CN103406152B - Visible light-responded metal/organic semiconductor photochemical catalyst and preparation method thereof and application - Google Patents
Visible light-responded metal/organic semiconductor photochemical catalyst and preparation method thereof and application Download PDFInfo
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Abstract
The invention discloses and a kind of there is visible light-responded photochemical catalyst and preparation method thereof and application, catalyst provided by the invention is made up of metal nanoparticle, semiconducting organic polymer, inorganic carrier, adopt semiconducting organic polymer modification metal nanoparticle, and load forms visible light-responded photochemical catalyst on inorganic carrier.The load-type nanometer metal catalyst of this organic semiconductor doping, effectively by excited by visible light, can keep again stability and the high catalytic activity of load-type nanometer metal catalyst, manufacturing process is simple simultaneously.
Description
Technical field
The present invention relates to a kind of photochemical catalyst field, particularly relate to a kind of have visible light-responded photochemical catalyst and preparation method thereof and photocatalysis treatment and reaction in application.
Background technology
Along with the development of modern industry, the raising of people's living standard, problem of environmental pollution is very serious.In China, the river of nearly 1/2 is polluted, and 1.64 hundred million people drink the serious water of organic contamination, and Indoor Air Pollution with outdoor Air Pollution is serious.Wherein the difficult proportion decomposing toxic organic pollutant is also sharply increasing, and many toxic organic pollutants cannot be processed with existing microbial technique, or cannot thoroughly remove.Conductor photocatalysis obtains as a kind of green technology and pays close attention to widely in solution environmental problem.Conductor photocatalysis occurs based on following process: when the energy of incident light is more than or equal to the band-gap energy of semiconductor, excited electron transits to conduction band from valence band, this thing conduction band obtains light induced electron valence band and leaves photohole, the substrate generation redox reaction of advanced table photo-generated carrier and semiconductor surface.Compound in this process between photo-generated carrier is inevitable all the time, and this will cause photocatalysis efficiency to reduce.
In recent years, photocatalysis technology has made great progress, many nano inorganic semi-conducting materials, as titanium dioxide, zinc oxide, cadmium sulfide and composite semiconductor etc., be all found can degradable organic pollutant effectively, this type of document has " chemistry summary " magazine 1995,95, article " environmental applications of conductor photocatalysis " (the M. R. Hoffmann that 69-96 delivers, S. T. Martin, W. Choi, D. W. Bahnemann, Environmental Application of Semiconductor Photocatalysis, Chem. Rev.).Wherein to have photocatalysis efficiency high because of it for titanium deoxide catalyst, good stability, the advantage such as cheap and be subject to research and apply widely.But because titanium dioxide has the energy gap of 3.2eV, the ultraviolet light only having wavelength to be less than 385nm could be excited effectively, and ultraviolet light only occupy the ratio of 3-5% in sunshine, as used artificial ultraviolet source then can the electric energy of at substantial.Therefore, attempt the visible ray of cheap, inexpensive or sunshine purify air or process waste water to environmental protection with to be energy-conservationly all extremely important.How making photochemical catalyst have visible light-responded, can be a difficult problem urgently to be resolved hurrily by excited by visible light effectively.
