CN110787795A - Multilayer double-hole structure composite photocatalyst and preparation and application thereof - Google Patents
Multilayer double-hole structure composite photocatalyst and preparation and application thereof Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 120
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- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 8
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 8
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/52—Gold
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
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- 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
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- C02F2101/00—Nature of the contaminant
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Abstract
The invention discloses a multi-level double-hole structure composite photocatalyst, and preparation and application thereof2Template, TiO2Au nanoparticles, mesoporous SiO2A shell layer; the invention overcomes the defects of the conventional TiO2The catalyst can only degrade the organic dye molecules in the ultraviolet light wave band, thereby effectively relaxing the defects of TiO2The use condition of the photocatalyst is utilized by utilizing the metal-semiconductor synergistic effectThe photocatalyst has a multi-level double-hole structure, the openness of a catalytic site is greatly improved while the loading capacity of functional elements is improved, the interaction between the photocatalyst and substrate molecules is facilitated, the photocatalytic efficiency is improved, meanwhile, the structure can improve the stability of the catalyst, the photocatalyst can be repeatedly and efficiently used, and the waste of products is avoided.
Description
(I) technical field
The invention relates to a photocatalyst, in particular to a multi-layer double-hole structure composite photocatalyst and preparation and application thereof.
(II) background of the invention
With the development of society and the improvement of living standard of human beings, environmental problems are attracting more and more attention of human beings. The industrial wastewater seriously threatens the health of people, wherein the organic dye wastewater is one of the main industrial wastewater. The organic dye is mainly from a dyeing and printing process in a physicochemical treatment process of textiles, and the organic dye wastewater has the characteristics of high concentration, high chromaticity, toxicity, more complex components and the like, so that the treatment of the organic dye wastewater becomes a difficult problem. At present, the processing method mainly comprises the following steps: chemical coagulation, biological methods, adsorption methods, photocatalytic oxidation methods, etc., wherein the photocatalytic oxidation method is widely studied as a novel approach for treating organic dye wastewater. Nano TiO22Has attracted much attention in recent years as a highly efficient photocatalytic material and has been commercialized. However, the current TiO2The photocatalyst still has the defects of low light energy utilization rate (only absorbing ultraviolet wave bands), easy generation of light to generate electron-hole recombination, poor stability, difficulty in repeated high-efficiency utilization and the like, and needs to be improved urgently, so that the application prospect of the photocatalytic material is severely limited.
To promote TiO2The application prospect of the photocatalyst is that TiO is loaded by a carrier2The nano-elements are loaded in the mesoporous carrier to prepare the heterogeneous catalyst, and the heterogeneous catalyst can be effectively separated and recycled from a reaction medium while the liquid phase dispersion of the heterogeneous catalyst is maintained. Li et al report on SiO2/TiO2Photocatalyst of core-shell structure prepared by reacting TiO2Loaded on spherical SiO2The surface is easy to separate, so that the cycle number of the photocatalyst can be increased, the problem of recycling is solved, and the loading capacity is too low due to the adoption of surface loading; kamegawa et al reported that SiO2/TiO2Photocatalyst having a porous structure, prepared by reacting TiO2The mesoporous MCM-41 is filled in the internal pore channel, the loading efficiency is improved, but the catalytic site thereofThe dots are limited in the carrier, so that the dots are difficult to effectively contact with external reactants, and the catalytic efficiency is not improved; in addition, at present most TiO2The nanometer element adopts a water phase synthesis method, a water phase in-situ growth method and the like to prepare the TiO2The general crystallinity of the crystal is poor, the surface chemical modification is single, the crystal structure is difficult to control, and the like, so that the regulation and control of the nano structure and the catalytic performance are influenced. Meanwhile, the semiconductor-precious metal composite photocatalyst is obtained through a structure and function integration strategy, and TiO can be effectively solved2The catalyst can only degrade organic dye molecules in the ultraviolet light wave band. Ding et al reported Au/TiO2Photocatalyst of heterostructure with Au particles supported on TiO2And on the surface, effective visible light catalysis is realized. However, the whole composite particle may have problems such as stability in use and difficulty in separation and recovery due to lack of support and protection. Based on the current research situation, high-efficiency TiO is developed2Carrier load technique of nano-elements and function cooperation strategy for simultaneous reality of TiO2The visible light high-efficiency catalysis of the photocatalyst, the improvement of the liquid phase dispersion/reaction performance and the separation, recovery and reutilization performance have important significance.
Disclosure of the invention
The present invention is directed to TiO2The photocatalyst has the defects of low solar energy utilization rate, difficult reutilization and the like, and provides the arborescent mesoporous SiO with the multi-level double-hole structure2/TiO2/Au/SiO2The composite photocatalyst has a multi-layer double-hole structure, can degrade organic dye in a visible light region, has good photocatalytic performance and high light energy utilization rate, and can be repeatedly used.
The technical scheme adopted by the invention is as follows:
the invention provides a multi-level double-hole structure composite photocatalyst which is prepared from arborescent mesoporous SiO2Template, TiO2Au nanoparticles, mesoporous SiO2A shell layer; the mass contents of the components are as follows: SiO2245％ ～65％，TiO235 to 40 percent of Au nanoparticles, 1 to 10 percent of Au nanoparticles, and the total amount of Au nanoparticles100 percent. The catalyst is prepared by first sulfhydrylation dendriform mesoporous SiO2Oleate modified TiO2Assembling nanoparticles, replacing oleic acid ligand with reduced glutathione ligand, converting oil phase into water phase, growing Au nanoparticles in situ, and coating mesoporous SiO2Calcining the shell layer to obtain the multi-level double-hole structure composite photocatalyst, namely the arborescent mesoporous SiO2/TiO2/Au/SiO2A composite photocatalyst is provided. The multilayer structure of the composite photocatalyst is tree-shaped mesoporous SiO2Formed center-radial pore canal and surface mesoporous SiO2The mesoporous pore canal formed by the shell layer forms a multi-level double-pore structure with internal and external permeability and a structure protection effect.
