CN104815699A - Full-color-photoresponsive titanium-dioxide-base photocatalytic material and preparation method thereof, and application of photocatalytic material in hydrogen production - Google Patents
Full-color-photoresponsive titanium-dioxide-base photocatalytic material and preparation method thereof, and application of photocatalytic material in hydrogen production Download PDFInfo
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Abstract
The invention discloses a full-color-photoresponsive titanium-dioxide-base photocatalytic material and a preparation method thereof, and application of the photocatalytic material in hydrogen production, belonging to the technical field of photocatalytic hydrogen production. The preparation method comprises the following steps: adding nano TiO2 powder into an ascorbic acid water solution, stirring, carrying out solid-liquid separation to obtain a khaki product visible-light-responsive titanium-dioxide-base photocatalytic material, adding into an asymmetric zinc phthalocyanine derivative ethanol solution, stirring, and carrying out solid-liquid separation to obtain a full-color-photoresponsive titanium-dioxide-base photocatalytic material, wherein the addition sequence of the ascorbic acid water solution and asymmetric zinc phthalocyanine derivative ethanol solution can also be exchanged to obtain the full-color-photoresponsive titanium-dioxide-base photocatalytic material. The ascorbic acid and phthalocyanine dye are utilized for the first time to prepare the full-color-photoresponsive titanium-dioxide-base photocatalytic material on the TiO2 surface, which integrates the ligand-to-metal charge transfer and dye sensitization mechanisms. The full-color-photoresponsive titanium-dioxide-base photocatalytic material can be used for photocatalytic hydrogen production, and has wide spectral response range (400-800nm).
Description
Technical field
The invention belongs to Photocatalyzed Hydrogen Production technical field, be specifically related to a kind of titanium dioxide (TiO of panchromatic photoresponse
2) base optic catalytic material and preparation method thereof and the application of product hydrogen.
Background technology
The sustainable development of human society in the problem serious threats such as the environmental pollution of petering out and increasingly sharpening of the fossil energy (as coal, oil and natural gas) that the industrialized process at full speed of human society is brought.Therefore, oneself is extremely urgent for the new forms of energy that exploitation is clean.Photocatalysis a kind ofly has development prospect " Solar fuels (solar energy fuel) " technology of preparing.At present, titanium dioxide (TiO
2) become extensive, the most most popular catalysis material of research because having the characteristics such as cheapness, stable and nontoxic pollution-free, but TiO
2maximum deficiency be its greater band gap (~ 3.2eV), only to utilize in sunshine ~ the ultraviolet light of 4%, and to account for solar energy total amount ~ visible ray of 53% and ~ 43% infrared light helpless.Therefore, people are around TiO
2developed a series of regulating strategy (as ion doping, noble-metal-supported, with narrow gap semiconductor compound and dye sensitization etc.) improve its responding ability to visible ray (even infrared light), to building the catalysis material of efficient, stable, economic and panchromatic photoresponse to meet the requirement of Sustainable Development in Future.
Dye sensitization promotes wide band gap semiconducter (as TiO
2deng) effective to the one of the responding ability of visible ray, and the strategy extensively adopted.Ideal situation should be that a kind of dyestuff can all have very strong absorbability to the visible of sunshine and infrared light district, but actual conditions are often kind of dyestuffs substantially only has certain photoresponse ability to respective characteristic absorption scope.Such as, ruthenium-bipyridyliums complex, porphyrin complex, organic dyestuff etc. only have good absorbability (J.Am.Chem.Soc.2009,131,18457 to the visible region of 400-600nm substantially; ACS Catal.2014,4,2763); Phthalocyanines complex and square type dye then usual ruddiness/near infrared light to 600-800nm have stronger absorbability (Phys.Chem.Chem.Phys., 2010,12,13020; J.Mater.Chem.A, 2015,3,2320).As can be seen here, be difficult to build the dye sensitization TiO with panchromatic photoresponse ability by the method for homogencous dyes sensitization
2base optic catalytic material.In addition, because ruthenium-bipyridyliums complex etc. exists high cost and potential heavy metal pollution, although and organic dyestuff environmental hazard is relatively little also there is the problems such as synthesis technique is complicated.Therefore, developing more cheap, eco-friendly dye-sensitized semiconductor system is also imperative for Photocatalyzed Hydrogen Production field.
Summary of the invention
Producing the deficiency of hydrogen technology in order to overcome above-mentioned existing dye-sensitized semiconductor, the object of the present invention is to provide a kind of titanium dioxide (TiO of panchromatic photoresponse
2) base optic catalytic material and preparation method thereof and the application of product hydrogen.Cheap, nontoxic, the free of contamination ascorbic acid of the present invention (AA, molecular structure as shown in Figure 1) is at TiO
2surface in situ forms surface charge transfer complex (AA-TiO
2), it has visible light-responded ability within the scope of 400-600nm and the active high of Photocatalyzed Hydrogen Production.Then adopt asymmetric ZnPc (Zn-tri-PcNc, the molecular structure as shown in Figure 1) sensitization altogether within the scope of 600-800nm with ruddiness/near infrared light responding ability, be structured in the TiO of the panchromatic photoresponse within the scope of 400-800nm
2base optic catalytic material (Zn-tri-PcNc-TiO
2-AA).