At present, the band structure that a large amount of research work concentrates on based on extraneous element doping regulates and controls to overcome above-mentioned drawback.Representing document has article " the quantum size TiO that " physical chemistry " magazine 1994,98,13669-13679 is delivered
2the effect of middle doped metal ion: correlation (Choi, the W. of photocatalytic activity and photo-generated carrier recombination kinetcs; Termin, A.; Hoffmann, M. R. The role of metal ion dopants in quantum-sized TiO
2: Correlation between photoreactivity and charge carrier recombination dynamics. J. Phys. Chem.).Have studied doping and the Ti0 of many kinds of metal ions in detail
2relation between photocatalytic activity.They find that the electron configuration of photocatalytic activity and doped metal ion is closely related.In 21 metal ion species adulterants selected by it, the doping of Fe, Mo, Ru, Os, Re, V and Rh can significantly improve TiO
2photocatalytic activity.Although these methods can utilize titanium dioxide under the irradiation of visible ray, but regrettably, extraneous element doping carrys out the problem of heat endurance not only can to photocatalysis body frenulum, the complex centre of carrier can be introduced in doped semiconductor, but also the redox ability of matrix semiconductors photo-generated carrier can be affected.Some researchers take the method for dye sensitization, the dye load that can absorb visible ray at catalyst surface to effectively utilize visible ray, this type of document has " Chinese science " magazine 2002,45, article " 2; 4-Dichlorophenol is at the semiconductor surface visible light photocatalytic degradation of sensitization " (the X. Z. Li that 421-425 delivers, W. Zhao, J. C. Zhao, Visibel light-sensitized semiconductor photocatalytic degradation of 2,4-dichlorophenol
sci, China B).To there is the wide semiconductor of smaller strip (as cadmium sulfide) load at titanium dioxide surface, this type of document has " physical chemistry " magazine 1995,99, article that 10329-10335 delivers " what connect with titanium dioxide key has the cadmium sulfide nano-particles that dual-use function blocks a shot " (D. Lawless, S. Kapoor, D. Meisel, Bifunctional capping of CdS nanoparticles and binding to TiO
2,
j. Phys. Chem.).
At a kind of method of modifying that photocatalyst surface depositing noble metal is also comparatively general.Noble metal loading can change the Carrier Profile of semiconductor surface, forms Schottky barrier, effectively can suppress the compound of electron-hole, extend its life-span at the two interface, thus improves photocatalysis efficiency.Article " visible light catalysis activity of layered titanate load gold nano particulate material " (Ide, Y. that document " JACS " 2010,132,16762-16764 such as, deliver; Matsuoka, M.; Ogawa, M. Efficient visible-light-induced photocatalytic activity on gold-nanoparticle-supported layered titanate. J. Am. Chem. Soc.).Utilized semiconducting organic polymer doping vario-property inorganic semiconductor catalyst particularly to pay close attention in recent years in the world, representing document has " kinetics, mechanism and catalysis "
2010,
101, article " under sunshine, the photocatalysis performance of conducting polymer polythiophene sensitized titanium dioxide nano particle strengthens " (Xu, the S. H. that 237 – 249 deliver; Li, S. Y.; Wei, Y. X.; Zhang, L.; Xu, F. Improving the Photocatalytic Performance of Conducting Polymer Polythiophene Sensitized TiO
2nanoparticles Under Sunlight Irradiation.
reaction Kinetics, Mechanisms and Catalysis).this research finds the composite using polythiophene-titanium dioxide, can produce light induced electron, and electron lifetime is longer compared with the light induced electron of titanium dioxide under excited by visible light.
The main active component of photochemical catalyst of the prior art is inorganic semiconductor material, even if by doping vario-property, its photocatalysis efficiency is usually all lower.And the load type metal catalyst of traditional chemical industry has the advantage of high catalytic activity and high stability, but not there is photocatalytic activity.If can carry out modification to conventional load type metallic catalyst, making it have visible light-responded catalytic activity, will be a quantum jump in photocatalyst technology field.But up to now, there is not yet the application example of organic semiconductor modification non-semiconductor load type metal catalyst in visible light photocatalysis reaction.
Summary of the invention
The object of the invention is to for the deficiencies in the prior art, there is provided a kind of and there is visible light-responded photochemical catalyst, the load-type nanometer metal catalyst of this organic semiconductor doping, can effectively by excited by visible light, can keep again stability and the high catalytic activity of load-type nanometer metal catalyst, manufacturing process is simple simultaneously.
Catalyst provided by the invention is made up of metal nanoparticle, semiconducting organic polymer, inorganic carrier, adopt semiconducting organic polymer modification metal nanoparticle, and load forms visible light-responded photochemical catalyst on inorganic carrier.