The tree-shaped mesoporous SiO2The diameter of the porous material is 200 nm-400 nm, the aperture is 20 nm-50 nm, and preferably 35-50 nm; the oleic acid-modified TiO2Is anatase type TiO with the particle size of 7-12 nm2Preferably 7 to 9 nm.
The oleate modified TiO of the invention2The nanoparticles are prepared by the following method:
adding oleylamine, oleic acid, absolute ethyl alcohol and tetrabutyl titanate into a beaker, stirring at room temperature for 10min, transferring the mixture into a tetrafluoroethylene-lined stainless steel reaction kettle containing 96% ethanol water solution by volume, reacting at 180 ℃ for 14-18 h, and washing with absolute ethyl alcohol for 3 times after the reaction is finished to obtain oleate modified TiO2The nanoparticles are then dispersed in toluene for storage. The volume ratio of oleylamine to oleic acid, absolute ethyl alcohol and tetrabutyl titanate is 1: 1.5-2.5: 0.5-1: 0.1 to 0.5, preferably 1: 1.93: 0.76: 0.23; the volume ratio of the oleylamine to the 96% ethanol aqueous solution with the volume concentration is 1: 2-3, preferably 1: 2.6.
the sulfhydrylation arborescent mesoporous SiO of the invention2The preparation method comprises the following steps:
dissolving Triethanolamine (TEA) in ultrapure water, magnetically stirring at 80 deg.C in oil bath for 30min, adding Cetyl Trimethyl Ammonium Bromide (CTAB) and sodium salicylate (NaSal), stirring for 1 hr, adding tetraethyl orthosilicate (TEOS), and reactingReacting for 3 hours, and washing the product for 3 times by using absolute ethyl alcohol a after the reaction is finished; then dissolving the mixture into a mixed solution of hydrochloric acid and methanol with the volume ratio of 1:1, stirring the mixture in a water bath at the temperature of 60 ℃ for 6 hours, and repeatedly adding hydrochloric acid and methanol and stirring the mixture once; washing the product with anhydrous ethanol b for 3 times, re-dispersing in anhydrous ethanol c, adding ammonia water (25-28%) and (3-mercaptopropyl) trimethoxysilane (MPS), stirring at room temperature for 12h, and washing the product with anhydrous ethanol d for 3 times to obtain the thiol-modified dendritic mesoporous SiO22Dispersing in absolute ethyl alcohol e for preservation. The volume usage of the ultrapure water is 300-500 ml/g, preferably 367.65ml/g, based on the weight of triethanolamine, and the weight ratio of cetyl trimethyl ammonium bromide to triethanolamine is 5-7: 1, preferably 5.59: 1, the weight ratio of the triethanolamine to the sodium salicylate is 1: 2-4, preferably 1: 3.21; the volume dosage of the ethyl orthosilicate is 50-70 ml/g, preferably 58.82ml/g, based on the weight of the triethanolamine; the volume dosage of the mixed solution of the hydrochloric acid and the methanol is 1-2L/g, preferably 1.5L/g calculated by the weight of the triethanolamine; the volume dosage of the absolute ethyl alcohol c is 1-5L/g, preferably 2.9L/g based on the weight of the triethanolamine; the volume usage of the ammonia water is 30-40 ml/g, preferably 36.76ml/g, based on the weight of the triethanolamine; the volume usage of the (3-mercaptopropyl) trimethoxysilane is 10-20 ml/g, preferably 14.7ml/g, based on the weight of triethanolamine. The absolute ethyl alcohol a to the absolute ethyl alcohol d are absolute ethyl alcohol, are named for the convenience of distinguishing the use amount of different steps, and have no meaning by letters.