Object of the present invention is achieved through the following technical solutions:
A kind of visible light-responded titanium dioxide (TiO
2) base optic catalytic material, be the surface charge transfer complex (AA-TiO that ascorbic acid (AA) is formed at nano titanium oxide surface in situ
2).This material can respond the visible ray of 400-600nm wavelength.
A kind of titanium dioxide (TiO of panchromatic photoresponse
2) base optic catalytic material (Zn-tri-PcNc-TiO
2-AA), for shifting complex (AA-TiO in above-mentioned surface charge
2) upper load has the catalysis material of asymmetric ZnPc derivative (Zn-tri-PcNc) or shift complex for the surface charge having the nano titanium oxide surface in situ of asymmetric ZnPc derivative to be formed in load, both essence is a kind of material, and both all can respond the panchromatic light in 400-800nm wave-length coverage.In this catalysis material, the load capacity of asymmetric ZnPc derivative is preferably 4-8 μm of ol/g.
The preparation method of above-mentioned visible light-responded titanium dioxide based photocatalytic material, comprises the steps: nano-TiO
2powder joins in colourless ascorbic acid (AA) aqueous solution, stir, suspension becomes khaki immediately, obtains khaki product (as shown in Figure 2) after Separation of Solid and Liquid, and this product is visible light-responded titanium dioxide based photocatalytic materials A A-TiO
2.
The concentration of described aqueous ascorbic acid is preferably 10-100mM, nano-TiO
2the mass volume ratio (mg/mL) of powder and aqueous ascorbic acid is preferably 1:1.
The preparation method of the titanium dioxide based photocatalytic material of above-mentioned panchromatic photoresponse is method A or method B,
Wherein, method A comprises the steps: to prepare AA-TiO according to the method described above
2, then joined in asymmetric ZnPc derivative (Zn-tri-PcNc) ethanolic solution, stir after 12-24 hour, Separation of Solid and Liquid obtains the titanium dioxide based photocatalytic material Zn-tri-PcNc-TiO of panchromatic photoresponse
2-AA.
Method B comprises the steps: nano-TiO
2powder joins in asymmetric ZnPc derivative ethanolic solution, and stir after 12-24 hour, Separation of Solid and Liquid, gained solid joins in aqueous ascorbic acid, and stir, Separation of Solid and Liquid obtains the titanium dioxide based photocatalytic material of panchromatic photoresponse.
Described asymmetric ZnPc derivative is the unsymmetrical phthalocyanine dyestuff of the electronics rolled into a ball according to the peripheral substituent of the phthalocyanine effect that " pushes away-La " synthesis.The concentration of described asymmetric ZnPc derivative ethanolic solution is preferably 0.13-0.27mM, nano-TiO
2the mass volume ratio (mg/mL) of powder and asymmetric ZnPc derivative ethanolic solution is preferably 100:3.
Above-mentioned visible light-responded titanium dioxide based photocatalytic material (AA-TiO
2) or panchromatic photoresponse titanium dioxide based photocatalytic material (Zn-tri-PcNc-TiO
2-AA) application in Photocatalyzed Hydrogen Production field.
For a photochemical catalyst for Photocatalyzed Hydrogen Production, prepared by the method comprising following steps: nano-TiO load being had Pt
2or to join in aqueous ascorbic acid to obtain photochemical catalyst; Or the nano-TiO of Pt is had in load
2on the asymmetric ZnPc derivative of load again, to be joined in aqueous ascorbic acid to obtain photochemical catalyst.Namely this photochemical catalyst being used for Photocatalyzed Hydrogen Production is the titanium dioxide based photocatalytic materials A A-TiO that load has Pt
2or Zn-tri-PcNc-TiO
2-AA.
The pH of described aqueous ascorbic acid is preferably 2.6.
The present invention is with AA and TiO of cheapness
2for raw material, prepared the surface charge transfer complex (AA-TiO with visible light-responded ability by simple " original position formation " method
2) catalysis material, then with the sensitization altogether of the asymmetric phthalocyanine dye with strong ruddiness/near infrared light responding ability, prepared the TiO with panchromatic photoresponse Photocatalyzed Hydrogen Production ability
2base optic catalytic material (Zn-tri-PcNc-TiO
2-AA), for the H2-producing capacity of the spectral response range and raising dye-sensitized semiconductor of expanding wide bandgap semiconductor materials further provides brand-new thinking.
The present invention has the following advantages and effect relative to prior art:
(1) raw material ascorbic acid is cheap and easy to get, and phthalocyanine dye synthesis technique is simply ripe.
(2) surface charge transfer complex (AA-TiO
2) " original position formation " method of catalysis material is quick, efficient.