Wherein said metal nanoparticle is platinum, ruthenium, palladium, rhodium noble metal, and the mass percent that metal accounts for inorganic carrier is 0.1% ~ 20%, and the average grain diameter of metal nanoparticle is between 1 nanometer to 20 nanometers.
Semiconducting organic polymer is polypyrrole, polyaniline, polythiophene conductive polymer, and the mass percent that semiconducting organic polymer accounts for inorganic carrier is 0.1% ~ 20%.
Inorganic carrier is active carbon, aluminium oxide (Al
2o
3), silicone substance, its particle diameter is between 5 nanometers are to 5 microns.
The preparation method with visible light-responded photochemical catalyst of the present invention is as follows:
(1) preparation of semiconducting organic polymer
Typical case's synthesis of polypyrrole.Getting 3-hexyl pyrrole monomer (about 2mL) is dissolved in 100mL chloroform solvent, stirs after 20 minutes, adds 5.0g anhydrous ferric trichloride in reaction system, and room temperature under nitrogen protection lower magnetic force stirs 4 hours.Add 400mL distilled water after reaction to stir, remove unnecessary ferric trichloride, be separated with separatory funnel, repeated washing is colourless to upper strata.Add that anhydrous sodium sulfate drying process dewaters, rotary evaporation removing solvent molecule, then vacuum drying, obtain bright black solid.
Typical case's synthesis of polyaniline.By 50mL ammonium persulfate (0. 5mo l/L) chloroform soln be added drop-wise to be equipped with aniline (0. 4mo l/L) and sulfuric acid (1. 0mo l/L) solution round-bottomed flask in, magnetic agitation, ice-water bath temperature control.After reaction 3h, stop stirring.Suction filtration, with dilute sulfuric acid, acetone washing leaching cake 3 times, to remove unreacted organic matter and oligomer, is then washed till about filtrate is pH=6 by a large amount of deionized water.Vacuum drying is to constant weight, and grind into powder, obtains polyaniline.
Typical case's synthesis of polythiophene.50mL chloroform and 3.25g (20mmol) anhydrous ferric trichloride are added in 100mL there-necked flask; after the protection lower magnetic force stir about 1h of nitrogen; 50mL is dropwise added containing the chloroformic solution constant pressure funnel of 5mmol thiophene-based monomer; after reacting 24h under room temperature; poured into by excessive methanol in mixed solution and carry out slow sedimentation, suction filtration obtains polymer.Resulting polymers uses methyl alcohol cyclic washing repeatedly in apparatus,Soxhlet's, removes excessive ferric trichloride and some oligomer.Product, through vacuum drying, obtains red solid.
(2) preparation of the load type metal catalyst of semiconducting organic polymer modification
Get a certain amount of semiconducting organic polymer (0.1%-20% of inorganic carrier quality) with inorganic carrier (as aluminium oxide, active carbon or silica gel etc.) fully mix, pour in the metal salt solution of 0.001-0.1M that (the metal precursor aqueous solution is metal nitrate saline solution into, metal accounts for the 0.1%-20% of inorganic carrier mass ratio), reducing agent (hydrazine hydrate is dripped under room temperature vigorous stirring, sodium borohydride or ethanol) solution, reducing agent consumption is suitable with the metal precursor aqueous solution, and concentration is the aqueous solution of 0.1mol/L, stirring at normal temperature places sedimentation aging 1 ~ 10 day after 2 ~ 8 hours.Revolve and steam except desolventizing final vacuum is dry.Gained sample 150-350 DEG C of hydrogen reducing can obtain catalyst fines after 4 hours.
The present invention has the photocatalysis treatment that visible light-responded photochemical catalyst can be used for air, Organic Pollutants in Wastewater, also can be used for the light-catalyzed reactions such as photocatalysis synthesis.
Semiconducting organic polymer is incorporated in conventional load type metal catalyst system by the original ground of the present invention, thus gives catalyst visible light-responded characteristic, has the advantage of load type metal catalyst high stability and high catalytic activity concurrently.Semiconducting organic polymer molecular structure can coordination activity site can grappling metal nanoparticle, thus there is organic/inorganic interface electron interaction, illumination excites lower this interface electron interaction to be enhanced, thus catalytic activity is improved further.
