquor, add ethyl acetate separating out to there being product, decompress filter, with ethyl acetate, methyl alcohol successively cyclic washing, dry, obtain black or blue solid powder, namely obtain amido phthalocyanine;
(3) sol-gel process is adopted to prepare amido phthalocyanine-TiO
2near infrared light catalyst:
In reaction vessel, add absolute ethyl alcohol, slowly drip TiO wherein under agitation
2precursor solution, stir and obtain solution A; In another reaction vessel, add deionized water, concentrated hydrochloric acid and glacial acetic acid, stir to obtain solution B; B solution at the uniform velocity stirred at 30 ~ 40 DEG C, solution A be slowly added drop-wise in B solution subsequently, 1 ~ 2h drips, and fully stirs and obtains TiO
2colloidal sol;
To TiO
2add the amido phthalocyanine of the obtained difference amount of step (2) in colloidal sol, be stirred to amido phthalocyanine and dissolve, obtain the amido phthalocyanine-TiO of clear
2colloidal sol, by amido phthalocyanine-TiO
2colloidal sol sealing, ageing 2 ~ 4d at 60 ~ 70 DEG C, uncovered oven dry is to powder afterwards, with absolute ethanol washing for several times, dry, obtain the amido phthalocyanine-TiO of different content
2near infrared light catalyst.
2. the preparation method of a kind of solubility amido phthalocyanine-titanium dioxide near infrared light catalyst according to claim 1, it is characterized in that: in described step (1), nitro phthalic nitrile is 3-nitro phthalic nitrile or 4-nitro phthalic nitrile, organic amine is n-butylamine, n-octyl amine or dimethylamine agueous solution, weak base is triethylamine, potash or potassium acetate, and solvent is DMSO, DMF or DMAC.
3. the preparation method of a kind of solubility amido phthalocyanine-titanium dioxide near infrared light catalyst according to claim 1, it is characterized in that: phthalic nitrile, organic amine, weak base rate of charge are mol ratio=1:(0.11 ~ 0.15 in described step (1)): (0.2 ~ 0.25), the consumption of solvent is make to feed intake the molar concentration of total amount at 8 ~ 9mol/L.
4. the preparation method of a kind of solubility amido phthalocyanine-titanium dioxide near infrared light catalyst according to claim 1, is characterized in that: obtaining amido phthalic nitrile in described step (1) is 3-n-butylamine-based phthalic nitrile (α-nBAPn), 3-dimethylamino phthalic nitrile (α-DMAPn), 4-n-butylamine-based phthalic nitrile (β-nBAPn) or 3-n-octyl amine base phthalic nitrile (α-nOAPn).
5. the preparation method of a kind of solubility amido phthalocyanine-titanium dioxide near infrared light catalyst according to claim 1, is characterized in that: in described step (2), slaine is MnCl
24H
2o or CuCl
22H
2o, solvent is n-hexyl alcohol, n-amyl alcohol or n-heptanol, and phthalocyanine that need not be metal-doped is without the need to adding slaine.
6. the preparation method of a kind of solubility amido phthalocyanine-titanium dioxide near infrared light catalyst according to claim 1, it is characterized in that: amido phthalic nitrile, slaine, DBU rate of charge are mol ratio=1:(0.25 ~ 0.3 in described step (2)): (0.25 ~ 0.3), the consumption of solvent is make to feed intake the molar concentration of total amount at 0.55 ~ 0.85mol/L.
7. the preparation method of a kind of solubility amido phthalocyanine-titanium dioxide near infrared light catalyst according to claim 1, it is characterized in that: obtaining amido phthalocyanine in described step (2) is 3,3 ', 3 ", 3 " '-four n-butylamine-based manganese phthalocyanines (α-TnBAMnPc), 3,3 ', 3 ", 3 " '-four n-butylamine-based copper phthalocyanines (α-TnBACuPc), 3,3 ', 3 ", 3 " '-four n-butylamine-based phthalocyanine (α-TnBAH
2pc), 4,4 ', 4 "; 4 " '-four n-butylamine-based manganese phthalocyanines (β-TnBAMnPc), 3,3 ', 3 ", 3 " '-four dimethylamino manganese phthalocyanines (α-TDMAMnPc), 3,3 ', 3 ", 3 " '-four dimethylamino copper phthalocyanines (α-TDMACuPc) or 3,3 ', 3 ", 3 " '-four n-octyl amine base manganese phthalocyanines (α-TnOAMnPc).
8. the preparation method of a kind of solubility amido phthalocyanine-titanium dioxide near infrared light catalyst according to claim 1, is characterized in that: TiO in described step (3)
2precursor solution be butyl titanate, TiCl
4, isopropyl titanate or metatitanic acid n-propyl.
9. the preparation method of a kind of solubility amido phthalocyanine-titanium dioxide near infrared light catalyst according to claim 1, is characterized in that: TiO in described step (3)
2the concentration of precursor solution be 0.5 ~ 10g/mL, in solution B, the content of hydrochloric acid is 5 ~ 20wt%, and the content of acetic acid is 10 ~ 40wt%, and the volume ratio of solution A and solution B is 1:2 ~ 5, and the addition of amido phthalocyanine is relative to TiO
2be 0.5 ~ 8wt%.
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| CN108371958A (en) * | 2018-01-22 | 2018-08-07 | 西北大学 | A kind of Asia phthalocyanine/titanium dioxide nano photocatalysis agent and its preparation method and application |
| CN109433274A (en) * | 2018-11-14 | 2019-03-08 | 郑州师范学院 | A kind of cupric organometallic complex-TiO2Composite material and preparation method and application |
| CN111998883A (en) * | 2020-04-16 | 2020-11-27 | 首都医科大学 | Manufacturing method of near-infrared light sensor based on DBU type eutectic solvent |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108371958A (en) * | 2018-01-22 | 2018-08-07 | 西北大学 | A kind of Asia phthalocyanine/titanium dioxide nano photocatalysis agent and its preparation method and application |
| CN109433274A (en) * | 2018-11-14 | 2019-03-08 | 郑州师范学院 | A kind of cupric organometallic complex-TiO2Composite material and preparation method and application |
| CN109433274B (en) * | 2018-11-14 | 2021-09-10 | 郑州师范学院 | Copper-containing organic metal complex-TiO2Composite material and preparation method and application thereof |
| CN111998883A (en) * | 2020-04-16 | 2020-11-27 | 首都医科大学 | Manufacturing method of near-infrared light sensor based on DBU type eutectic solvent |
| CN111998883B (en) * | 2020-04-16 | 2022-06-21 | 首都医科大学 | Manufacturing method of near-infrared light sensor based on DBU type eutectic solvent |
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