(3) first with cheap, free of contamination ascorbic acid and phthalocyanine at TiO
2the product hydrogen system of the catalysis material that part is integrated in one to Charger transfer and dye sensitization two kinds of mechanism of metal by surface construction and panchromatic photoresponse thereof, and synthesis technique is simple, spectral response range wide (400-800nm), hydrogen generation efficiency are high, with low cost, are applicable to large-scale production.
Accompanying drawing explanation
Fig. 1 is the structure chart of ascorbic acid (AA) and asymmetric ZnPc (Zn-tri-PcNc).
Fig. 2 is TiO
2add the surface charge transfer complex (AA-TiO that the AA aqueous solution obtains
2) structure and color diagram.
Fig. 3 is surface charge transfer complex (AA-TiO
2) and be total to sensitization TiO
2base optic catalytic material (Zn-tri-PcNc-TiO
2-AA) UV-Vis DRS absorption spectrum (left figure) and by its calculate obtain energy diagram (right figure).
Fig. 4 is surface charge transfer complex (AA-TiO
2) visible ray (λ>=420nm) catalysis of catalysis material produces hydrogen activity with the change curve of the pH of light-catalyzed reaction system.
Fig. 5 is pH AA-Pt/TiO when being 2.60
2and Zn-tri-PcNc-Pt/TiO
2the H2-producing capacity comparing result figure of-AA under different cutoff wavelength is irradiated.
Fig. 6 is AA-Pt/TiO
2and Zn-tri-PcNc-Pt/TiO
2the stability experiment result figure of hydrogen activity is produced in visible ray (λ>=420nm) catalysis of-AA.
Fig. 7 is AA-Pt/TiO
2and Zn-tri-PcNc-Pt/TiO
2product hydrogen AQY curve map under the monochromatic light photograph of-AA.
Detailed description of the invention
Below in conjunction with embodiment and accompanying drawing, further detailed description is done to the present invention, but should not be construed as limitation of the present invention, without departing from the spirit and substance of the case in the present invention, amendment the inventive method, step or condition done or replace and all belong to scope of the present invention.If do not specialize, the conventional means that technological means used in embodiment is well known to those skilled in the art.
Embodiment 1
1, AA-TiO
2, Zn-tri-PcNc-TiO
2the preparation of-AA
(1) preparation of asymmetric ZnPc derivative Zn-tri-PcNc:
A: carry out synthesis cis-1 by the reaction equation shown in following route 1,2-dicyano tert-butyl vinyl part, detailed process is as follows:
Route 1
1) tert-butyl acetylene (500mg, 6mmol) and n-hexane (10mL) are placed in 25mL there-necked flask and are cooled to-10 DEG C.Under 125W high voltage mercury lamp radiation, drip dry bromine (1mL is mixed in 2mL n-hexane), after illumination reaction 4h, steam solvent and the complete bromine of unreacted, with benzinum silica gel column chromatography.Isolate two bands, the first band is the cis-product (cis-1,2-dibromo tert-butyl vinyl) of colorless oil; Second band is the trans product (trans-1,2-dibromo tert-butyl vinyl) of White crystal.For improving the conversion ratio of alkynes, bromine excessive about 20%.Major product cis-1,2-dibromo tert-butyl vinyl: 726mg; Productive rate: 50%.
1H NMR(CDCl
3,300MHz):δ＝6.65(s,1H),1.23ppm(s,9H)。
2) by above-mentioned cis-1; 2-dibromo tert-butyl vinyl (4.0g; 16.4mmol) with cuprous cyanide (2.88g; 32.8mmol) add in DMF (100mL); after the lower 100 DEG C of backflow 6 ~ 8h of nitrogen protection; add 200mL concentrated ammonia liquor, blast air 6 ~ 8h, until the cuprous cyanide not participating in reaction is fully oxidized.Then with toluene extraction, after evaporate to dryness, with carrene ultrasonic dissolution, filter, repeatedly washing leaching cake, after merging filtrate is spin-dried for, with pure benzinum silica gel column chromatography, isolate unreacted raw material.Drench lower product with carrene again, be spin-dried for rear ethyl alcohol recrystallization, obtain brilliant white flat crystal cis-1,2-dicyano tert-butyl vinyl.Product: 27mg; Productive rate: 52%.
1H NMR(CDCl
3,300MHz):δ＝5.86(s,1H),1.27ppm(s,9H)。
B: carry out synthesis 6-carboxymethyl-2,3-dicyano naphthalene part by the reaction equation shown in following route 2, detailed process is as follows:
Route 2
1) 3,4-mesitylenic acid (5.0g, 333mmol) is dissolved in 35mL methyl alcohol the 24h that refluxes, in course of reaction, drips watery hydrochloric acid simultaneously.Reaction terminates rear decompression and steams solvent, mix with 20mL water, extract with ethyl acetate (35mL × 3), 10% sodium carbonate liquor (35mL × 3), water (35mL × 3) and saturated sodium-chloride (35mL × 3) successively again, finally spend the night with anhydrous magnesium sulfate drying, filtration obtains 3,4-dimethylbenzoate methyl ester.Productive rate: 99%.