Of the present invention there is visible light responsive photocatalyst can effectively by excited by visible light, visible ray is utilized to realize deodorizing, the sterilization of the public or confined space of family and hospital or other and decompose organic pollution in air, manufacturing process is simple simultaneously, promotes that light-catalyzed reaction is pushed to practical further.
Accompanying drawing explanation
Fig. 1 is the TEM photo of polythiophene carried metal palladium nanocatalyst, and in Fig. 1, TEM photo shows that the particle diameter of Pd nano particle is all at 4.5 ± 0.9 nm.
Fig. 2 is carbon load polythiophene modified metal palladium catalyst catalysis formic acid decomposition result under visible light, and Fig. 2 shows, when the content of PTh is 0.5%-2%, under non-illuminated conditions, catalytic activity is all adulterated higher than without PTh, and 2% time, rate of catalysis reaction is the twice of Pd/C catalyst.
In figure: curve a---carbon-containing palladium catalyst (embodiment 13);
Curve b---modify the carbon-containing palladium catalyst (embodiment 7) of 0.5wt% polythiophene;
Curve c---modify the carbon-containing palladium catalyst (embodiment 8) of 1.0wt% polythiophene;
Curve d---modify the carbon-containing palladium catalyst (embodiment 9) of 2.0wt% polythiophene;
Curve e---modify the carbon-containing palladium catalyst (embodiment 10) of 5.0wt% polythiophene;
Curve f---modify the carbon-containing palladium catalyst (embodiment 11) of 10.0wt% polythiophene;
Curve g---modify the carbon-containing palladium catalyst (embodiment 12) of 20.0wt% polythiophene.
Reaction condition is: isolated illumination, under room temperature (25 degrees Celsius), 30 mg catalyst drop into 10 mL 50v/v% aqueous formic acids, and mixing speed is 500 rpm.
Fig. 3 is the formic acid decomposition rate comparing result of catalyst under isolated illumination and illumination condition.A figure is the carbon-containing palladium catalyst modifying 1.0wt% polythiophene; B figure is the carbon-containing palladium catalyst modifying 2.0wt% polythiophene.
Fig. 3 shows, under illumination condition, formic acid decompose speed comparatively non-illuminated conditions high 2 times (
a1% He
b2% PTh-C), and 2%PTh-C carrier for Pd decompose formic acid ability compared with the C carrier (embodiment 13) under equal conditions, improve 6 times.
Detailed description of the invention
Embodiment 1
Getting 3-hexyl pyrrole monomer (about 2mL) is dissolved in 100mL chloroform solvent, stirs after 20 minutes, adds 5.0g anhydrous ferric trichloride in reaction system, and room temperature under nitrogen protection lower magnetic force stirs 4 hours.Add 400mL distilled water after reaction to stir, remove unnecessary ferric trichloride, be separated with separatory funnel, repeated washing is colourless to upper strata.Add that anhydrous sodium sulfate drying process dewaters, rotary evaporation removing solvent molecule, then vacuum drying, obtain bright black solid polypyrrole.
Get 0.005g polypyrrole fully to mix with 1g alumina support (average grain diameter 150nm), add in 10mL palladium nitrate solution (concentration is 0.0434mol/L), drip 10mL reducing agent hydrazine hydrate solution (concentration is 0.1mol/L) under room temperature vigorous stirring, stirring at normal temperature places sedimentation aging 1 day after 2 hours.Revolve and steam except desolventizing final vacuum is dry.Gained sample 150 DEG C of hydrogen reducings can obtain catalyst fines (the Metal Palladium nano particle average grain diameter that TEM characterizes institute's load is 5.9nm) after 4 hours.
Embodiment 2
Polypyrrole synthesis is with embodiment 1.