The multi-level double-hole structure composite photocatalyst is prepared by the following steps:
(1) oil phase tree-shaped mesoporous SiO2/TiO2Synthesis of assembly and phase transfer process: sulfhydrylation dendriform mesoporous SiO2Centrifuging the ethanol solution (10000r/min, 10min) to obtain precipitate, and then adding oleic acid modified TiO2Adding the toluene solution, assembling for 10min under the ultrasonic (preferably 40KHz) condition, centrifuging, and dissolving the precipitate in chloroform to obtain a solution 1; dissolving reduced glutathione in BR buffer solution with pH of 9, adjusting pH to 9 with 0.8M NaOH aqueous solution, and marking as solution 2; then adding the solution 2 into the solution 1 in an adherent manner to form an oil-water two-phase system, heating and stirring the system in a water bath at the temperature of 60 ℃ for 8 to 9 hours,realization of SiO2/TiO2Phase transfer of the assembly, taking out the upper solution, centrifuging, washing the precipitate with anhydrous ethanol for 3 times to obtain water phase dendriform mesoporous SiO2/TiO2The assembly is dispersed in ultrapure water for storage; the sulfhydrylation arborescent mesoporous SiO2SiO in ethanol solution2TiO modified with oleic acid2TiO in toluene solution2The mass ratio is 1.5:1, SiO in solution 12With TiO2The total mass concentration is 1-5mg/ml (preferably 2.5-3.5 mg/ml), and the oleic acid modified TiO2The concentration of the toluene solution is 0.0082-0.011 g/ml; the volume consumption of the BR buffer solution is 25-75 ml/g based on the weight of reduced glutathione; the volume ratio of the solution 1 to the solution 2 is 1: 1;
(2) au nanoparticle growth, SiO2Coating and calcining processes: under the condition of ice bath, 20g/L of HAuCl4Aqueous solution, 0.2M K2CO3Sequentially adding the aqueous solution into water, stirring for 10min, and adding the aqueous phase dendriform mesoporous SiO2/TiO2Stirring the assembly for 10min, adding 0.5g/L sodium borohydride aqueous solution, reacting for 1min, centrifuging, dispersing the precipitate in water, and washing once; centrifuging, dispersing the precipitate into 5mM CTAB aqueous solution, adding 0.1M NaOH aqueous solution, adding TEOS solution (mass concentration is more than or equal to 99%) three times, stirring at room temperature for 24h, washing with ultrapure water for 3 times, placing the obtained precipitate in a vacuum tube furnace, calcining at 500 ℃ for 3h in air atmosphere to obtain the dendriform mesoporous SiO2/TiO2/Au/SiO2A composite photocatalyst; the water, HAuCl4Aqueous solution, K2CO3The volume dosage of the aqueous solution is dendritic mesoporous SiO2/TiO2The assembly quality is 0.4ml/mg, 0.02-0.04ml/mg and 0.03-0.6ml/mg (preferably 0.03-0.06ml/mg) respectively; the volume dosages of the sodium borohydride aqueous solution, the CTAB aqueous solution, the NaOH aqueous solution and the TEOS solution are determined by the water-phase tree-shaped mesoporous SiO2/TiO2The assembly body mass is 4-16ml/g (preferably 4-8 ml/g), 1500-2500 ml/g, 15-25 ml/g and 3-5 ml/g.
The invention also provides the tree-shaped mesoporous SiO2/TiO2/Au/SiO2The application of the composite photocatalyst in degrading organic dye is as follows: firstly, tree-shaped mesoporous SiO2/TiO2/Au/SiO2Adding the composite photocatalyst into an organic dye aqueous solution, stirring for 30min at room temperature to ensure that the catalyst and the organic dye reach adsorption-desorption balance, then turning on a xenon lamp, and carrying out photocatalytic degradation under the condition of 300W; the organic dye is rhodamine B, and the concentration of the organic dye is preferably 10-30 mg/ml and is preferably 20 mg/ml; the volume usage of the organic dye aqueous solution is 1-3 ml/g, preferably 2.5ml/g, calculated by the mass of the catalyst.
The principle of the invention is as follows:
tree-shaped mesoporous SiO2The photocatalyst has larger specific surface area, pore diameter and pore volume, high thermal stability and mechanical stability, and can be used as a carrier of the photocatalyst, so that the specific surface area utilization rate of the photocatalyst is improved, and the photocatalytic efficiency is improved; oleic acid modified TiO2Belongs to anatase type, has higher crystallinity and good photocatalytic performance, and can be used as Au nano-particles and TiO2The interface contact between the noble metal and the semiconductor can be realized after the combination and the high-temperature calcination treatment, and further the function synergy of the noble metal and the semiconductor is realized: the Au nanoparticles can be made into TiO2Organic dye is degraded in a visible light area, and the method is helpful for the effective separation of photo-generated electrons and holes, thereby greatly improving TiO2The photoresponse range and the catalytic efficiency of (2); through mixing tree-shaped mesoporous SiO2With TiO2/Au photocatalyst composition and coating mesoporous SiO2The arborescent mesoporous SiO can be prepared by the processes of shell layer, calcination treatment and the like2/TiO2/Au/SiO2The multi-layer double-pore structure of the composite photocatalyst has good permeability from inside to outside, and ensures the efficient contact between catalytic sites and a reaction medium; meanwhile, the degradation of organic dye under visible light and the improvement of TiO can be realized2Photocatalytic efficiency; and the catalyst is easy to centrifugally separate, so that the repeated utilization rate of the photocatalyst can be obviously improved.
Compared with the prior art, the invention has the beneficial effects that:
the composite type photocatalysis prepared by the inventionThe agent has the advantages of complete degradation under visible light, high photocatalytic efficiency and the like, and overcomes the defects of the conventional TiO2The catalyst can only degrade the organic dye molecules in the ultraviolet light wave band, thereby effectively relaxing the defects of TiO2The photocatalyst is used under the condition that the metal-semiconductor synergistic effect is utilized to inhibit the photo-generated electron-hole recombination so as to improve the catalytic efficiency. The catalyst can degrade rhodamine B solution to 10.7% in 90min under the degradation of visible light, and the pure rhodamine B is degraded to 94.8% in 90min under the irradiation of visible light, which indicates that the catalyst has better catalytic effect.
The composite photocatalyst prepared by the invention has a multi-level double-pore structure, greatly improves the openness of catalytic sites while improving the loading capacity of functional elements, and is beneficial to the interaction between the photocatalyst and substrate molecules so as to improve the photocatalytic efficiency.
The composite photocatalyst prepared by the invention has a multi-level double-hole structure, improves the stability of the catalyst, is easy to centrifugally separate, can be repeatedly and efficiently used, and avoids the waste of products.
(IV) description of the drawings
FIG. 1 shows a dendriform mesoporous SiO2/TiO2/Au/SiO2XRD patterns in the catalyst synthesis process, wherein a, b and c are respectively TiO2Nanoparticles, aqueous phase SiO2/TiO2Arborescent mesoporous SiO2/TiO2/Au/SiO2A composite photocatalyst is provided.