1HNMR(CDCl
3,300MHz):δ＝7.78-7.72(m,2H),7.16-7.13(d,1H),3.86(s,3H),2.26ppm(s,6H)。
2) get the NBS that above-mentioned 3,4-dimethylbenzoate methyl ester (5.0g, 304mmol) add 30.0g, then add solvent C Cl
4(45mL).Reflux under the high voltage mercury lamp radiation of 125W after 48h, cross filtering insoluble matter, with n-hexane recrystallization, obtain yellow solid product (3,4-bis-or two bromomethyl Methyl Benzoate).Productive rate: 58%.
1H NMR(CDCl
3,300MHz):δ＝8.29(s,1H),8.04～8.02(d,1H),7.83(s,1H),7.27-7.26(d,2H),3.97ppm(s,3H)。
3) fumaric acid (30g, 258mmol) is dissolved in 200mL methyl alcohol the 8h that refluxes, in course of reaction, drips watery hydrochloric acid simultaneously.After completion of the reaction mixed liquor is cooled to room temperature, filters, with rare Na
2cO
3solution and distilled water washing leaching cake, dry, obtain white shiny product, be fumaric acid methyl esters.Productive rate: 58%.
1H NMR(CDCl
3,300MHz):δ＝7.44～7.42(m,2H),4.38ppm(s,6H)。
4) the fumaric acid methyl esters (30g, 263mmol) obtained and 100mL concentrated ammonia liquor are at room temperature stirred 24h, filter, with cold water and acetone washing leaching cake, dry, obtain white product fumaramide (productive rate 77%).
5) fumaramide (10g, 88mmol) and P is got
2o
5(10g, 71mmol) mixes, and at 120 ~ 140 DEG C, dehydration is carried out in decompression, makes product distillation crystallization, collects product as white needles, be anti-maleic nitrile at air setting tube wall.Productive rate: 43%.
1H NMR(CDCl
3,300MHz):δ＝6.23ppm(s,2H)。
6) in the DMF of 63mL, add above-mentioned 3,4-bis-two bromomethyl Methyl Benzoates (5.0g, 10mmol), anti-maleic nitrile (3.75g, 43mmol) and anhydrous Na I (7.79g, 52mmol), after 80 DEG C of stirring 12h, pour reactant mixture into Na
2s
2o
3solution (Na
2s
2o
312.9g, water 347mL), yellow mercury oxide is filtered, with acetone hot recrystallization, dry, obtain light yellow 6-carboxymethyl-2,3-dicyano naphthalene part.Productive rate: 50%.
1H NMR(CDCl
3,300MHz):δ＝8.71(s,1H),8.47(s,1H),8.41(s,1H),8.38-8.37(d,1H),8.07-8.05(d,1H),4.31ppm(s,3H)。
C: carry out synthesis 3,10,17-tri-tert-23,24-(4-carboxyl) benzo Phthalocyanine Zinc (Zn-tri-PcNc) by the reaction equation shown in following route 3, detailed process is as follows:
Route 3
1) the part 6-carboxymethyl-2 of above-mentioned synthesis is got, 3-dicyano naphthalene (80mg, 0.22mmol) with 4-tert-butyl o dicyanobenzenes (374mg, 2.2mmol), two water zinc acetate (222mg, 0.66mmol) add in n-butanol (5mL), instill several catalyst DBU again, reactant mixture is in the nitrogen protection environment of anhydrous and oxygen-free, after 120 DEG C of reaction 6-8h, find that reactant mixture cannot with methyl alcohol, n-hexane equal solvent is recrystallized, therefore drain solvent with vavuum pump, 6 ‰ ethanol/methylene, the long silica gel column chromatography of 12cm is separated, obtain 3, 10, 17-tri-tert-23, 24-(4-carboxylic butyl) benzo Phthalocyanine Zinc.Product: 30mg, productive rate: 10%.
1h NMR (DMSO-d
6, 300MHz): δ=9.39 (s, 1H), 9.34 (s, 1H), 9.32 ~ 9.19 (d, 3H), 9.12 ~ 9.0 (m, 2H), 8.59 (s, 1H), 8.35 ~ 8.19 (m, 6H), 4.54 ~ 4.50 (m, 2H), 1.94 ~ 1.19 (m, 2H), 1.73 ~ 1.67 (m, 2H), 1.17 (s, 27H), 0.84 ~ 0.78ppm (m, 3H) .:TOF-MS (m/z) calcd.for C
53h
50n
8o
2zn [M+H]
+896.40, found895.59; Elementary analysis: C
53h
50n
8o
2zn theoretical value: C 71.01, H 5.62, N 12.50; Test value: C 71.38, H 5.81, N 12.37.
