CN1680022A - Supersonic preparation of phthalocyanin sensitized nano cobalt dioxide powder - Google Patents

Abstract

A process for preparing the phthalocyanine sensitized TiO2 nanoparticles by in-situ ultrasonic method includes such steps as preparing the precurse liquid of TiO2 nanoparticles, and adding phthalocyanine as sensitizer while preparing TiO2 nanoparticles in ultrasonic condition. Its advantages are high dispersity and stability, high catalytic activity to visual light and broadband.

Description

The preparation method ultrasonic on the throne of phthalocyanine-sensitized nano TiO 2 powder

Technical field

The present invention relates to a kind of preparation method ultrasonic on the throne of phthalocyanine-sensitized nano TiO 2 powder, this phthalocyanine-sensitized titanium dioxide powder possesses the performance of high photocatalysis quantum efficiency and wide spectral response.

Background technology

TiO ₂Be a kind of important semi-conducting material,, indissoluble stable because of its chemical property, nontoxic, low cost and other advantages are widely used in photocatalysis, and are acknowledged as more satisfactory photochemical catalyst at present.But single TiO ₂Absorbing wavelength less than 400nm, visible light is not almost absorbed, sunshine absorbed account for 4% of its gross energy.In order to improve the utilization rate of sunshine, must be to TiO ₂Carry out modification and handle, make it have visible light-responded photocatalysis performance.

Adopt organic sensitization composite Ti O ₂The main advantage of photochemical catalyst is to reach the synergy of realizing improving the photocatalysis quantum efficiency and widening spectral response; Organic sensitizer molecule is easy to carry out chemical modification simultaneously, realizes sensitization altogether, thereby further expands its absorption region and raising photo-quantum efficiency at visible light wave range.Contain a big π delocalization system in the phthalocyanine structure, have two absorption band: Q band light absorption wavelength in the 600-700nm scope, to change usually; B band light absorption wavelength changes in the 300-400nm scope, the phthalocyanine of different central ions has different absorption spectrums, four phenyl ring of phthalocyanine can also sulfonation, halo, alkoxylate wait and change its absorption band position, and this just is extended to visible region and MOLECULE DESIGN has been created condition for the wavelength response of phthalocyanine-sensitized catalyst from ultraviolet.

Current phthalocyanine-sensitized nano-TiO ₂What the preparation of photochemical catalyst was adopted all is direct complex method, is about to phthalocyanine and nano-TiO ₂Powder or porous TiO ₂Film directly produces physics or chemical bond by chemical reaction method, physical blending method, vacuum sublimation sedimentation and dipping absorption method etc.Obviously, the system dispersing uniformity is poor, and doping content and microstructure such as are difficult to regulate and control at shortcoming makes phthalocyanine-sensitized composite Ti O by these direct complex methods preparations ₂Photochemical catalyst has unstable properties, production technology is difficult to shortcomings such as control and cost height, has limited it to promote the use of, therefore must the new preparation technology of exploitation.

Summary of the invention

The object of the invention provide a kind of stable, reliably, the preparation method ultrasonic on the throne of the phthalocyanine-sensitized nano TiO 2 powder of high visible light catalytic activity cheaply.

It is to adopt under the effect of high power density ultrasonic wave, makes titanium dioxide nano-particle form the preparation method of the phthalocyanine-sensitized nano TiO 2 powder that carries out with phthalocyanine-sensitized composite sync.

The concrete steps of this method are:

1) preparation of nano-powder pioneer liquid:

Nano-powder precursor, diluent, reaction controlling agent and sensitizer are mixed, mixeding liquid temperature is controlled to be 0 ℃～100 ℃, obtain the nano-powder pioneer liquid of homogeneous transparent, the molar fraction that nano-powder pioneer liquid is formed is: nano-powder precursor 10, diluent 10～250, reaction controlling agent 0～20, sensitizer 0.05～4; The nano-powder precursor is inorganic salts or metatitanic acid or their mixture that contains the alkoxide of titanium ion or contain titanium ion, diluent is water or organic solvent or their mixture, the reaction controlling agent is inorganic acid or inorganic base or organic acids and base or their mixture, and sensitizer is solubility metal-free phthalocyanine or metal phthalocyanine or their mixture;

2) preparation of nano-powder under the ultrasound condition:

Under 0 ℃～100 ℃ temperature, be 10～500kHz with nano-powder pioneer liquid in frequency, power density is 50～200W/cm ²Ultrasound condition handled 0.5～10 hour down; Centrifugation goes out precipitation, cleans, and 30 ℃～200 ℃ vacuum drying obtain the phthalocyanine-sensitized nano TiO 2 powder of high visible light catalytic activity.