FIG. 2 shows a dendriform mesoporous SiO2/TiO2/Au/SiO2TEM image of catalyst synthesis process, wherein a, b, c, d, e and f are TiO respectively2Nanoparticle and sulfhydrylation dendriform mesoporous SiO2Oil phase dendriform mesoporous SiO2/TiO2Aqueous phase of SiO2/TiO2Arborescent mesoporous SiO2/TiO2Au, arborescent mesoporous SiO2/TiO2/Au/SiO2A composite photocatalyst is provided.
FIG. 3 shows a dendriform mesoporous SiO2/TiO2/Au/SiO2The catalyst degrades a degradation map of rhodamine B under visible light.
FIG. 4 shows a dendriform mesoporous SiO2/TiO2/Au/SiO2The catalyst can degrade the recycling performance of rhodamine B under visible light.
(V) detailed description of the preferred embodiments
The invention will be further described with reference to specific examples, but the scope of the invention is not limited thereto:
the room temperature in the embodiment of the invention is 25-30 ℃, and the ultrapure water is water with the resistivity of 18M omega cm (25 ℃).
Example 1:
(1) oleic acid modified TiO2Preparation of nanoparticles
Adding 4.53ml oleylamine, 8.75ml oleic acid, 3.43ml absolute ethyl alcohol and 1.021ml tetrabutyl titanate into a 50ml beaker, stirring for 10min, transferring to a 50ml stainless steel reaction kettle with a tetrafluoroethylene lining containing 11.77ml ethanol water solution (volume concentration is 96%), reacting for 14h at 180 ℃, and washing 3 times by using absolute ethyl alcohol after the reaction is finished to obtain the TiO modified by the oleic acid20.273g of nanoparticles having an average particle diameter of 7.52nm as shown by XRD (curve a in FIG. 1) and transmission electron microscopy (curve a in FIG. 2) were dispersed in 30ml of toluene.
(2) Sulfhydrylation arborescence mesoporous SiO2Preparation of
Dissolving 0.068g of TEA in 25ml of water, magnetically stirring for 30min in an oil bath at 80 ℃, adding 0.38g of CTAB and 0.218g of NaSal, stirring for 1h, adding 4ml of TEOS, reacting for 3h, washing a product for 3 times by using absolute ethyl alcohol after the reaction is finished, dissolving the product in 100ml of a mixed solution (volume ratio is 1:1) of hydrochloric acid and methanol, stirring and extracting for 6h in a water bath at 60 ℃, repeatedly adding hydrochloric acid and methanol, stirring for one time, washing the product for 3 times by using absolute ethyl alcohol, re-dispersing the product in 200ml of absolute ethyl alcohol, adding 2.5ml of ammonia water (25-28%) and 1ml of MPS, stirring for 12h at room temperature, washing the product for 3 times by using absolute ethyl alcohol, and obtaining 0.384g of thiolated dendrimer mesoporous SiO2The diameter is 200 nm-400 nm, the pore diameter is 30 nm-50 nm, and the transmission electron micrograph is shown as b in figure 2, and the material is dispersed in 30mL of absolute ethyl alcohol.
(3) Oil phase tree-shaped mesoporous SiO2/TiO2Of assembliesSynthesis and phase transfer process
10ml of sulfhydrylation dendriform mesoporous SiO in the step (2)2Centrifuging the ethanol solution to obtain a precipitate, and then adding 21.1ml of oleic acid-modified TiO in the step (2)2In toluene to make TiO2With SiO2The mass ratio is 1.5:1, assembling for 10min under 40KHz ultrasonic condition, centrifuging for 10min at 10000r/min, dissolving the precipitate in 100ml chloroform to obtain solution 1, and the transmission electron microscope picture is shown as c in FIG. 2; dissolving 2g of reduced glutathione in 100ml of BR buffer solution with the pH value of 9, and adjusting the pH value to 9 by using NaOH solution, and marking as solution 2; then adding the solution 2 into the solution 1 in an adherence manner (the volume ratio of the solution 1 to the solution 2 is 1:1) to form an oil-water two-phase system, heating and stirring the system in a water bath at the temperature of 60 ℃ for 8 to 9 hours to realize SiO2/TiO2Phase transfer of the assembly, taking out the upper solution, centrifuging, washing with anhydrous ethanol for 3 times to obtain water phase dendriform mesoporous SiO2/TiO20.232g of the assembly, XRD pattern shown by curve b in FIG. 1, and transmission electron microscopy pattern shown by d in FIG. 2, was dispersed in 30ml of ultrapure water.
(4) Preparation of multi-layer double-hole composite photocatalyst
Under ice-bath conditions, 0.39ml of 20g/L HAuCl4Aqueous solution, 0.585ml of 0.2M K2CO3Adding the aqueous solution into 7.8ml of ultrapure water in sequence, stirring for 10min, and then adding 19.5mg of the water phase dendriform mesoporous SiO in the step (3)2/TiO2The assembly was stirred for 10min, then 78. mu.L of 0.5g/L NaBH was added4Reacting the aqueous solution for 1min, centrifuging, dispersing the precipitate in water, and washing once, wherein the transmission electron microscope picture is shown as e in figure 2; centrifuging (10000r/min, 10min), dispersing into 40ml of 5mMCTAB aqueous solution, adding 0.4ml of 0.1M NaOH aqueous solution, adding TEOS solution with the mass concentration of more than or equal to 99% in three times, adding 27 mu L of TEOS solution each time at the time interval of 0.5h, stirring at room temperature for 24h, washing with ultrapure water for 3 times, placing the obtained precipitate in a vacuum tube furnace, calcining at 500 ℃ for 3h in the air atmosphere, and obtaining the final product, namely the multi-layer double-hole composite photocatalyst, namely the tree-shaped mesoporous SiO2/TiO2/Au/SiO20.0283g of composite photocatalyst, the XRD pattern is shown as a curve c in figure 1, and the transmission electron microscope pattern is shown asShown as f in figure 2.