2) by above-mentioned asymmetric ZnPc derivative 3,10,17-tri-tert-23,24-(4-carboxylic butyl) benzo Phthalocyanine Zinc (80mg, 0.9mmol), ethanol 250mL, sodium metal block (3.0g, 130mmol) adds in reactor, and 80 DEG C are refluxed 7 days, after having reacted, be spin-dried for ethanol and obtain sodium alkoxide solid, then add suitable quantity of water dissolving, separate out with concentrated hydrochloric acid neutralization reaction product, filter, washing, methanol wash column obtains asymmetric ZnPc derivative 3,10,17-tri-tert-23,24-(4-carboxyl) benzo Phthalocyanine Zinc (Zn-tri-PcNc).Product: 98mg, productive rate: 98%.
1h NMR (DMSO-d
6, 300MHz): δ=11.23 (s, 1H), 9.16 (s, 3H), 8.89 ~ 8.11 (m, 8H), 7.85 ~ 7.72 (m, 3H), 1.83 (s, 9H), 1.14 (s, 9H), 0.73ppm (s, 9H): TOF-MS (m/z) calcd.for C
49h
42n
8o
2zn [M+H]
+840.30, found 838.91; Elementary analysis: C
49h
42n
8o
2zn0.4CHCl
3, theoretical value: C 66.81, H 4.81, N 12.62; Test value: C 66.97, H 4.82, N 12.73.
(2) AA-TiO
2, Zn-tri-PcNc-TiO
2the preparation of-AA
1) AA-TiO
2preparation
By 100mg nano-TiO
2powder (P25) joins in the colourless AA aqueous solution of 100mL 50mM, and solution changes khaki into rapidly, obtains khaki product (Fig. 2) after Separation of Solid and Liquid, and namely the on-the-spot surface charge that formed shifts complex (AA-TiO
2).
2) Zn-tri-PcNc-TiO
2-AA is prepared by following method:
2.1): by 100mg nano-TiO
2powder (P25) joins the Zn-tri-PcNc (3 of 3mL 0.17mM, 10,17-tri-tert-23,24-(4-carboxyl) benzo Phthalocyanine Zinc) in ethanolic solution, stirring at room temperature is after 24 hours, and Separation of Solid and Liquid obtains Zn-tri-PcNc-TiO
2.By Zn-tri-PcNc-TiO
2join in the colourless AA aqueous solution of 100mL 50mM, because scene forms AA-TiO
2, namely obtain common sensitization TiO
2base optic catalytic material Zn-tri-PcNc-TiO
2-AA, Zn-tri-PcNc content is 5.0 μm of ol/g.
Or 2.2): by 1) the khaki product that obtains joins the Zn-tri-PcNc (3 of 3mL 0.17mM, 10,17-tri-tert-23,24-(4-carboxyl) benzo Phthalocyanine Zinc) in ethanolic solution, stirring at room temperature is after 24 hours, and Separation of Solid and Liquid obtains sensitization TiO altogether
2base optic catalytic material (Zn-tri-PcNc-TiO
2-AA), Zn-tri-PcNc content is 5.0 μm of ol/g.
Due to AA-TiO
2by TiO
2powder joins in the AA aqueous solution, is formed immediately, therefore Zn-tri-PcNc-TiO
2first AA-TiO is formed in the preparation process of-AA
2join in Zn-tri-PcNc solution again or first form Zn-tri-PcNc-TiO
2it is the same for joining in the AA aqueous solution again.
2, AA-TiO
2, Zn-tri-PcNc-TiO
2the UV-Vis DRS absorption spectroanalysis of-AA
By AA-TiO obtained above
2, Zn-tri-PcNc-TiO
2, Zn-tri-PcNc-TiO
2-AA (method 2.1) gained) after centrifugation, 60 DEG C of vacuum drying, carry out UV-Vis DRS absorption spectromtry.
TiO
2, AA, AA-TiO
2, Zn-tri-PcNc-TiO
2and Zn-tri-PcNc-TiO
2the UV-Vis DRS absorption spectrum (DRS) of-AA is shown in Fig. 3 (left side).No matter be TiO
2or AA does not all have visible absorption ability, AA-TiO
2but have good visible absorption ability, it absorbs band edge even can extend to about 800nm, but main light absorption range concentrates on 400-650nm, and the visible absorption ability of this new generation is by AA and TiO
2between form surface charge transfer complex and to cause; Zn-tri-PcNc-TiO
2there is good ruddiness/near infrared light (600-800nm) absorbability; Meanwhile, Zn-tri-PcNc-TiO
2-AA has the panchromatic photoresponse ability within the scope of 400-800nm.
Can be inferred easily by DRS spectrum and its general band gap, TiO
2band gap magnitude be about 3.05eV, AA-TiO
2visible absorption capability list due to its excellence reveals less band gap magnitude (about 1.59eV).
