CN106732781B - Tetraploid rice/zinc oxide composite membrane nano material primary reconstruction preparation method - Google Patents

Tetraploid rice/zinc oxide composite membrane nano material primary reconstruction preparation method Download PDF

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CN106732781B
CN106732781B CN201610994174.3A CN201610994174A CN106732781B CN 106732781 B CN106732781 B CN 106732781B CN 201610994174 A CN201610994174 A CN 201610994174A CN 106732781 B CN106732781 B CN 106732781B
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tetraphenylporphyrin
zno
solution
zinc oxide
conductive glass
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CN106732781A (en
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潘海波
黄慧涵
张俊贤
沈水发
姜蓉
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Fuzhou University
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    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
    • B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J35/39—
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/30—Treatment of water, waste water, or sewage by irradiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
    • B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
    • B01J2531/025—Ligands with a porphyrin ring system or analogues thereof, e.g. phthalocyanines, corroles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
    • B01J2531/26—Zinc
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/308—Dyes; Colorants; Fluorescent agents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
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    • C02F2101/34—Organic compounds containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/34—Organic compounds containing oxygen
    • C02F2101/345—Phenols
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/38—Organic compounds containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/10—Photocatalysts

Abstract

The present invention discloses a kind of primary reconstruction preparation method of Tetraploid rice/zinc oxide composite membrane nano material.It the steps include: 1) to synthesize nest like ZnO nano membrane material on ITO electro-conductive glass；2) tetraphenylporphyrin (H is synthesized2TPP)；3) tetraphenylporphyrin is dissolved in chloroform solvent；4) the ZnO nano membrane material being attached to above ITO electro-conductive glass is immersed in H2In TPP solution, uniform spin coating attachment is realized immediately；5) it is placed in tube furnace and is calcined in nitrogen.During the preparation process, Tetraploid rice (ZnTPP) primary reconstruction on the surface ZnO is formed, the interface cleanness of obtained organic matter and composite material of inorganic matter, chemical bonding, stability are good, not only widen the visible absorption frequency spectrum of composite material, the separative efficiency of photogenerated charge can be improved simultaneously, photocatalytic degradation efficiency is greatly improved, and shows hydrophobicity and the obvious selectivity to organic dyestuff.

Description

The preparation of Tetraploid rice/zinc oxide composite membrane nano material primary reconstruction Method
Technical field
The invention belongs to the preparation fields of nano-functional material, and in particular to a kind of Tetraploid rice/zinc oxide is compound The primary reconstruction preparation method of film nano material.
Background technique
In numerous ambient water pollutant abatement technologies, photocatalysis oxidation technique is with its room temperature deep reaction and catalytic condition letter The special performances such as single and become a kind of ambient water pollutant abatement technology with broad prospect of application.Currently, mainly with nanometer half Conductor ZnO has ZnO small size, bigger serface and surface largely as photochemical catalyst, due to using nanotechnology Dangling bonds, and come into full contact with water pollutant, catalytic rate is not only increased, reduces reaction temperature, and method is simple, easy Row.But conventional ZnO, as a kind of wide (3.37eV) semiconductor material of band gap, absorption spectrum is located at ultraviolet region, photoproduction electricity Lotus is easily compound, while ZnO photocatalyst does not have selectivity, makes the extensive use of the technology by a degree of restriction.Mesh Before, it is recognized that ZnO photocatalytic mechanism are as follows: when irradiation energy is greater than its forbidden bandwidth, photohole has very strong electronics Ability has strong oxidizing property, can be with the OH in the oxygen and water in air-In conjunction with OH (hydroxyl free radical) is generated, it can be with oxygen Change the various organic matters including bio-refractory, and is allowed to permineralization.
The quantum yield for how improving photochemical catalyst, widen light absorbing frequency band and degradation selectivity target degradation product at For the research focus of current international photocatalysis field.Light-catalysed over-all quantum efficiency is determined by two critical process: first, photic The competition for recombining and being captured of electrons and holes；Second, trapped electron and hole recombine between interface The competition of electric charge transfer.In recent years, to improve photocatalysis quantum efficiency, most of researchs are concentrated mainly on the surface of photochemical catalyst It is modified, including surface chela and surface metal be co-deposited and transient metal doped etc., but there is quantum efficiency increase rates Limited (~2 times), conversion ratio is low (about 80%), and light application time is longer (a few hours), has selectivity to relevant degradation product.