Example 2:
(1) oleic acid modified TiO2Preparation of nanoparticles
Adding 4.53ml oleylamine, 8.75ml oleic acid, 3.43ml absolute ethyl alcohol and 1.021ml tetrabutyl titanate into a 50ml beaker, stirring for 10min, transferring to a 50ml stainless steel reaction kettle with a tetrafluoroethylene lining containing 11.77ml ethanol water solution (volume concentration is 96%), reacting for 18h at 180 ℃, and washing for 3 times by using absolute ethyl alcohol after the reaction is finished to obtain the TiO modified by the oleic acid20.316g of nanoparticles, with an average particle size of 11.3nm, were dispersed in 30ml of toluene.
(2) Sulfhydrylation arborescence mesoporous SiO2Preparation of
Dissolving 0.068g of TEA in 25ml of water, magnetically stirring for 30min in an oil bath at 80 ℃, adding 0.38g of CTAB and 0.168g of NaSal, stirring for 1h, adding 4ml of TEOS, reacting for 4h, washing a product for 3 times by using absolute ethyl alcohol after the reaction is finished, dissolving the product in 100ml of a mixed solution (volume ratio is 1:1) of hydrochloric acid and methanol, stirring and extracting for 6h in a water bath at 60 ℃, repeatedly adding hydrochloric acid and methanol, stirring for one time, washing the product for 3 times by using absolute ethyl alcohol, re-dispersing the product in 200ml of absolute ethyl alcohol, adding 2.5ml of ammonia water (25-28%) and 1ml of MPS, stirring for 12h at room temperature, washing the product for 3 times by using absolute ethyl alcohol, and obtaining 0.413g of thiolated dendrimer mesoporous SiO2The diameter is 200 nm-350 nm, the pore diameter is 20 nm-30 nm, and the nano-particles are dispersed in 30mL of absolute ethyl alcohol.
(3) Oil phase tree-shaped mesoporous SiO2/TiO2Synthesis of assemblies and phase transfer process
10ml of sulfhydrylation dendriform mesoporous SiO in the step (2)2Centrifuging the ethanol solution to obtain a precipitate, and then adding 19.6ml of oleic acid-modified TiO in the step (2)2In toluene to make TiO2With SiO2The mass ratio is 1.5:1, assembling for 10min under 40KHz ultrasonic condition, centrifuging for 10min at 10000r/min, dissolving the precipitate in 100ml chloroform to obtain solution 1; dissolving 2g of reduced glutathione in 100ml of BR buffer solution with the pH value of 9, and adjusting the pH value to 9 by using NaOH solution, and marking as solution 2; solution 2 was then added adherently to solution 1 (volume ratio of solution 1 to solution 2 1:1) forming an oil-water two-phase system, heating and stirring for 8-9 h in a water bath at 60 ℃ to realize SiO2/TiO2Phase transfer of the assembly, taking out the upper solution, centrifuging, washing with anhydrous ethanol for 3 times to obtain water phase dendriform mesoporous SiO2/TiO20.265g of the assembly was dispersed in 30ml of ultrapure water.
(4) Preparation of multi-layer double-hole composite photocatalyst
Under ice-bath conditions, 0.78ml of HAuCl4(20g/l) aqueous solution, 1.17ml K2CO3Adding (0.2M) water solution into 7.8ml of ultrapure water in sequence, stirring for 10min, and adding 19.5mg of oil phase tree-shaped mesoporous SiO in step (3)2/TiO2The assembly was stirred for 10min, then 156. mu.L of NaBH was added4(0.5g/L) water solution, reacting for 1min, centrifuging, and dispersing the precipitate in water to wash once; centrifuging (10000r/min, 10min), dispersing into 40ml CTAB (5mM) water solution, adding 0.4ml NaOH (0.1M) water solution, adding TEOS solution (the mass concentration is more than or equal to 99%) three times, adding 27 mu L each time, the time interval is 0.5h, then stirring for 24h at room temperature, washing for 3 times with ultrapure water, placing the obtained precipitate into a vacuum tube furnace, calcining for 3h at 500 ℃ in air atmosphere, and obtaining the final product of tree-shaped mesoporous SiO2/TiO2/Au/SiO20.0291g of composite photocatalyst.
Example 3:
(1) oleic acid modified TiO2Preparation of nanoparticles
Adding 4.53ml oleylamine, 10.5ml oleic acid, 3.43ml absolute ethyl alcohol and 1.021ml tetrabutyl titanate into a 50ml beaker, stirring for 10min, transferring to a 50ml stainless steel reaction kettle with a tetrafluoroethylene lining containing 11.77ml ethanol water solution (volume concentration is 96%), reacting for 14h at 180 ℃, and washing 3 times by using absolute ethyl alcohol after the reaction is finished to obtain the TiO modified by the oleic acid20.398g of nanoparticles, having an average particle diameter of 10.3nm, were dispersed in 30ml of toluene.