Get 0.005g polypyrrole fully to mix with 1g alumina support (average grain diameter 150nm), add in 10mL platinum nitrate solution (concentration is 0.0313mol/L), drip 10mL reducing agent hydrazine hydrate solution (concentration is 0.1mol/L) under room temperature vigorous stirring, stirring at normal temperature places sedimentation aging 1 day after 2 hours.Revolve and steam except desolventizing final vacuum is dry.Gained sample 150 DEG C of hydrogen reducings can obtain catalyst fines (the metal platinum nano-particle average grain diameter that TEM characterizes institute's load is 4.7nm) after 4 hours.
Embodiment 3
Polypyrrole synthesis is with embodiment 1.
Get 0.005g polypyrrole fully to mix with 1g absorbent charcoal carrier (average grain diameter 30nm), add in 10mL platinum nitrate solution (concentration is 0.0313mol/L), drip 10mL reducing agent hydrazine hydrate solution (concentration is 0.1mol/L) under room temperature vigorous stirring, stirring at normal temperature places sedimentation aging 1 day after 2 hours.Revolve and steam except desolventizing final vacuum is dry.Gained sample 150 DEG C of hydrogen reducings can obtain catalyst fines (the metal platinum nano-particle average grain diameter that TEM characterizes institute's load is 3.9nm) after 4 hours.
Embodiment 4
By 50mL ammonium persulfate (0. 5mo l/L) be added drop-wise to be equipped with aniline (0. 4mo l/L) and sulfuric acid (1. 0mo l/L) solution round-bottomed flask in, magnetic agitation, ice-water bath temperature control.After reaction 3h, stop stirring.Suction filtration, with dilute sulfuric acid, acetone washing leaching cake 3 times, to remove unreacted organic matter and oligomer, is then washed till about filtrate is pH=6 by a large amount of deionized water.Vacuum drying is to constant weight, and grind into powder, obtains polyaniline.
Get 0.010g polyaniline fully to mix with 1g alumina support (average grain diameter 150nm), add in 10mL platinum nitrate solution (concentration is 0.0313mol/L), drip 10mL borane reducing agent sodium hydride solution (concentration is 0.1mol/L) under room temperature vigorous stirring, stirring at normal temperature places sedimentation aging 1 day after 2 hours.Revolve and steam except desolventizing final vacuum is dry.Gained sample 150 DEG C of hydrogen reducings can obtain catalyst fines (the metal platinum nano-particle average grain diameter that TEM characterizes institute's load is 4.5nm) after 4 hours.
Embodiment 5
The synthesis of polyaniline is with embodiment 3.
Get 0.010g polyaniline fully to mix with 1g alumina support (average grain diameter 150nm), add in 10mL nitric acid ruthenium solution (concentration is 0.0315mol/L), drip 10mL borane reducing agent sodium hydride solution (concentration is 0.1mol/L) under room temperature vigorous stirring, stirring at normal temperature places sedimentation aging 1 day after 2 hours.Revolve and steam except desolventizing final vacuum is dry.Gained sample 200 DEG C of hydrogen reducings can obtain catalyst fines (the metal Ru nano particle average grain diameter that TEM characterizes institute's load is 5.3nm) after 4 hours.
Embodiment 6
The synthesis of polyaniline is with embodiment 3.
Get 0.010g polyaniline and 1g silica-gel carrier (commercial silica gel, average grain diameter 5.0mm) fully mix, add in 10mL nitric acid ruthenium solution (concentration is 0.0315mol/L), drip 10mL borane reducing agent sodium hydride solution (concentration is 0.1mol/L) under room temperature vigorous stirring, stirring at normal temperature places sedimentation aging 1 day after 2 hours.Revolve and steam except desolventizing final vacuum is dry.Gained sample 200 DEG C of hydrogen reducings can obtain catalyst fines (the metal Ru nano particle average grain diameter that TEM characterizes institute's load is 7.2nm) after 4 hours.
