CN104785304A - Preparation and application of novel nano-heterostructure solar photocatalyst - Google Patents

Preparation and application of novel nano-heterostructure solar photocatalyst Download PDF

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CN104785304A
CN104785304A CN201510227925.4A CN201510227925A CN104785304A CN 104785304 A CN104785304 A CN 104785304A CN 201510227925 A CN201510227925 A CN 201510227925A CN 104785304 A CN104785304 A CN 104785304A
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梅立维
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A20/00—Water conservation; Efficient water supply; Efficient water use
    • Y02A20/20—Controlling water pollution; Waste water treatment
    • Y02A20/208—Off-grid powered water treatment
    • Y02A20/212—Solar-powered wastewater sewage treatment, e.g. spray evaporation
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/30—Wastewater or sewage treatment systems using renewable energies
    • Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy

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Abstract

The invention discloses a preparation method and application of a nano-heterostructure modified TiO2 solar photocatalyst. By using amino organic acid and heterocyclic nitrogen compounds as modifiers, a sol/gel-microwave irradiation combined preparation technique is adopted to perform doping modification on the TiO2 photocatalytic material base, so that defects or oxygen vacancies exist in the photocatalyst molecules, thereby generating an impurity energy level and further implementing red shift of response wavelength. The preparation method of the catalyst is simple, is mild and clean in conditions, and basically can not generate environmental pollution in the preparation process. The catalyst can be widely used in the fields of photocatalytic degradation of high-concentration organic industrial wastewater, catalytic hydrogen production, solar cells, sterilization and the like.