The main method for expanding optical response range is surface sensitization, infusion process is mainly used, by Photoactive compounds Absorption or physical absorption are learned on ZnO, to expand excitation wavelength range, increases the efficiency of light-catalyzed reaction, but since it is used Infusion process, Photoactive compounds are to be combined with a kind of surface physics effect with ZnO, and there are crystal boundaries between two kinds of substances, when light is living Property substance can only the light of certain spectral range irradiation under, so that charge and energy transmission between two kinds of substances is received a fixed limit System, photosensitizer and quantum efficiency are affected to some extent.
Currently, the research emphasis of many photochemical catalysts is placed on the degradation efficiency for how improving photocatalytic pollutant degradation, but It is to lack research in the sequencing and its selectivity of different catalysates of degrading in photochemical catalyst.How to make catalyst One time, target product of effectively and rapidly degrading, rather than " making no exception " ground all organic matters of degrading, by more researchs Pay attention to and favors.Semiconductor oxidation photocatalyst is generally believed that it is to urge without selectivity according to light in processing pollutant Change the free radical mechanism of reaction, that is, substrate to be degraded is including strong oxidizer hydroxyl radical free radical fast-attack, and there is no selections The characteristics of property.The photocatalysis to selectively of metal oxide semiconductor material is improved, can mainly pass through following several ways at present Diameter: (1) reinforce the attraction that catalyst treats catalysis substrate；(2) by being modified to catalyst surface, to enhance catalyst Treat the attraction of degradation substrate in surface；(3) catalyst surface is modified, so that not needing the substance degraded from catalyst Surface separation；(4) catalyst itself is doped.
In recent years, researchers are obtained by changing porphyrin intermetallic metal and substituent group type and number on its chow ring To some macromolecular derivatives of porphyrin with good characteristic, it can satisfy the various demands of people.Metalloporphyrins (Porphyrin) there is π-electron system plane macrocycle molecule of height conjugation, with good light, thermal stability, In visible light region, (400~700nm) has strong absorption, makes it in catalyst (including photochemical catalyst), photocell, dyestuff, light note Record material, biomedical material etc. have excellent characteristic.Therefore, Metalloporphyrins are called 21st century New material, relevant basic and applied research become recent study hot spot.It will be with hydrophilic or hydrophobic substituent metal Metalloporphyrin complex is respectively attached to ZnO nano film surface, on ZnO nano particle, rings to widen spectrum as optical active substance It answers, to improve lighting efficiency, photoelectric conversion efficiency, photocatalytic activity and photocatalysis to selectively.
The situ synthesis techniques of organic/inorganic composite are to have specific physical, change in inorganic substrate surface fabricated in situ Learn the new method of property substance.The technology is to utilize target inorganic and organic respective presoma, through a series of short range physics, is changed The molecular level organic/inorganic composite presoma that reaction process is formed is learned, during the reaction, is formed due to organic matter skeleton The presence of " cage " limits ZnO molecule and makees migration at a distance, the collision probability with porphyrin macromolecular increased, due to anti- The size of " cage " is smaller during answering, and constantly shrinks reduction with the progress of process, through certain heat treatment, easily forms gold Belong to the monomer of metalloporphyrin complex, as fabricated in situ main Connotation.It is easily formed moreover, this method can avoid Metalloporphyrins The unfavorable factors such as dimerization form uniform nanocomposite.
Summary of the invention
It is an object of the invention to insufficient for the prior art, a kind of Tetraploid rice/zinc oxide composite membrane is provided and is received The primary reconstruction preparation method of rice material.Composite material of the invention by Tetraploid rice on the surface ZnO it is in situ from Assembling is formed, and interface cleanness, chemical bonding, the stability of obtained organic matter and composite material of inorganic matter are good, is not only widened multiple The visible absorption frequency spectrum of condensation material, improves the separative efficiency of photogenerated charge, greatly improves photocatalytic degradation efficiency.Meanwhile There are hydrophobic phenyl ring on tetraphenylporphyrin chow ring, so that composite photo-catalyst shows hydrophobicity, in organic mixing of degrading In liquid, apparent selectivity is shown to organic dyestuff such as hydrophobic phenol.