(2) Sulfhydrylation arborescence mesoporous SiO2Preparation of
Dissolving 0.068g TEA in 25ml water, magnetically stirring in an oil bath at 80 deg.C for 30min, and adding 0.38g CStirring TAB and 0.168g NaSal for 1h, adding 4ml TEOS, reacting for 3h, after the reaction is finished, washing the product with absolute ethyl alcohol for 3 times, dissolving in 100ml mixed solution of hydrochloric acid and methanol (volume ratio 1:1), stirring and extracting for 6h in 60 ℃ water bath, repeatedly adding hydrochloric acid and methanol for one time, washing the product with absolute ethyl alcohol for 3 times, re-dispersing in 200ml absolute ethyl alcohol, adding 2.5ml ammonia water (25-28%) and 1ml MPS, stirring for 12h at room temperature, washing the product with absolute ethyl alcohol for 3 times, and obtaining 0.339g of thiolated arborescent mesoporous SiO2The diameter is 300 nm-400 nm, the pore diameter is 25 nm-35 nm, and the nano-particles are dispersed in 30mL of absolute ethyl alcohol.
(3) Oil phase tree-shaped mesoporous SiO2/TiO2Synthesis of assemblies and phase transfer process
10ml of sulfhydrylation dendriform mesoporous SiO in the step (2)2Centrifuging the ethanol solution to obtain a precipitate, and then adding 12.78ml of oleic acid-modified TiO in the step (2)2In toluene to make TiO2With SiO2The mass ratio is 1.5:1, assembling for 10min under 40KHz ultrasonic condition, centrifuging for 10min at 10000r/min, dissolving the precipitate in 100ml chloroform to obtain solution 1; dissolving 2g of reduced glutathione in 100ml of BR buffer solution with the pH value of 9, adjusting the pH value to 9 by using NaOH solution, and marking as solution 2; then adding the solution 2 into the solution 1 in an adherence manner (the volume ratio of the solution 1 to the solution 2 is 1:1) to form an oil-water two-phase system, heating and stirring the system in a water bath at the temperature of 60 ℃ for 8 to 9 hours to realize SiO2/TiO2Phase transfer of the assembly, taking out the upper solution, centrifuging, washing with anhydrous ethanol for 3 times to obtain water phase dendriform mesoporous SiO2/TiO20.2473g of the assembly was dispersed in 30ml of ultrapure water.
(4) Preparation of multi-layer double-hole composite photocatalyst
Under ice-bath conditions, 0.39ml of 20g/L HAuCl4Aqueous solution, 0.585ml of 0.2M K2CO3Adding the aqueous solution into 7.8ml of ultrapure water in sequence, stirring for 10min, and then adding 19.5mg of the water phase dendriform mesoporous SiO in the step (3)2/TiO2The assembly was stirred for 10min, then 78. mu.L of 0.5g/L NaBH was added4Reacting in water solution for 1min, centrifuging, dispersing the precipitate in water, washing once, and taking transmission electron microscope pictureAs shown in fig. 2 e; centrifuging (10000r/min, 10min), dispersing into 40ml of 5mMCTAB aqueous solution, adding 0.4ml of 0.1M NaOH aqueous solution, adding TEOS solution with the mass concentration of more than or equal to 99% in three times, adding 27 mu L of TEOS solution each time at the time interval of 0.5h, stirring at room temperature for 24h, washing with ultrapure water for 3 times, placing the obtained precipitate in a vacuum tube furnace, calcining at 500 ℃ for 3h in air atmosphere, and obtaining the final product of the tree-shaped mesoporous SiO2/TiO2/Au/SiO20.0294g of composite photocatalyst.
Example 4:
(1) oleic acid modified TiO2Preparation of nanoparticles
Adding 4.53ml oleylamine, 8.75ml oleic acid, 3.43ml absolute ethyl alcohol and 1.4ml tetrabutyl titanate into a 50ml beaker, stirring for 10min, transferring to a 50ml stainless steel reaction kettle with a tetrafluoroethylene lining containing 11.77ml ethanol water solution (volume concentration is 96%), reacting for 14h at 140 ℃, and washing 3 times with absolute ethyl alcohol after the reaction is finished to obtain the oleic acid modified TiO2The nanoparticles were 0.359g and had an average particle size of 9.23nm and then dispersed in 30ml of toluene.
(2) Sulfhydrylation arborescence mesoporous SiO2Preparation of
Dissolving 0.068g of TEA in 25ml of water, magnetically stirring for 30min in an oil bath at 80 ℃, adding 0.38g of CTAB and 0.218g of NaSal, stirring for 1h, adding 4ml of TEOS, reacting for 4h, washing a product for 3 times by using absolute ethyl alcohol after the reaction is finished, dissolving the product in 100ml of a mixed solution (volume ratio is 1:1) of hydrochloric acid and methanol, stirring and extracting for 6h in a water bath at 60 ℃, repeatedly adding hydrochloric acid and methanol, stirring for one time, washing the product for 3 times by using absolute ethyl alcohol, re-dispersing the product in 200ml of absolute ethyl alcohol, adding 2.5ml of ammonia water (25-28%) and 1ml of MPS, stirring for 12h at room temperature, washing the product for 3 times by using absolute ethyl alcohol, and obtaining 0.315g of thiol-based dendriform mesoporous SiO2The diameter is 200 nm-400 nm, the pore diameter is 20 nm-30 nm, and the nano-particles are dispersed in 30mL of absolute ethyl alcohol.