Description

A kind of preparations and applicatio of novel nano heterojunction solar photochemical catalyst
Technical field
The present invention relates to catalyst preparation technical field, be specifically related to a kind of modification TiO with nano-heterogeneous structure 2the preparation method of photochemical catalyst and application.
Background technology
It is an emerging green technology progressively grown up that photocatalysis oxidation technique is applied to environmental protection and treatment.Surface energy is by the characteristic of activation under light illumination to utilize metal oxide semiconductor material, and luminous energy can oxidation Decomposition organic matter, reducing heavy metal ion, kill bacteria and elimination peculiar smell effectively.Because photocatalysis technology can utilize sunshine or other natural daylight at room temperature to react, therefore both economical.And in fact photocatalysis technology has obtained initial success in indoor air purification, self-cleaning material, Superhydrophilic material etc., the market that catalysis material is applied in environment has progressively been formed.
Nearly ten years, place high hopes both at home and abroad to photocatalysis technology, many companies also inject capital into and carry out studying and commercial development both at home and abroad, have applied for a large amount of Patents.Although through the development of recent two decades, achieve obvious achievement in the research in photocatalysis technology field both at home and abroad, the Developing Application of solar energy photocatalytic material also also exist many deficiencies and defect, is mainly manifested in:
1. the spectral response of solar energy photocatalytic material is still partially narrow.
2. the photo-quantum efficiency of solar energy is lower.
3. the stability of catalyst needs to be improved further.
4. most work is still in the experimental study stage, and the industrialized unit with practical significance is few.
5. catalyst is more expensive, and the cost of device is higher, and integrated operation expense also needs to reduce further.
In order to improve TiO 2to utilization and the photocatalytic activity of sunshine, the way comparatively concentrated at present is to TiO by methods such as semiconductors coupling, ion doping and dye photoactivations 2catalysis material carries out modification, improves TiO to some extent 2to utilization and the photocatalytic activity of sunshine.But energy and TiO 2the narrow gap semiconductor of effective compound is less, and novel narrow gap semiconductor all adopts high temperature solid state reaction to synthesize substantially, and the specific surface area of catalyst finally obtained is less, makes its visible light catalysis activity on the low side; And metal ion mixing TiO 2then utilize the metal ion of doping at TiO 2define impurity energy level in band gap, although photoresponse scope can be extended to visible region, form again new light induced electron and the complex centre in hole simultaneously, reduce TiO 2catalytic activity; As for dye sensitization method, be then because sensitizer is at TiO 2surface easily desorption and from degraded, thus cause degradation product cannot permineralization, also result in secondary pollution simultaneously.
The present invention is directed at present TiO 2the technological deficiency that photochemical catalyst matrix modification exists and deficiency, develop and a kind ofly have that photoresponse scope is wide, conversion quantum efficiency is high, the novel nano heterojunction structure solar energy photocatalytic material of stable in catalytic performance, and use it for high-concentration organic industrial waste water process.
The thinking of product development of the present invention is exactly micro-structural, valence band and conduction band positions by regulating and controlling catalysis material, reduces band gap width to correct position, makes photochemical catalyst can realize response in visible-range.Specifically, the present invention is using amino organic acid and heterocyclic nitrogen compound as modifier, take Titanium alkoxides as presoma, Organic Alcohol is solvent, the preparation technology adopting sol/gel to combine with Microwave Radiation in Manufacturing, realizes the doping vario-property to conductor photocatalysis material matrix, makes the inner existing defects of photocatalyst elements or Lacking oxygen, produce impurity energy level, and then realize the red shift of response wave length.Method for preparing catalyst of the present invention is simple, mild condition cleans, and can not produce secondary pollution in preparation process.
Summary of the invention
As previously mentioned, the present invention, by the basis keeping above-mentioned existing photocatalysis technology advantage, for the deficiency that prior art exists, develops a kind of new type solar energy catalysis material for high-concentration organic industrial waste water process.This novel photocatalyst can respond preferably to solar energy, and accomplish to carry out controlled degradation (appropriateness degraded or mineralizing and degrading) to the organic matter in waste water, solar energy photocatalytic technology can be coupled preferably with other sewage disposal technologies various practical at present, and the optimization process for the dense organic industrial sewage of height provides a new practical approach.Realize especially by following technical step:
(1), by a certain amount of presoma, inhibitor and organic solvent mix, stir, obtain mother liquor.Slowly add a small amount of alcoholic solution and water to mother liquor again, stir evenly, drip acid and regulate pH value, form Homogeneous phase mixing liquid.