To achieve the above object, the present invention adopts the following technical scheme:
A kind of primary reconstruction preparation method of Tetraploid rice/zinc oxide composite membrane nano material, specific steps Are as follows:
(1) nest like ZnO nano membrane material (ZnO NAs) is synthesized on ITO electro-conductive glass；
(2) tetraphenylporphyrin (H is synthesized with Adler method2TPP belongs to metal-free porphyrin)；
(3) it takes 0.05g tetraphenylporphyrin in beaker, chloroform is added dropwise dropwise under agitation, until tetraphenyl Porphyrin is completely dissolved, and forms tetraphenylporphyrin solution；
(4) the nest like ZnO nano membrane material being attached on ITO electro-conductive glass that step (1) synthesizes is immersed in step (3) in the tetraphenylporphyrin solution obtained, 1s is impregnated, then takes out to be placed on spin coating instrument and carries out rotation 30s, rotation speed is 1000r/min；
(5) the ITO electro-conductive glass after step (4) spin coating is placed in tube furnace, calcines 2h at 500 DEG C in nitrogen, Tetraploid rice/zinc oxide composite membrane nano material (ZnTPP/ZnO NAs) is made；
The synthesis step of nest like ZnO nano membrane material as described in step (1) are as follows: weigh 0.5g PVP and be dissolved in 30mL Water in, be then respectively adding 0.2g glycine, 0.2g zinc acetate and 0.2g Na2SO4, and stir evenly and to form solution A, separately Outside, it weighs 0.19g ammonium carbonate and is dissolved in 20mL water and form solution B；Then under stirring conditions, slowly dropwise by solution B It is added drop-wise in solution A and forms mixed solution；Then the ITO cleaned up is put into ptfe autoclave, is then existed Above-mentioned mixed solution is added in reaction kettle, then reaction kettle is placed in chamber type electric resistance furnace, reacts 3h under conditions of 180 DEG C, The ITO in reaction kettle is taken out after cooling, dry 12h is placed in baking oven at 80 DEG C with distilled water absorption, obtains preceding body Body Zn (OH)2, then presoma calcined into 2h at 500 DEG C, it finally obtains the nest like ZnO being attached on ITO electro-conductive glass and receives Rice membrane material.
The synthesis step of tetraphenylporphyrin described in step (2) are as follows: to three equipped with reflux unit, constant pressure funnel It is added 60mL propionic acid, 20mL nitrobenzene and 3.85mL benzaldehyde, agitating and heating in mouthful flask, i.e. temperature when drop starts reflux 140 DEG C, stirring is lower to instill 2.1mL pyrroles and 15mL nitrobenzene mixed liquor by constant pressure funnel, continues the state in reflux Lower reaction 4h, cooling and standings are stayed overnight after reaction stops, and suction filtration is dried to obtain crude product, and purification obtains tetraphenylporphyrin.
The beneficial effects of the present invention are:
(1) composite photo-catalyst (ZnTPP/ZnO NAs) produced by the present invention is walked by three-step approach and is synthesized, in metalloporphyrin Heart metal is directly provided by inorganic substrates, in situ in synthesis process, no metal tetraphenylporphyrin (H2TPP hydrogen on), by Zn (II) displacement, and it is closely chemically bonded (ZnTPP) by being chemically bound in inorganic substrates, it is not that simple physics is inhaled It is attached, it is different with traditional synthesis technology；
(2) in the structure of ZnTPP/ZnO NAs with nano hybridization microstructure, can sufficiently eliminate organic matter with it is inorganic The mutually separation of object and phase boundary give full play to the two of different attribute to improve the effect of the strong interface between inorganic matrix and organic matter The synergistic effect of kind component；
(3) present invention is formed by the dangling bonds and organic moiety of inorganic part and is chemically bonded, and not only increases photocatalysis The quantum yield of agent widens the light absorbing frequency of composite material to visible region by ultraviolet region, solves ZnO conduct A kind of problem that broad-band gap (3.37eV) semiconductor material absorption spectrum is relatively narrow；Meanwhile photogenerated charge can pass through ZnO and ZnTPP Between chemical bond, realize efficiently separating for photogenerated charge.It is of particular importance that based on the phenyl ring on ZnTPP complex chow ring, tool Have stronger hydrophobicity, can specificity absorption to the hydrophobicity toxic target object in degradation product, it can be achieved that visible light-responded, high Selectivity and high efficiency photocatalysis.