Embodiment 7
50mL chloroform and 3.25g (20mmol) anhydrous ferric trichloride are added in 100mL there-necked flask; after the protection lower magnetic force stir about 1h of nitrogen; 50mL is dropwise added containing the chloroformic solution constant pressure funnel of 5mmol thiophene-based monomer; after reacting 24h under room temperature; all be added in reaction mixture by excessive methanol and carry out slow sedimentation, suction filtration obtains polymer.Resulting polymers uses methyl alcohol cyclic washing repeatedly in apparatus,Soxhlet's, removes excessive ferric trichloride and some oligomer.Product, through vacuum drying, obtains red solid polythiophene.
Get 0.005g polythiophene fully to mix with 1g absorbent charcoal carrier (average grain diameter 30nm), add in 10mL palladium nitrate solution (concentration is 0.0434mol/L), drip 10mL reducing agent ethanol (concentration is 0.1mol/L) under room temperature vigorous stirring, stirring at normal temperature places sedimentation aging 1 day after 4 hours.Revolve and steam except desolventizing final vacuum is dry.Gained sample 150 DEG C of hydrogen reducings can obtain catalyst fines (the Metal Palladium nano particle average grain diameter that TEM characterizes institute's load is 5.4nm) after 4 hours.
Embodiment 8
The synthesis of polythiophene is with embodiment 7.
Get 0.010g polythiophene fully to mix with 1g absorbent charcoal carrier (average grain diameter 30nm), add in 10mL palladium nitrate solution (concentration is 0.0434mol/L), drip 10mL reducing agent ethanol (concentration is 0.1mol/L) under room temperature vigorous stirring, stirring at normal temperature places sedimentation aging 1 day after 4 hours.Revolve and steam except desolventizing final vacuum is dry.Gained sample 150 DEG C of hydrogen reducings can obtain catalyst fines (the Metal Palladium nano particle average grain diameter that TEM characterizes institute's load is 5.1nm) after 4 hours.
Embodiment 9
The synthesis of polythiophene is with embodiment 7.
Get 0.020g polythiophene fully to mix with 1g absorbent charcoal carrier (average grain diameter 30nm), add in 10mL palladium nitrate solution (concentration is 0.0434mol/L), drip 10mL reducing agent ethanol (concentration is 0.1mol/L) under room temperature vigorous stirring, stirring at normal temperature places sedimentation aging 1 day after 4 hours.Revolve and steam except desolventizing final vacuum is dry.Gained sample 150 DEG C of hydrogen reducings can obtain catalyst fines (the Metal Palladium nano particle average grain diameter that TEM characterizes institute's load is 4.5nm) after 4 hours.
Embodiment 10
The synthesis of polythiophene is with embodiment 7.
Get 0.050g polythiophene fully to mix with 1g absorbent charcoal carrier (average grain diameter 30nm), add in 10mL palladium nitrate solution (concentration is 0.0434mol/L), drip 10mL reducing agent ethanol (concentration is 0.1mol/L) under room temperature vigorous stirring, stirring at normal temperature places sedimentation aging 1 day after 4 hours.Revolve and steam except desolventizing final vacuum is dry.Gained sample 150 DEG C of hydrogen reducings can obtain catalyst fines (the Metal Palladium nano particle average grain diameter that TEM characterizes institute's load is 4.3nm) after 4 hours.
Embodiment 11
The synthesis of polythiophene is with embodiment 7.
Get 0.10g polythiophene fully to mix with 1g absorbent charcoal carrier (average grain diameter 30nm), add in 10mL palladium nitrate solution (concentration is 0.0434mol/L), drip 10mL reducing agent ethanol (concentration is 0.1mol/L) under room temperature vigorous stirring, stirring at normal temperature places sedimentation aging 1 day after 4 hours.Revolve and steam except desolventizing final vacuum is dry.Gained sample 150 DEG C of hydrogen reducings can obtain catalyst fines (the Metal Palladium nano particle average grain diameter that TEM characterizes institute's load is 4.0nm) after 4 hours.
Embodiment 12
The synthesis of polythiophene is with embodiment 7.