The normally inorganic or organic titanium alkoxide of presoma.Different Titanium alkoxides can form different structures, usually has monomer structure, dimer structure and trimer structure.Generally speaking, single polymers has less steric hindrance than oligomer, thus has higher hydrolytic-polymeric reaction active.Described Titanium alkoxides can be one in titanyl sulfate, butyl titanate, isopropyl titanate, titanium tetrachloride, titanium trichloride and (or) several, preferred titanium propanolate.
Add the hydrolysis that inhibitor can control Titanium alkoxides, different inhibitor has different impacts to particle outward appearance and physical property.Usual employing acid regulates the pH value of colloidal sol as inhibitor, can control the state of gel time and colloidal sol so preferably.Described inhibitor can be one in hydrochloric acid, glacial acetic acid, acetylacetone,2,4-pentanedione, oxalic acid and (or) several, preferred hydrochloric acid.
Solvent by substitution reaction, the complex reaction of alkyl, scold electrical, empty inhibition effect and complexing power to affect the hydrolysis of metal alkoxide and the degree of polycondensation.Different solvents is in collosol and gel heat treatment process, different with the temperature of burning owing to decomposing, and also can affect the crystallization process of material.Described solvent can be one in methyl alcohol, ethanol, isopropyl alcohol, n-butanol and (or) several, preferred isopropyl alcohol.
Add the hydrolysis rate that acid as catalyst not only can accelerate alkoxide, the polymerization rate of the alkoxide that simultaneously can slow down.Described acid can be one in hydrochloric acid, sulfuric acid, boric acid, phosphoric acid and (or) several, preferred hydrochloric acid.
(2) add a certain amount of modifier in the Homogeneous phase mixing liquid, to step one obtained, form stable sol system in the solution.Slowly be polymerized after ageing after a while, being formed with presoma is three-dimensional polymer or the particle space network of skeleton again, makes solvent become gel without mobility or poor fluidity.
As previously mentioned, the present invention is by carrying out doping vario-property to conductor photocatalysis material, makes the inner existing defects of photocatalyst elements or Lacking oxygen, produces impurity energy level, and then realize the response to visible ray.
Specifically, the present invention carries out modification by the method for nonmetal/metal composite doping to semiconductor light-catalyst matrix.
Nonmetal modifiers comprises amino organic acid and heterocyclic nitrogen compound.
Described amino organic acid can be one in sulfamic acid, ethylenediamine tetra-acetic acid, glutamic acid, secondary nitrilotriacetic acid, hydroxyethylethylene diamine tri-acetic acid, phenylalanine, histidine and (or) several, preferred sulfamic acid.
Described heterocyclic nitrogen compound can be one in nitrogen propane, pyridine, Phen, phenthazine, choline and (or) several, preferred nitrogen propane.
Metal modifiers is mainly transistion metal compound.
Described metal modifiers can be one in the oxide of Fe, Mn, V, Co, Cu, Zn, Ni, Ce, Sc element or chloride and (or) several, preferred FeCl 3.
(3), by step 2 obtain molten-gel rubber system rapid draing under the effect of microwave, remove solvent therebetween and become the xerogel of space structure, finally obtaining required catalysis material through grinding sub-sieve again.
Compare other and widen TiO by doping vario-property 2the technology of photochemical catalyst spectral response range, catalyst preparation process of the present invention has following innovative point:
1. there is the compound of special molecular structure as modifier using some, introduce nitrogenous source and the carbon source with heterocycle structure, grafting is on Ti atom, all or part of replacement oxygen atom and form the R-N-Ti-C-R structure of compound state, make the inner existing defects of photocatalyst elements or Lacking oxygen, produce impurity energy level, and then realize the red shift of response wave length.
2. by introducing certain amino organic acid, itself and TiO is made 2produce chelating grafting, thus make photocatalyst surface be provided with certain complexing power, this just makes material internal and surface create a large amount of defective bit, makes catalyst to O 2adsorption capacity strengthen.
3. the transition metal ions adulterated is highly dispersed in semiconductor catalyst, lattice structure be there occurs and distort and form Ti 2o 2m bridging oxygen structure.This structure restrained effectively the formation of the single crystalline phase of catalyst and makes catalysis material crystal grain have inside and outside two-layer crystalline phase, and effectively improve electron-hole separative efficiency in internal layer crystalline phase, catalyst crystal structure obtains obvious improvement.
4. in traditional sol-gel preparation process, due to the limitation by heating means itself, often there is larger contraction thus cause catalysis material active reduction when reality uses in catalyst surface.In view of this, the present invention adopts Microwave Radiation in Manufacturing to substitute traditional gel drying method.Test shows, the catalyst after microwave treatment, and when processing the industrial wastewater of higher concentration, the deactivation rate of catalyst has had obvious reduction.
To sum up, material preparation technology, photocatalysis technology and environment project have been merged in the present invention, and multi-crossed disciplines, infiltration and combination are carried out to material, physics, chemistry, environment and the energy, the some innovative technology points of final formation, have developed a kind of new type solar energy catalysis material for high-concentration organic industrial waste water process and technology supporting with it.