Detailed description of the invention
Fig. 1 is the flow chart of fabricated in situ ZnTPP/ZnO NAs；
Fig. 2 is (500 DEG C, 2h sintering) X-ray diffractogram of ZnO NAs and ZnTPP/ZnO NAs fabricated in situ material；
Fig. 3 be ZnO NAs(a) and ZnTPP/ZnO NAs(b) scanning electron microscope (SEM) photograph；
Fig. 4 is the UV-Vis DRS spectrum of fabricated in situ ZnTPP/ZnO NAs composite material (500 DEG C, 2h sintering)；
Fig. 5 is fabricated in situ ZnTPP/ZnO NAs composite material (500 DEG C, 2h sintering) CHCl3It is extracted it is ultraviolet-can See absorption spectrum；
(500 DEG C, 2h sintering) CDCl of Fig. 6 fabricated in situ ZnTPP/ZnO NAs composite material3H extracted1NMR nuclear-magnetism Resonate spectrogram；
Fig. 7 is the change procedure that ZnTPP is sensitized ZnO NAs membrane material and water surface contact angle, and figure (a) is without sensitization plays Pure ZnO NAs membrane material and water surface contact angle change procedure, figure (b) be ZnTPP sensitization after ZnO NAs membrane material with The change procedure of water surface contact angle；
Fig. 8 be fabricated in situ ZnTPP/ZnO NAs(500 DEG C, 2h sintering) photochemical catalyst sunlight photocatalysis degradation sieve Red bright B(RhB) and phenol (PL) degradation figure (76~85 milliwatts of illuminance/square centimeter, 25 DEG C)；
Fig. 9 be fabricated in situ ZnTPP/ZnO NAs(500 DEG C, 2h sintering) photochemical catalyst sunlight photocatalysis degradation sieve Red bright B(RhB) and phenol (PL) mixed solution degradation figure (76~85 milliwatts of illuminance/square centimeter, 25 DEG C).
Specific embodiment
Below in conjunction with specific embodiment, the present invention will be further described, but the present invention is not limited only to these embodiments.
Embodiment
A kind of primary reconstruction preparation method of Tetraploid rice/zinc oxide composite membrane nano material, specific steps Are as follows:
(1) ITO electro-conductive glass is cleaned by ultrasonic with cleaning agent, acetone, ethyl alcohol and deionized water respectively, and every minor tick is Then 10min is placed on 80 DEG C of drying for standby in baking oven；
(2) 0.5g PVP is weighed to be dissolved in the water of 30mL, be then respectively adding 0.2g glycine, 0.2g zinc acetate and 0.2g Na2SO4, and stir evenly and to form solution A, solution B is formed in addition, weighing 0.19g ammonium carbonate and being dissolved in 20mL water；So Afterwards under stirring conditions, solution B is slowly added drop-wise in solution A dropwise and forms mixed solution；Then the ITO that will be cleaned up It is put into ptfe autoclave, is then poured into reaction kettle by above-mentioned mixed solution, then reaction kettle is placed in box In resistance furnace, 3h is reacted under conditions of 180 DEG C, ITO in reaction kettle is taken out after temperature is cooling, is adsorbed with distilled water It is placed in baking oven at 80 DEG C dry 12h, forms precursor Zn (OH) at this time2, then presoma calcined into 2h at 500 DEG C, Finally obtain the nest like ZnO(ZnO NAs being attached on ITO electro-conductive glass) nano-sized membrane；
(3) to equipped with reflux unit, constant pressure funnel three-necked flask in be added 60mL propionic acid, 20mL nitrobenzene, 3.85mL benzaldehyde, agitating and heating, drop start when reflux i.e. about 140 DEG C of temperature, and stirring is lower to be instilled by constant pressure funnel 2.1mL newly steams pyrroles and 15mL nitrobenzene mixed liquor, and 4h is reacted in continuation in the state of reflux, and reaction cools down after stopping in refrigerator In stand overnight, filtered with Buchner funnel, be placed on inside baking oven and be dried to obtain crude product tetraphenylporphyrin；
(4) step (3) resulting crude product (4g) is substantially soluble in chloroform (500mL), there are about 1g DDQ's for addition 35mL dry benzene, mixture are stirred at reflux 3h, yellow solution glass sand filtering (the 60g Al for being covered with activated alumina2O3With CH2Cl2After mixing, paved in organdy funnel, cover a filter paper), filter cake CH2Cl2Washing, washing lotion and filtrate merge, It is concentrated into 30mL, 6mL methanol is added, is cooled to room temperature, high-purity tetraphenylporphyrin (H is obtained by filtration2TPP)；
(5) tetraphenylporphyrin of 0.05g is taken out in beaker, chloroform is added dropwise dropwise under agitation, until four Phenyl porphyrin is completely dissolved, and forms tetraphenylporphyrin solution；
(6) the ITO electro-conductive glass piece for the attachment Nano-ZnO Films material for taking step (2) to synthesize, is fully immersed in tetraphenyl porphin Quinoline solution, takes out to be placed on spin coating instrument at once and at the uniform velocity rotates 30s with the speed of 1000r/min；
(7) the ITO electro-conductive glass piece after spin coating is placed in tube furnace in N2In lower 500 DEG C of calcinings 2h, it is multiple that nanometer is made Light combination catalyst Z nTPP/ZnO NAs.