According to Charger transfer (LMCT) mechanism of part to metal, AA-TiO
2light induced electron under visible light directly transits to TiO by the HOMO of AA
2conduction band (about-0.5eV), can infer and AA-TiO
2the HOMO position of the intermediate level of new formation is about 1.09eV (as Suo Shi Fig. 3 (right side)).It can thus be appreciated that, following A A-TiO
2visible light catalytic H_2-producing mechanism is the charge transfer process of part to metal, that is: visible ray shines the highest occupied molecular orbital (HOMO) of lower generation from AA to TiO
2the charge transtion of conduction band.
3, pH is to AA-TiO
2, Zn-tri-PcNc-TiO
2-AA produces the impact of hydrogen activity
Pt/TiO is prepared by photoreduction met hod
2, concrete steps are: 0.2g nano-TiO
2powder (P25) joins in 40mL water and 10mL ethanol, adds the H that 0.0133mL concentration is 0.07723M
2ptCl
6the aqueous solution, after ultrasonic disperse is even, centrifugation after 500W mercury lamp illumination 3h, 70 DEG C are drying to obtain.
Zn-tri-PcNc-Pt/TiO
2preparation process with above-mentioned Zn-tri-PcNc-TiO
2preparation process, by nano-TiO
2powder (P25) changes the Pt/TiO of above-mentioned preparation into
2.
The concrete steps of Photocatalyzed Hydrogen Production experiment are: the cumulative volume adopting Photoreactor is 75mL.By 10mg Pt/TiO
2(0.1wt%Pt) or Zn-tri-PcNc-Pt/TiO
2join in the AA aqueous solution of the different pH (regulating with HCl or NaOH of 1.0M) of 10mL 50mM, original position immediately can form AA-Pt/TiO
2or Zn-tri-PcNc-Pt/TiO
2-AA photochemical catalyst, ultrasonic disperse is even, then vacuumizes the O removed in suspension
2, then being equipped with>=the 300W Xe lamp of 420nm optical filter under illumination, then carry out hydrogen output detection every 1h, hydrogen output detect adopt SP6890 gas-chromatography (Shandong Lunan, TCD detector,
molecular sieve column, Zhejiang intelligence reaches N2000 and to work online station).
Photocatalyzed Hydrogen Production experimental result shows, independent Pt/TiO
2or the AA aqueous solution does not all have visible ray (λ>=420nm) catalysis and produces hydrogen activity, but when the two mixes time, except the obvious color of generation changes, also present beat all visible light catalytic product hydrogen activity.As seen from Figure 4, in above-mentioned Photocatalyzed Hydrogen Production system, its hydrogen generation efficiency can significantly be promoted by the pH value of adjustment AA solution.The pH of 50mM AA solution (initial pH is about 1.5-1.8) is regulated gradually toward alkaline direction, AA-Pt/TiO
2under visible ray shines, within the scope of wider acidity and alkalescent, (1.5-8.5) all shows certain product hydrogen activity, and reaches peak when about pH=2.60.Compared with the system regulated without pH, produce hydrogen activity during about pH=2.60 and improve about 114%.As seen from Figure 5, sensitization catalyst Z n-tri-PcNc-Pt/TiO is total to
2the product hydrogen activity of-AA improves 28.6% further, along with the prolongation of cutoff wavelength, and AA-Pt/TiO
2product hydrogen activity sharply decline, and almost do not produce hydrogen activity when λ>=600nm; Zn-tri-PcNc-Pt/TiO
2the product hydrogen activity of-AA also presents downward trend along with the prolongation of cutoff wavelength, but under λ>=600nm illumination, still show higher product hydrogen activity, and this part produces the optical sensibilization that hydrogen activity derives from Zn-tri-PcNc.To be contrasted by H2-producing capacity and DRS figure can find out, surface charge transfer complex AA-Pt/TiO
2practical function scope be ruddiness/near infrared light that 400-600nm, Zn-tri-PcNc then can catch 600-800nm.
4, AA-TiO
2, Zn-tri-PcNc-TiO
2the stability of-AA Photocatalyzed Hydrogen Production
The concrete steps of Photocatalyzed Hydrogen Production stability experiment are: the cumulative volume adopting Photoreactor is 350mL.By 50mg Pt/TiO
2(0.1wt%Pt) or Zn-tri-PcNc-Pt/TiO
2join in the AA aqueous solution of 50mL 50mM pH=2.60, original position immediately can form AA-Pt/TiO
2or Zn-tri-PcNc-Pt/TiO
2-AA photochemical catalyst, ultrasonic disperse is even, then vacuumizes the O removed in suspension
2, then being equipped with>=the 300W Xe lamp of 420nm optical filter under illumination, then carry out hydrogen output detection every 1h, hydrogen output detect adopt SP6890 gas-chromatography (Shandong Lunan, TCD detector,
molecular sieve column, Zhejiang intelligence reaches N2000 and to work online station).Every hydrogen photoproduction 5h takes turns, and then by catalyst suspension centrifugation, is again changing the AA aqueous solution of pH=2.60, carries out next round and produces hydrogen experiment.