The phthalocyanine-sensitized nano-TiO of the present invention and direct complex method preparation ₂Photochemical catalyst is compared, and has following outstanding advantage:

1. preparation process is carried out at low temperatures, and the gained precipitation need not carried out high-temperature heat treatment and promptly be had anatase crystal and high visible light catalytic activity preferably;

2. the preparation of nano TiO 2 powder and one step of photoactivate finish, and manufacturing cycle is short, and technology is simple, is fit to produce in batches;

3. have highlight catalytic active under the visible light, greatly improved nano-TiO ₂Photocatalysis efficiency and solar energy utilization ratio, certain kind organic pollution of effectively degrading;

5. stability is high, can repeatedly recycle repeatedly.

The specific embodiment

Elaborate below in conjunction with embodiment:

The preparation method ultrasonic on the throne of phthalocyanine-sensitized nano TiO 2 powder utilizes ultrasonic cavitation effect instantaneous localized hyperthermia high pressure that produces and the microjet with powerful impulsive force to promote chemical reaction and cenotype to form, suppress the nano powder preparation technology that crystal grain is reunited and grown up, adjusts the product crystal formation, add synchronously as phthalocyanine molecule with sensitizer, make it participate in nano particle forming process and compound with it, so be uniformly dispersed, stable performance and have the phthalocyanine-sensitized nano TiO 2 powder of high visible light catalytic activity.

Embodiment 1

The nano-powder pioneer liquid that adopts is formed (mole composition): titanium tetrachloride 10 ± 0.2, triethanolamine 10 ± 0.2, ethanol 30 ± 1.2, deionized water 15 ± 2.5, aluminum phthalocyanine 0.12 ± 0.05.Regulate mixeding liquid temperature to 25 ℃～30 ℃, stir after 30 ± 5 minutes blue pioneer's liquid of evenly being clarified.Adding ammoniacal liquor accent pH value is 3～6, obtains translucent blue sol shape pioneer liquid;

The container that fills this pioneer's liquid is put into 90 ± 5 ℃ of water-baths, is 100W/cm with frequency for the 20kHz power density ²The probe of ultrasonic generator immerse in the colloidal sol, ultrasonic 2 ± 0.5 hours, centrifugation was cleaned, 50 ℃ of vacuum drying 24 hours obtain phthalocyanine-sensitized nano TiO 2 powder.

X-ray diffraction analysis (XRD) shows: the gained nano TiO 2 powder has better Detitanium-ore-type structure; We are set at the catalytic organism object with the methyl orange solution of 20mg/L, have carried out the photocatalysis experiment.Powder-like is 10mg, methyl orange solution is got 10ml, with the German Ou Silang HQI-BT 400W/D of company metal halide lamp is light source, the same terms down contrast at visible light according to the (photocatalysis performance of 30min of λ＞450nm), phthalocyanine-sensitized nano TiO 2 powder (degradation rate 80%), compare with the nano-titanium dioxide powder (degradation rate 48%) of the not same recipe preparation of compound phthalocyanine, its photocatalytic activity has improved nearly 1 times, compare with the commodity titanium dioxide P25 (degradation rate 10%) of international popular, its photocatalytic activity has improved nearly 7 times; This explanation phthalocyanine has played tangible sensibilization in visible-range, improved the photocatalysis quantum efficiency and widened scope of spectral response.