The flow chart of above-mentioned fabricated in situ ZnTPP/ZnO NAs is as shown in Figure 1.
One, the structural characterization of ZnTPP/ZnO NAs:
(1) fabricated in situ ZnTPP/ZnO NAs composite film material, from Figure of description 2 and attached drawing 3 it is found that photocatalysis The principal crystalline phase of agent is ZnO, and is hexagonal system structure and nest like structure.
(2) in the product to identify fabricated in situ, there is the presence of object Tetraploid rice (ZnTPP), wherein H2The chemical structural formula of TPP, ZnTPP are respectively as follows:
(Figure of description 4), CHCl are composed using powder UV-Vis DRS3Ultraviolet-visible light after solvent extraction is inhaled Receive spectrum (Figure of description 5) and CDCl3H extracted1Nuclear magnetic resonance spectrogram is characterized (Figure of description 6), in attached drawing 4 Composite photo-catalyst significantly improves the utilization rate of visible light in the visible-range of 400-700nm, 419nm in attached drawing 5 The B band (also known as Soret band) that absorption peak is ZnTPP, this feature peak is stronger, so that therefore composite catalyst shows Chinese red, 547nm(β absorption band) and 584nm(α absorption band) be metalloporphyrin Q band, metal-free porphyrin formed metal porphyrins after, Four absorption peaks of visible light merge into 2, and the Soret band near ultraviolet band, which absorbs, to be still remained, only the position of Soret band Have blue shift or red shift.For different metals, it is seen that the position of two absorption peaks in area and relative intensity show as different Feature, therefore metal porphyrins can uniquely be confirmed according to the uv-visible absorption spectra of compound；Attached drawing 6 is The nmr spectrum of composite catalyst, top right plot tetraphenylporphyrin nmr spectrum, spectrogram are pyrrole ring at 8.98ppm The resonance absorbing peak of upper 8 hydrogen, 8.26ppm are the resonance absorbing peak of 8 hydrogen on four phenyl ring ortho positions, 7.99-7.65ppm tetra- The resonance absorbing peak of 12 hydrogen between a phenyl ring in contraposition, volume ratio 2:2:3.Compared with tetraphenylporphyrin ,- Do not occur the formant of two H of N-H key on pyrrole ring at 2.74ppm, is combined with UV-vis spectrum (attached drawing 4) and can determine hydrogen original Son is replaced by zinc ion, is formed metal complex (ZnTPP).
Two, hydrophobicity and photocatalysis performance test
1. hydrophobicity.By contact angle instrument, ZnO and ZnTPP/ZnO composite material is respectively dropped by distilling water droplet Surface, at the same 5 after recording, 10, in 15s drop and interfacial contact angle variation dynamic process (attached drawing 7), it is seen that ZnO The surface NAs shows hydrophily, and the interfacial contact angle of ZnTPP/ZnO NAs composite material is all larger than ZnO NAs, show compared with Apparent hydrophobicity.
2. photocatalysis performance.(select organic pollutant for rhodamine B (RhB) analytical reagents in sunlight degradation of dye With phenol (PL) analytical reagents) photocatalytic degradation experiment in, experiment condition is that environment temperature is 25 DEG C, irradiation level be 76~ 85mW/cm2, steps are as follows:
(a) certain density rhodamine B (phenol, rhodamine B and phenol mixed solution) aqueous solution (1 × 10 is prepared-6mol/ L)。
(b) the ito glass piece (2cm × 2cm) for taking ZnO NAs and ZnTPP/ZnO NAs composite material respectively, is placed in 40mL Rhodamine B (phenol, rhodamine B and phenol mixed solution) aqueous solution (1 × 10-6Mol/L) bottom, the quartz with aeration aperture In cup.