Accompanying drawing explanation
The transmission electron microscope picture of the sample of Fig. 1 obtained by embodiment one.
The wide-angle XRD collection of illustrative plates of the sample of Fig. 2 obtained by embodiment one.
The nitrogen Adsorption and desorption isotherms of the sample of Fig. 3 obtained by embodiment one and BJH graph of pore diameter distribution.
Detailed description of the invention
Be making further detailed, clear and complete description of how realizing below in conjunction with specific embodiment to the present invention, listed embodiment is only be further described the present invention, not thereby limiting the invention:
Embodiment one
Get 9mL metatitanic acid four isopropyl ester (99%) to pour into and be equipped with in the 200mL beaker of 22mL ethanol, stir evenly.Then, in beaker, add glacial acetic acid 1.7mL, sulfamic acid 7.3mL (15%) and polyethylene imine 8.8mL (99%), stir and evenly mix.Add deionized water 35mL, FeCl again 3solution 10mL (10%), and regulate pH value with appropriate watery hydrochloric acid.Occur after a certain amount of precipitation until solution system, then add 20mL deionized water, stir and form colloidal sol in 2 hours.
Put into by obtained colloidal sol in microwave reaction stove, under 80% power, irradiation took out after 5 ~ 7 minutes, cooling.Pulverized, be sized to 200 orders by cooled gel solids, products obtained therefrom is the catalysis material with nano-heterogeneous structure.
Structural characterization
Fig. 1 is the appearance structure that the transmission electron microscope photo adopting HIT H-7650 high resolution transmission electron microscopy to obtain analyzes sample, and as can be seen from Figure, sample is formed by the nano particle of two kinds of different sizes.
Fig. 2 adopts the sample structure that Rigaku Rigaku Miniflex type X-ray diffractometer is measured, and as can be seen from XRD spectra, the sample obtained is sharp titanium/rutile TiO 2out-phase structure.
Fig. 3 is the specific area and the pore structure that adopt the automatic physical adsorption appearance working sample of U.S. Micromeritics company ASAP-2020 type, and calculate according to BJH, the specific area of sample is 79.6m 2/ g, average pore size is 5.64nm.
Embodiment two
The fracturing outlet liquid of certain pressing crack construction well domestic is adopted to be indoor handling object.This fracturing fluid is aqueous fracturing fluid, and thickener is hydroxypropyl level guar gum (HPG), in addition also containing additives such as a certain amount of gel breaker, cleanup additive, bactericide, surfactants.Outward appearance thickness, in brown color.Water analysis is in table 1:
Table 1 fracturing outlet liquid Analysis Results of Water Quality
Index PH Viscosity (mPa.S) SS(mg/L) COD cr(mg/L) Colourity (extension rate) BOD 5(mg/L) TDS(mg/L)
Numerical value 7.4 13 700 7300 55 220 7700
As seen from Table 1, this fracturing outlet liquid is the industrial wastewater that typical height is sticky, high COD, high chroma, biochemical are extremely low.Single materialization or biochemical technology is adopted almost to be difficult to process standard discharge.
Under outdoor open-air condition, the pretreated supernatant 350ml of the AOP that learns from else's experience pours in 500ml beaker, adds the made photochemical catalyst 0.3g of embodiment one, under the effect of magnetic agitation, photochemical catalyst is disperseed in the solution.Meanwhile, open air aeration machine and be filled with air to solution.Now, under the acting in conjunction of sunshine, photochemical catalyst and air, circular response 5 ~ 10 hours, utilizes photocatalytic oxidation degradation until pollutant in mineralizing solution.By carrying out water analysis to solution sampling after reaction, data are in table 2:
Table 2 fracturing outlet liquid photocatalysis treatment effluent quality analysis result
Index PH Viscosity (mPa.S) SS(mg/L) COD cr(mg/L) Colourity (extension rate) TDS(mg/L)
Numerical value 7.4 0.7 22 75 10 3300
Can be clear that by table 2, the pressure after photocatalysis treatment returns the discharge standard that liquid water outlet can reach national regulations completely.
Embodiment three
Repeat the step of embodiment three, just change light-catalyzed reaction time to 2 ~ 5 hour, measure water quality parameter after being filtered by solution, data are in table 3:
Table 3 fracturing outlet liquid photocatalysis treatment effluent quality analysis result _ 2
Index PH viscosity (mPa.S) SS (mg/L) COD cr(mg/L) colourity (extension rate) BOD 5(mg/L) TDS(mg/L)
Numerical value 7.51.53077012345 3200
Clearly, although water outlet does not now reach the numerical value that discharge standard specifies yet, BOD 5/ COD crvalue is greater than 0.3, and bioanalysis rule of thumb can be adopted to carry out subsequent treatment.Membrane bioreaction technology (MBR) is used membrane separation technique to be combined with activated sludge process, sludge sewage is selected to do mud kind, maintain MLSS7500 (mg/L), dissolved oxygen concentration 4 ~ 6 (mg/L), biochemical reaction 6 ~ 8 hours, after UF membrane, effluent quality analyzes data in table 4:
Table 4 fracturing outlet liquid photocatalysis treatment effluent quality analysis result _ 3
Index PH Viscosity (mPa.S) SS (mg/L) COD cr(mg/L) Colourity (extension rate) TDS (mg/L)
Numerical value 7.4 0.52370 53100
Found out by table 4, return liquid due to the pressure after photocatalysis treatment and there is good bio-degradable, adopt bioremediation just can realize organic matter degradation and the target of standard discharge, the optimization process for the dense organic industrial sewage of height provides a new practical approach.