(3) Oil phase tree-shaped mesoporous SiO2/TiO2Synthesis of assemblies and phase transfer process
10ml of sulfhydrylation dendriform mesoporous SiO in the step (2)2Ethanol solution separationThe core was precipitated and then 13.16ml of oleic acid-modified TiO was added in step (2)2In toluene to make TiO2With SiO2The mass ratio is 1.5:1, assembling for 10min under 40KHz ultrasonic condition, centrifuging for 10min at 10000r/min, dissolving the precipitate in 100ml chloroform to obtain solution 1; dissolving 2g of reduced glutathione in 100ml of BR buffer solution with the pH value of 9, adjusting the pH value to 9 by using NaOH solution, and marking as solution 2; then adding the solution 2 into the solution 1 in an adherence manner (the volume ratio of the solution 1 to the solution 2 is 1:1) to form an oil-water two-phase system, heating and stirring the system in a water bath at the temperature of 60 ℃ for 8 to 9 hours to realize SiO2/TiO2And (3) phase transfer of the assembly, taking out the upper layer solution, centrifuging, washing with absolute ethyl alcohol for 3 times to obtain 0.219g of the aqueous phase dendritic mesoporous SiO2/TiO2 assembly, and dispersing in 30ml of ultrapure water.
(4) Preparation of multi-layer double-hole composite photocatalyst
Under ice-bath conditions, 0.39ml of 20g/L HAuCl4Aqueous solution, 0.585ml of 0.2M K2CO3Adding the aqueous solution into 7.8ml of ultrapure water in sequence, stirring for 10min, and then adding 19.5mg of the water phase dendriform mesoporous SiO in the step (3)2/TiO2The assembly was stirred for 10min, then 78. mu.L of 0.5g/L NaBH was added4Reacting the aqueous solution for 1min, centrifuging, and dispersing the precipitate in water for washing once; centrifuging (10000r/min, 10min), dispersing into 40ml of 5mM CTAB aqueous solution, adding 0.4ml of 0.1M NaOH aqueous solution, adding TEOS solution with the mass concentration of more than or equal to 99% in three times, adding 27 mu L of TEOS solution each time at the time interval of 0.5h, stirring at room temperature for 24h, washing with ultrapure water for 3 times, placing the obtained precipitate in a vacuum tube furnace, calcining at 500 ℃ for 3h in the air atmosphere to obtain the final product, namely the tree-shaped mesoporous SiO2/TiO2/Au/SiO20.0261g of composite photocatalyst.
Example 5: characteristics of photodegradation
A300W xenon lamp plus a filter (lambda is more than 420nm) is used for simulating visible light to catalyze and degrade rhodamine B: first, 6mg of catalyst (the arborescent mesoporous SiO prepared in example 1)2/TiO2/Au/SiO2Composite photocatalyst) is added into 15ml of rhodamine B aqueous solution (the concentration is 20mg/ml) and the mixture is put at room temperatureAnd then, stirring for 30min to enable the catalyst and rhodamine B to reach adsorption-desorption balance, then turning on a xenon lamp for photocatalytic degradation, taking 0.75ml of sample every 15min, centrifuging, taking supernatant, measuring the absorbance at 553nm by using a spectrophotometer to obtain a photocatalytic degradation curve, taking the sample without adding the catalyst as a blank control under the same condition, wherein the result is shown in figure 3, and the result in figure 3 shows that the rhodamine B solution is degraded to 10.7% in 90min, and the pure rhodamine B is degraded to 94.8% in 90min under the irradiation of visible light, which indicates that the catalyst has better catalytic effect.
Arborescent mesoporous SiO prepared in examples 2-4 under the same conditions2/TiO2/Au/SiO2The degradation condition of the composite photocatalyst for degrading rhodamine B is similar to that of the catalyst in the example 1.
Example 6 catalyst recycle Properties
The reaction solution in example 5 was centrifuged, and the precipitate was washed with ultrapure water 3 times to recover the catalyst, and the experiment was repeated under the same conditions, and the results are shown in FIG. 4, from which: the catalyst has good catalytic performance, can be repeatedly used for 4 times, the degradation rate of each time reaches about 90%, and the reuse rate of products is improved, so that the waste of the products is avoided.
Claims (10)
1. The multi-level double-hole structure composite photocatalyst is characterized by consisting of dendritic mesoporous SiO2Template, TiO2Au nanoparticles, mesoporous SiO2A shell layer; the mass contents of the components are as follows: SiO2245％～65％，TiO235-40 percent of Au nanoparticles, 1-10 percent of Au nanoparticles and 100 percent of Au nanoparticles.
2. The multi-level double-hole structure composite photocatalyst as claimed in claim 1, wherein the catalyst is prepared by first sulfhydrylation of dendritic mesoporous SiO2Oleate modified TiO2Assembling nanoparticles, replacing oleic acid ligand with reduced glutathione ligand to convert oil phase into water phase, and performing in-situ water phase conversionControllable growth of Au nano-particles and coating of mesoporous SiO2And calcining the shell layer to obtain the multi-level double-pore structure composite photocatalyst.
3. The multi-layer double-pore structured composite photocatalyst as claimed in claim 2, wherein said oleate-modified TiO is selected from the group consisting of2The nanoparticles are prepared by the following method: mixing oleylamine, oleic acid, absolute ethyl alcohol and tetrabutyl titanate, stirring at room temperature for 10min, adding an ethanol aqueous solution with the volume concentration of 96%, reacting at 180 ℃ for 14-18 h, and washing with absolute ethyl alcohol after the reaction is finished to obtain oleate modified TiO2A nanoparticle; the volume ratio of oleylamine to oleic acid, absolute ethyl alcohol and tetrabutyl titanate is 1: 1.5-2.5: 0.5-1: 0.1 to 0.5; the volume ratio of the oleylamine to the 96% ethanol aqueous solution with the volume concentration is 1:2 to 3.