(c) it is tested through sunlight photocatalysis degradation, 4 milliliters of solution degraded was taken every 30 minutes, take about 3 milliliters of upper layers Solution after centrifugation, the measurement for ultraviolet-visible spectrum.
(d) in ultraviolet-visible light spectrometry, use molar absorptivity intensity at the principal absorption wavelength to degradation product as light The measurement standard of catalytic degradation, and the photochemical catalyst situation for preparing pure ZnO NAs with same method is compared.
By illustrate attached drawing 8 and attached drawing 9 it is found that the ZnTPP/ZnO NAs through fabricated in situ photochemical catalyst, not only visible Can be with degradable organic pollutant under light, not only rate of photocatalytic oxidation is greatly improved, and the degradation rate of independent degradation of phenol can It is 3.03 times of pure zinc oxide (31.62%) up to 95.73%, while the ZnTPP/ZnO NAs degradation PL in mixed solution (56.4%) be RhB(16.84%) 3.35 times, selectivity is shown to hydrophobic degradation product (PL).
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with Modification, is all covered by the present invention.

Claims (4)

1. a kind of Tetraploid rice/zinc oxide composite membrane nano material primary reconstruction preparation method, it is characterised in that: its Specific steps are as follows:
(1) nest like ZnO nano membrane material is synthesized on ITO electro-conductive glass；The synthesis of the nest like ZnO nano membrane material walks Suddenly are as follows: weigh 0.5g PVP and be dissolved in the water of 30mL, be then respectively adding 0.2g glycine, 0.2g zinc acetate and 0.2g Na2SO4, and stir evenly and to form solution A, solution B is formed in addition, weighing 0.19g ammonium carbonate and being dissolved in 20mL water；Then exist Under conditions of stirring, solution B is slowly added drop-wise in solution A dropwise and forms mixed solution；Then the ITO cleaned up is put into Into ptfe autoclave, then above-mentioned mixed solution is added in reaction kettle, then reaction kettle is placed in chamber type electric resistance furnace In, 3h is reacted under conditions of 180 DEG C, takes out the ITO in reaction kettle after cooling, is placed in baking oven with distilled water absorption Dry 12h, obtains precursor Zn (OH) at 80 DEG C2, then presoma calcined into 2h at 500 DEG C, it finally obtains and is attached to ITO Nest like ZnO nano membrane material on electro-conductive glass；
(2) tetraphenylporphyrin is synthesized with Adler method；
(3) it takes 0.05g tetraphenylporphyrin in beaker, chloroform is added dropwise dropwise under agitation, until tetraphenylporphyrin It is completely dissolved, forms tetraphenylporphyrin solution；
(4) the nest like ZnO nano membrane material being attached on ITO electro-conductive glass that step (1) synthesizes step (3) are immersed in obtain To tetraphenylporphyrin solution in, impregnate 1s, then take out to be placed on spin coating instrument and rotated；
(5) the ITO electro-conductive glass after step (4) spin coating is placed in tube furnace, calcines 2h at 500 DEG C in nitrogen, is made Tetraploid rice/zinc oxide composite membrane nano material.
2. preparation method according to claim 1, it is characterised in that: the synthesis of tetraphenylporphyrin described in step (2) Step are as follows: 60mL propionic acid, 20mL nitrobenzene and 3.85mL are added into the three-necked flask equipped with reflux unit, constant pressure funnel Benzaldehyde, agitating and heating, drop start when reflux i.e. 140 DEG C of temperature, and stirring is lower to instill 2.1mL pyrroles by constant pressure funnel With 15mL nitrobenzene mixed liquor, 4h is reacted in continuation in the state of reflux, and cooling and standings are stayed overnight after reaction stops, and filters dry To crude product, purification obtains tetraphenylporphyrin.
3. preparation method according to claim 1, it is characterised in that: rotation speed is 1000r/min, rotation in step (4) Turning the time is 30s.
4. Tetraploid rice made from preparation method according to claim 1/zinc oxide composite membrane nano material is answered With, it is characterised in that: tetraphenylporphyrin/zinc oxide surface shows hydrophobicity, waits for for selective photocatalysis degradation hydrophobicity Degradation product.
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