Claims (11)

1. a preparation method for novel nano heterojunction solar photochemical catalyst, is characterized in that, comprises the following steps:
(1) a certain amount of presoma, inhibitor and organic solvent are mixed, stir, obtain mother liquor.Slowly add a small amount of alcoholic solution and water to mother liquor again, stir evenly, drip acid and regulate pH value, form Homogeneous phase mixing liquid.
(2) add a certain amount of modifier in the Homogeneous phase mixing liquid obtained to step one, form stable sol system in the solution.Slowly be polymerized after ageing after a while, being formed with presoma is three-dimensional polymer or the particle space network of skeleton again, makes solvent become gel without mobility or poor fluidity.
(3) step 2 is obtained molten-gel rubber system rapid draing under the effect of microwave, remove solvent therebetween and become the xerogel of space structure, finally obtaining required catalysis material through grinding sub-sieve again.
2. according to claim 1, said presoma can be one in titanyl sulfate, butyl titanate, isopropyl titanate, titanium tetrachloride, titanium trichloride and (or) several, preferred isopropyl titanate.
3. according to claim 1, said inhibitor can be one in hydrochloric acid, glacial acetic acid, acetylacetone,2,4-pentanedione, oxalic acid and (or) several, preferred hydrochloric acid.
4. according to claim 1, said solvent can be one in methyl alcohol, ethanol, isopropyl alcohol, n-butanol and (or) several, preferred isopropyl alcohol.
5. according to claim 1, the acid of said adjustment pH value can be one in hydrochloric acid, sulfuric acid, boric acid, phosphoric acid and (or) several, preferred hydrochloric acid.
6. according to claim 1, said modifier comprises nonmetal and metallic compound.
7. according to claim 1, said nonmetal modifiers comprises amino organic acid and heterocyclic nitrogen compound.
8. according to claim 1, said amino organic acid can be one in sulfamic acid, ethylenediamine tetra-acetic acid, glutamic acid, secondary nitrilotriacetic acid, hydroxyethylethylene diamine tri-acetic acid, phenylalanine, histidine and (or) several, preferred sulfamic acid.
9. according to claim 1, said heterocyclic nitrogen compound can be one in nitrogen propane, pyridine, Phen, phenthazine, choline and (or) several, preferred nitrogen propane.
10. according to claim 1, said metal modifiers can be one in the oxide of Fe, Mn, V, Co, Cu, Zn, Ni, Ce, Sc element or chloride and (or) several, preferred FeCl 3.
11. according to claim 1, and said gel drying method is microwave drying.
CN201510227925.4A 2015-05-07 2015-05-07 Preparation and application of novel nano-heterostructure solar photocatalyst Pending CN104785304A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105131656A (en) * 2015-10-13 2015-12-09 中国石油化工股份有限公司 Modification method for nanometer titania
CN105618152A (en) * 2015-12-24 2016-06-01 南昌航空大学 Method for stabilizing and enhancing activity of TiO2 through one-step reaction
CN105797763A (en) * 2016-04-22 2016-07-27 华南师范大学 Method for preparing carbon and nitrogen-doped titanium dioxide
CN108926994A (en) * 2018-07-04 2018-12-04 绍兴臣工新材料科技有限公司 Visible light removes the multifunctional air cleaning agent and its preparation method of formaldehyde and antibacterial
CN113546091A (en) * 2021-09-08 2021-10-26 常州市妇幼保健院 Titanium dioxide compound with anti-tumor effect

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CN101890343A (en) * 2010-06-29 2010-11-24 浙江大学 Low temperature surface modification method for titanium dioxide nanocrystal
CN103769188A (en) * 2013-12-26 2014-05-07 华北电力大学（保定） Three-atom-doped titanium dioxide as well as preparation method and application thereof

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Publication number Priority date Publication date Assignee Title
CN101890343A (en) * 2010-06-29 2010-11-24 浙江大学 Low temperature surface modification method for titanium dioxide nanocrystal
CN103769188A (en) * 2013-12-26 2014-05-07 华北电力大学（保定） Three-atom-doped titanium dioxide as well as preparation method and application thereof

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105131656A (en) * 2015-10-13 2015-12-09 中国石油化工股份有限公司 Modification method for nanometer titania
CN105618152A (en) * 2015-12-24 2016-06-01 南昌航空大学 Method for stabilizing and enhancing activity of TiO2 through one-step reaction
CN105618152B (en) * 2015-12-24 2017-12-01 南昌航空大学 One kind is by single step reaction stabilization and strengthens TiO2The method of activity
CN105797763A (en) * 2016-04-22 2016-07-27 华南师范大学 Method for preparing carbon and nitrogen-doped titanium dioxide
CN108926994A (en) * 2018-07-04 2018-12-04 绍兴臣工新材料科技有限公司 Visible light removes the multifunctional air cleaning agent and its preparation method of formaldehyde and antibacterial
CN113546091A (en) * 2021-09-08 2021-10-26 常州市妇幼保健院 Titanium dioxide compound with anti-tumor effect

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