Embodiment 2

The nano-powder pioneer liquid that adopts is formed (mole composition): butyl titanate 10 ± 0.5, acetylacetone,2,4-pentanedione 2 ± 0.5, ethanol 20 ± 5, deionized water 1.28 ± 0.5, sulfonated phthalocyanine copper 1.5 ± 0.3.Regulate mixeding liquid temperature to 25 ℃～30 ℃, stir after 30 ± 5 minutes blue pioneer's liquid of evenly being clarified; Adding less ammonia makes solution be transformed into blue sol shape pioneer liquid;

The container that fills this pioneer's liquid is put into 40 ± 5 ℃ of water-baths, is 150W/cm with frequency for the 50kHz power density ²The probe of ultrasonic generator immerse in the colloidal sol, ultrasonic 4 ± 0.5 hours, centrifugation was cleaned, 120 ℃ of dryings 24 hours obtain phthalocyanine-sensitized nano TiO 2 powder.

X-ray diffraction analysis (XRD) shows: the gained nano TiO 2 powder has better Detitanium-ore-type structure; Wavelength shows greater than photocatalytic degradation methyl orange test under the visible light of 450nm: products obtained therefrom has very high photocatalysis and lives under visible light, its photocatalytic activity is compared with the nano-titanium dioxide powder of the same recipe preparation of compound phthalocyanine not and has been improved nearly 1 times, and its photocatalytic activity has improved nearly 6 times than P25.

Embodiment 3

The nano-powder pioneer liquid that adopts is formed (mole composition): TiOSO ₄10 ± 2.5, ammoniacal liquor 0.5 ± 0.25, ethanol 350 ± 25, deionized water 900 ± 100, solubility metal-free phthalocyanine 0.25 ± 0.1.Regulate 80 ℃ ± 10 ℃ of mixeding liquid temperatures, during add sulfuric acid 0.01, stir after 60 ± 10 minutes, obtain pioneer's liquid of homogeneous transparent;

The container that fills this pioneer's liquid is put into 70 ± 5 ℃ of water-baths, is 150W/cm with frequency for the 400kHz power density ²The probe of ultrasonic generator immerse in the colloidal sol, ultrasonic 8 ± 0.5 hours, centrifugation was cleaned, 50 ℃ of dryings 24 hours obtain phthalocyanine-sensitized nano TiO 2 powder.

X-ray diffraction analysis (XRD) is similar to embodiment 1 greater than photocatalytic degradation methyl orange result of the test under the visible light of 450nm with wavelength.

Claims (2)

1. the preparation method ultrasonic on the throne of a phthalocyanine-sensitized nano TiO 2 powder, it is characterized in that: adopt under the effect of high power density ultrasonic wave, make titanium dioxide nano-particle form the preparation method of the phthalocyanine-sensitized nano TiO 2 powder that carries out with phthalocyanine-sensitized composite sync.

2. the preparation method ultrasonic on the throne of phthalocyanine-sensitized nano TiO 2 powder according to claim 1 is characterized in that, the concrete steps of method are:

1) preparation of nano-powder pioneer liquid:

Nano-powder precursor, diluent, reaction controlling agent and sensitizer are mixed, mixeding liquid temperature is controlled to be 0 ℃～100 ℃, obtain the nano-powder pioneer liquid of homogeneous transparent, the molar fraction that nano-powder pioneer liquid is formed is: nano-powder precursor 10, diluent 10～250, reaction controlling agent 0～20, sensitizer 0.05～4; The nano-powder precursor is inorganic salts or metatitanic acid or their mixture that contains the alkoxide of titanium ion or contain titanium ion, diluent is water or organic solvent or their mixture, the reaction controlling agent is inorganic acid or inorganic base or organic acids and base or their mixture, and sensitizer is solubility metal-free phthalocyanine or metal phthalocyanine or their mixture;

2) preparation of nano-powder under the ultrasound condition:

Under 0 ℃～100 ℃ temperature, be 10～500kHz with nano-powder pioneer liquid in frequency, power density is 50～200W/cm ²Ultrasound condition handled 0.5～10 hour down; Centrifugation goes out precipitation, cleans, and 30 ℃～200 ℃ vacuum drying obtain the phthalocyanine-sensitized nano TiO 2 powder of high visible light catalytic activity.