Photocatalyzed Hydrogen Production stability experiment result (Fig. 6) shows: 50mg Pt/TiO
2nano-powder joins the surface charge transfer complex (AA-Pt/TiO formed in the 50mL 50mM AA aqueous solution
2) when the pH of light-catalyzed reaction solution is 2.60, its 1st take turns 5 hours visible rays according under average light catalysis to produce hydrogen activity be 96.4 μm of ol/h, and after taking turns common 20h illumination through 4, the average hydrogen activity that produces does not show obvious decline.Sensitization TiO altogether
2base optic catalytic material (Zn-tri-PcNc-Pt/TiO
2-AA) show higher visible ray product hydrogen activity and stability.Under equal photocatalytic reaction conditions, its 1st take turns 5 hours visible rays according under average product hydrogen activity be 140.2 μm of ol/h, be AA-Pt/TiO
2active 1.45 times; And its average hydrogen activity that produces also has no obvious decline after taking turns common 35h illumination through 7.
5, AA-TiO
2, Zn-tri-PcNc-TiO
2-AA plays the spectral response range of photocatalysis
The concrete steps of Photocatalyzed Hydrogen Production experiment are: the cumulative volume adopting Photoreactor is 75mL.By 10mg Pt/TiO
2(0.1wt%Pt) or Zn-tri-PcNc-Pt/TiO
2join in the AA aqueous solution of 10mL 50mM pH=2.60, original position immediately can form AA-Pt/TiO
2or Zn-tri-PcNc-Pt/TiO
2-AA photochemical catalyst, ultrasonic disperse is even, then vacuumizes the O removed in suspension
2then be equipped with λ=420,450,500,550,600,660,685,700,735,760, illumination under the 300W Xe lamp of the monochromatic filter of 800 ± 10nm, then hydrogen output detection is carried out every 1h, hydrogen output detects and adopts SP6890 gas-chromatography (Shandong Lunan, TCD detector
molecular sieve column, Zhejiang intelligence reaches N2000 and to work online station).
For proving AA-TiO
2, Zn-tri-PcNc-TiO
2-AA can play the actual spectrum response range of photocatalysis, measures AA-Pt/TiO
2, Zn-tri-PcNc-Pt/TiO
2product hydrogen AQY (AQY) value of-AA under a series of monochromatic light shines.Result as shown in Figure 7, AA-Pt/TiO
2and Zn-tri-PcNc-Pt/TiO
2its corresponding UV-Vis DRS absorption spectrum (DRS) of variation tendency of the AQY curve of-AA is consistent substantially, and this shows the titanium dioxide (TiO of obtained panchromatic photoresponse
2) H2-producing capacity of base optic catalytic material is by TiO really
2the surface charge transfer complex that surface is formed and the Zn-tri-PcNc dye molecule of altogether sensitization dominate.AA-Pt/TiO
2within the scope of 400-600nm, show higher product hydrogen AQY value, but then almost do not produce hydrogen activity as monochromatic light irradiation wavelengths > 650nm; And Zn-tri-PcNc-Pt/TiO
2-AA all shows good AQY value in the visible/near infrared district of 400-800nm, and 400-600nm visible region substantially with AA-Pt/TiO
2the product hydrogen activity be consistent, and its variation tendency at the AQY curve of ruddiness/near infrared region is basic consistent with the absorption spectrum of Zn-tri-PcNc.In general, AA-Pt/TiO
2the AQY up to 16.1% is shown at 420nm monochromatic light place, and Zn-tri-PcNc-Pt/TiO
2-AA shows the AQY up to 16.9% and 0.97% respectively in 420 and 700nm monochromatic light place.This sufficient proof Zn-tri-PcNc-Pt/TiO
2-AA not only has panchromatic (visible/near infrared) light absorpting ability, also has panchromatic photoinduced Photocatalyzed Hydrogen Production ability.That is, the common sensitization TiO prepared by the present invention
2base optic catalytic material (Zn-tri-PcNc-TiO
2-AA) successfully part is combined to the Charger transfer of metal and dye sensitization two kinds of mechanism.
Embodiment 2
By 100mg nano-TiO
2powder (P25) joins the Zn-tri-PcNc (3 of 3mL 0.13mM, 10,17-tri-tert-23,24-(4-carboxyl) benzo Phthalocyanine Zinc) in ethanolic solution, stirring at room temperature is after 24 hours, and Separation of Solid and Liquid obtains Zn-tri-PcNc-TiO
2.By Zn-tri-PcNc-TiO
2join in the colourless AA aqueous solution of 100mL 50mM, because scene forms AA-TiO
2, namely obtain common sensitization TiO
2base optic catalytic material Zn-tri-PcNc-TiO
2-AA, Zn-tri-PcNc content is 4.0 μm of ol/g.
Through testing according to the method described in embodiment 1, result shows the Zn-tri-PcNc-TiO that this embodiment obtains
2spectral absorption scope and the H2-producing capacity trend of-AA are similar to Example 1.