Get 0.20g polythiophene fully to mix with 1g absorbent charcoal carrier (average grain diameter 30nm), add in 10mL palladium nitrate solution (concentration is 0.0434mol/L), drip 10mL reducing agent ethanol (concentration is 0.1mol/L) under room temperature vigorous stirring, stirring at normal temperature places sedimentation aging 1 day after 4 hours.Revolve and steam except desolventizing final vacuum is dry.Gained sample 150 DEG C of hydrogen reducings can obtain catalyst fines (the Metal Palladium nano particle average grain diameter that TEM characterizes institute's load is 3.6nm) after 4 hours.
Embodiment 13
1g absorbent charcoal carrier (average grain diameter 30nm) adds in 10mL palladium nitrate solution (concentration is 0.0434mol/L), drip 10mL reducing agent ethanol (concentration is 0.1mol/L) under room temperature vigorous stirring, stirring at normal temperature places sedimentation aging 1 day after 4 hours.Revolve and steam except desolventizing final vacuum is dry.Gained sample 150 DEG C of hydrogen reducings can obtain the carbon-containing palladium catalyst powder (the Metal Palladium nano particle average grain diameter that TEM characterizes institute's load is 5.7nm) modified without semiconducting organic polymer after 4 hours.
Claims (7)
1. visible light-responded metal/organic semiconductor photochemical catalyst, be made up of metal nanoparticle, semiconducting organic polymer and inorganic carrier, its structure is that the metal nanoparticle that semiconducting organic polymer is modified is carried on inorganic carrier, it is characterized in that, described metal nanoparticle is the one in platinum, ruthenium, palladium, rhodium, described semiconducting organic polymer is the one in polypyrrole, polyaniline, polythiophene, and described inorganic carrier is active carbon, aluminium oxide (Al
2o
3), one in silica gel, the mass percent that described metal nanoparticle accounts for inorganic carrier is 0.1% ~ 20%, and the average grain diameter of metal nanoparticle is between 1 nanometer to 20 nanometers.
2. visible light-responded metal/organic semiconductor photochemical catalyst according to claim 1, is characterized in that, the mass percent that described semiconducting organic polymer accounts for inorganic carrier is 0.1% ~ 20%.
3. visible light-responded metal/organic semiconductor photochemical catalyst according to claim 1, is characterized in that, the particle diameter of described inorganic carrier is between 5 nanometers are to 5 microns.
4. the preparation method of visible light-responded metal/organic semiconductor photochemical catalyst according to claim 1, it is characterized in that, comprise the following steps: after semiconducting organic polymer mixes with inorganic carrier, the metal precursor aqueous solution of dipping certain mass, reductant solution is dripped under vigorous stirring, stirring at normal temperature places sedimentation aging 1 ~ 10 day after 2 ~ 8 hours, revolve and steam except desolventizing final vacuum is dry, gained sample 150-350 DEG C of hydrogen reducing can obtain catalyst fines after 4 hours.
5. the preparation method of visible light-responded metal/organic semiconductor photochemical catalyst according to claim 4, is characterized in that, the described metal precursor aqueous solution is metal nitrate saline solution.
6. the preparation method of visible light-responded metal/organic semiconductor photochemical catalyst according to claim 5, is characterized in that, described reducing agent is hydrazine hydrate, sodium borohydride or ethanol.
7. the application of visible light-responded metal/organic semiconductor photochemical catalyst according to claim 1, its photocatalysis treatment for air, Organic Pollutants in Wastewater or the light-catalyzed reaction for photocatalysis synthesis, wherein said light-catalyzed reaction is carried out under visible ray, ultraviolet light or sunshine.
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| CN113828354A (en) * | 2018-09-14 | 2021-12-24 | 浙江大学台州研究院 | Preparation method of composite catalyst based on polypyrrole and carbon foam loaded gold nanowires |
| CN110898680B (en) * | 2019-12-03 | 2022-01-14 | 黎明职业大学 | Polythiophene sensitized TiO2Preparation method of polydopamine modified composite nanofiltration membrane |
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| 纳米Pt/TiO2催化剂上气相CH3OH光催化分解制氢的研究;崔文权等;《化学学报》;20051231;第63卷(第3期);第203-209页 * |
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