4. The multi-level double-pore structure composite photocatalyst as claimed in claim 2, wherein the thiolated dendritic mesoporous SiO is2The preparation method comprises the following steps: dissolving triethanolamine in ultrapure water, magnetically stirring in an oil bath at 80 ℃ for 30min, adding hexadecyl trimethyl ammonium bromide and sodium salicylate, stirring for 1h, adding tetraethoxysilane, reacting for 3h, and washing a product with absolute ethyl alcohol a after the reaction is finished; then dissolving the mixture into a mixed solution of hydrochloric acid and methanol with the volume ratio of 1:1, stirring the mixture in a water bath at the temperature of 60 ℃ for 6 hours, and repeatedly adding hydrochloric acid and methanol and stirring the mixture once; washing the product with absolute ethyl alcohol b, re-dispersing in absolute ethyl alcohol c, adding ammonia water and (3-mercaptopropyl) trimethoxysilane, stirring at room temperature for 12h, and washing the product with absolute ethyl alcohol d to obtain the thiolated arborescent mesoporous SiO2。
5. The multi-level double-hole structure composite photocatalyst as claimed in claim 4, wherein the volume usage amount of the ultrapure water is 300-500 ml/g based on the weight of triethanolamine, the weight ratio of the cetyl trimethyl ammonium bromide to the triethanolamine is 5-7: 1, and the weight ratio of the triethanolamine to the sodium salicylate is 1: 2-4; the volume usage of the ethyl orthosilicate is 50-70 ml/g based on the weight of triethanolamine; the volume consumption of the mixed solution of the hydrochloric acid and the methanol is 1-2L/g calculated by the weight of the triethanolamine; the volume dosage of the absolute ethyl alcohol c is 1-5L/g calculated by the weight of triethanolamine; the volume dosage of the ammonia water is 30-40 ml/g based on the weight of triethanolamine; the volume usage of the (3-mercaptopropyl) trimethoxysilane is 10-20 ml/g based on the weight of triethanolamine.
6. The multi-level double-hole structure composite photocatalyst as claimed in claim 2, which is prepared by the following steps:
(1) oil phase tree-shaped mesoporous SiO2/TiO2Synthesis of assembly and phase transfer process: sulfhydrylation dendriform mesoporous SiO2Centrifuging the ethanol solution to obtain a precipitate, and then adding the oleic acid modified TiO2Adding the toluene solution, assembling for 10min under the ultrasonic condition, centrifuging, and dissolving the precipitate in chloroform to obtain a solution 1; reduced glutathione was dissolved in BR buffer at pH 9 and adjusted to pH 9 with 0.8M NaOH aqueous solution, denoted as solution 2; then adding the solution 2 into the solution 1 in an adherent manner to form an oil-water two-phase system, heating and stirring for 8-9 h in a water bath at 60 ℃ to realize SiO2/TiO2Phase transfer of the assembly, taking out the upper solution, centrifuging, washing the precipitate with absolute ethanol to obtain water-phase dendritic mesoporous SiO2/TiO2Assembling the body;
(2) au nanoparticle growth, SiO2Coating and calcining processes: under the condition of ice bath, 20g/L of HAuCl4Aqueous solution, 0.2M K2CO3Sequentially adding the aqueous solution into water, stirring for 10min, and adding the aqueous phase dendriform mesoporous SiO2/TiO2Stirring the assembly for 10min, adding 0.5g/L sodium borohydride aqueous solution, reacting for 1min, centrifuging, dispersing the precipitate in water, and washing once; centrifuging, dispersing the precipitate into a 5mM CTAB aqueous solution, adding a 0.1M NaOH aqueous solution, adding a TEOS solution for three times, stirring at room temperature for 24h, washing with ultrapure water, and calcining the obtained precipitate at 500 ℃ for 3h in an air atmosphere to obtain the multi-level double-hole structure composite photocatalyst.
7. The multi-layer double-pore structure composite photocatalyst as claimed in claim 6, wherein the thiolated dendritic mesoporous SiO in step (1) is2TiO modified with oleic acid2The mass ratio is 1.5:1, SiO in solution 12With TiO2The total mass concentration is 1-5mg/ml, and the volume consumption of the BR buffer solution is 25-75 ml/g based on the weight of reduced glutathione; the volume ratio of the solution 1 to the solution 2 is 1: 1.
8. the multi-layer double-pore structure composite photocatalyst as claimed in claim 6, wherein the water and HAuCl in the step (2)4Aqueous solution, K2CO3The volume dosage of the aqueous solution is dendritic mesoporous SiO2/TiO2The quality of the assembly body is respectively 0.4ml/mg, 0.02-0.04ml/mg and 0.03-0.6 ml/mg; the volume consumption of the sodium borohydride aqueous solution, the CTAB aqueous solution, the NaOH aqueous solution and the TEOS solution is determined by the water-phase tree-shaped mesoporous SiO2/TiO2The assembly body weight is 4-16ml/g, 1500-2500 ml/g, 15-25 ml/g and 3-5 ml/g.
9. The application of the arborescent mesoporous multi-level double-pore structure composite photocatalyst disclosed by claim 1 in degradation of organic dyes.
10. The use according to claim 9, characterized in that the use is: firstly, tree-shaped mesoporous SiO2/TiO2/Au/SiO2Adding the composite photocatalyst into 10-30 mg/ml organic dye aqueous solution, stirring for 30min at room temperature to enable the catalyst and the organic dye to reach adsorption-desorption balance, then turning on a xenon lamp, and carrying out photocatalytic degradation under the condition of 300W; the organic dye is rhodamine B; the volume dosage of the organic dye aqueous solution is 1-3 ml/g based on the mass of the catalyst.
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