Embodiment 3
By 100mg nano-TiO
2powder (P25) joins the Zn-tri-PcNc (3 of 3mL 0.27mM, 10,17-tri-tert-23,24-(4-carboxyl) benzo Phthalocyanine Zinc) in ethanolic solution, stirring at room temperature is after 24 hours, and Separation of Solid and Liquid obtains Zn-tri-PcNc-TiO
2.By Zn-tri-PcNc-TiO
2join in the colourless AA aqueous solution of 100mL 50mM, because scene forms AA-TiO
2, namely obtain common sensitization TiO
2base optic catalytic material Zn-tri-PcNc-TiO
2-AA, Zn-tri-PcNc content is 8.0 μm of ol/g.
Through testing according to the method described in embodiment 1, result shows the Zn-tri-PcNc-TiO that this embodiment obtains
2spectral absorption scope and the H2-producing capacity trend of-AA are similar to Example 1.
Claims (10)
1. a visible light-responded titanium dioxide based photocatalytic material, is characterized in that: the surface charge transfer complex formed at nano titanium oxide surface in situ for ascorbic acid.
2. a titanium dioxide based photocatalytic material for panchromatic photoresponse, is characterized in that: on surface charge transfer complex according to claim 1, load has the catalysis material of asymmetric ZnPc derivative; Or be the surface charge transfer complex having the nano titanium oxide surface in situ of asymmetric ZnPc derivative to be formed in load.
3. the titanium dioxide based photocatalytic material of panchromatic photoresponse according to claim 2, is characterized in that: the load capacity of asymmetric ZnPc derivative is 4-8 μm of ol/g.
4. the preparation method of visible light-responded titanium dioxide based photocatalytic material according to claim 1, is characterized in that comprising the steps: nano-TiO
2powder joins in aqueous ascorbic acid, and stir, suspension becomes khaki immediately, obtains khaki product after Separation of Solid and Liquid, and this product is visible light-responded titanium dioxide based photocatalytic material.
5. preparation method according to claim 4, is characterized in that: the concentration of described aqueous ascorbic acid is 10-100mM, nano-TiO
2the mass volume ratio (mg/mL) of powder and aqueous ascorbic acid is 1:1.
6. the preparation method of the titanium dioxide based photocatalytic material of panchromatic photoresponse according to claim 2, is characterized in that: be method A or method B, wherein,
Method A comprises the steps: to prepare visible light-responded titanium dioxide based photocatalytic material according to the method described in claim 4 or 5, joined in asymmetric ZnPc derivative ethanolic solution, stir after 12-24 hour, Separation of Solid and Liquid obtains the titanium dioxide based photocatalytic material of panchromatic photoresponse;
Method B comprises the steps: nano-TiO
2powder joins in asymmetric ZnPc derivative ethanolic solution, and stir after 12-24 hour, Separation of Solid and Liquid, gained solid joins in aqueous ascorbic acid, and stir, Separation of Solid and Liquid obtains the titanium dioxide based photocatalytic material of panchromatic photoresponse.
7. preparation method according to claim 2, is characterized in that: the concentration of described asymmetric ZnPc derivative ethanolic solution is 0.13-0.27mM, nano-TiO
2the mass volume ratio (mg/mL) of powder and asymmetric ZnPc derivative ethanolic solution is 100:3.
8. the application of titanium dioxide based photocatalytic material in Photocatalyzed Hydrogen Production field described in any one of claim 1-3.
9., for a photochemical catalyst for Photocatalyzed Hydrogen Production, it is characterized in that the method by comprising following steps prepares: nano-TiO load being had Pt
2or to join in aqueous ascorbic acid to obtain photochemical catalyst; Or the nano-TiO of Pt is had in load
2on the asymmetric ZnPc derivative of load again, to be joined in aqueous ascorbic acid to obtain photochemical catalyst.
10. photochemical catalyst according to claim 9, is characterized in that: the pH of described aqueous ascorbic acid is 2.6.
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| CN110787626A (en) * | 2019-11-19 | 2020-02-14 | 四川大学 | Method for low-temperature plasma coupling photocatalytic oxidation of nitrogen oxide |
| CN111908994A (en) * | 2020-08-24 | 2020-11-10 | 济南大学 | Method for photocatalytic alkyne addition reaction and device used by method |
| CN114854034A (en) * | 2022-05-27 | 2022-08-05 | 武汉大学 | Cobalt phthalocyanine and metalloporphyrin coupled covalent organic framework polymer material, preparation method and application thereof |
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| CN110787626A (en) * | 2019-11-19 | 2020-02-14 | 四川大学 | Method for low-temperature plasma coupling photocatalytic oxidation of nitrogen oxide |
| CN111908994A (en) * | 2020-08-24 | 2020-11-10 | 济南大学 | Method for photocatalytic alkyne addition reaction and device used by method |
| CN114854034A (en) * | 2022-05-27 | 2022-08-05 | 武汉大学 | Cobalt phthalocyanine and metalloporphyrin coupled covalent organic framework polymer material, preparation method and application thereof |
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