CN108889329B - Carbon nitride quantum dot modified hierarchical pore TiO2-SiO2Photocatalyst and process for producing the same - Google Patents
Carbon nitride quantum dot modified hierarchical pore TiO2-SiO2Photocatalyst and process for producing the same Download PDFInfo
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- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 62
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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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Abstract
The invention relates to carbon nitride quantum dot modified hierarchical porous TiO2‑SiO2A photocatalyst and a preparation method thereof. The invention is mainly characterized in that ordered hierarchical porous TiO is synthesized by an in-situ loading method2‑SiO2In the process of the material, carbon nitride quantum dots are introduced, and the template agent is removed by a calcination method to obtain the carbon nitride quantum dot modified hierarchical pore structure TiO2‑SiO2A photocatalyst. Compared with the prior art, the method adopted by the invention is simple and easy to operate, can efficiently utilize the raw materials, can load the carbon nitride quantum dots on the pore walls of the hierarchical pore titanium oxide silicon oxide, promotes the improvement of the photocatalytic activity, and simultaneously provides a good channel for the diffusion and transmission of guest molecules by virtue of an ordered hierarchical pore structure, so that the prepared photocatalyst has good catalytic degradation activity on organic pollutants such as phenol, sulfadiazine and the like and the actual high-concentration antibiotic wastewater.
Description
Technical Field
The invention relates to the field of nano photocatalytic materials, and provides a novel photocatalyst and a preparation method thereof, wherein carbon nitride quantum dots are loaded in the wall of a hierarchical pore structure silicon oxide pore in an in-situ loading mode.
Background
The mesoporous silica is a novel nano material developed in recent years, and has the specific surface area as high as 1000m2/g, continuously adjustable pore diameter, highly long-range ordered pore channels, high thermal stability and the like. The excellent structural properties enable the compounds to have great application values in the aspects of catalysis, drug loading, waste gas adsorption, separation and purification, solar photoelectric conversion and the like, and once reported, the compounds are widely concerned in various related fields. Especially, in recent years, with the continuous innovation of synthesis technology, various structures such as KIT, MSU and SBA mesoporous silica are continuously reported, the research of mesoporous materials presents a vigorous development scene, and the research on the aspects of synthesis methods, synthesis mechanisms, applications and the like of the mesoporous materials has achieved great results.
Photonic Crystals (PCs) with ordered macroporous structures have become a hotspot in recent years. The self-assembly of periodic "opal" templates can guide the infiltration and deposition of precursor materials to produce "inverse opal" (IOs) photonic crystal structures. The slow light effect and the multiple light scattering effect of the inverse opal photonic crystal can prolong the light path and increase the light absorption, thereby improving the photocatalytic activity of the material. The silicon oxide material with multilevel pores is prepared by combining the photonic crystal structure and the mesoporous structure, and has the advantages of high specific surface area, high thermal stability and the structure of the photonic crystal material. However, since silica itself has no catalytic activity, the application of the multi-pore silica material in photocatalytic degradation of pollutants is limited. Titanium oxide is introduced into the hierarchical porous silicon oxide material to obtain the hierarchical porous TiO2-SiO2 photonic crystal photocatalyst, and the material has both the structural advantages of hierarchical pores and photocatalytic activity, and can effectively degrade pollutants. However, titanium oxide has a forbidden band width of 3.2eV, and is insufficient in visible light activity in response to absorption of ultraviolet light.
The graphite-phase carbon nitride (g-C3N4) has the forbidden band width of 2.7eV, is an excellent nonmetal semiconductor with chemical stability, and is widely applied to degradation of organic pollutants. In recent years, graphite phase Carbon Nitride Quantum Dots (CNQDs) have received much attention for strong blue light emission and up-conversion behavior. And a Z framework is formed by combining CNQDs and TiO2 in the titanium oxide silicon oxide with the hierarchical pore structure, so that the specific surface area of the material, the utilization rate of visible light and the charge transfer efficiency are improved, and the photocatalyst is favorable for effectively degrading organic pollutants.
Reports of designing photocatalysts based on carbon nitride quantum dots are few, and reports of preparing efficient photocatalysts by combining the carbon nitride quantum dots with hierarchical porous materials are basically absent. Based on the background, the invention makes the carbon nitride quantum dots loaded in the pore walls of the hierarchical pore titanium oxide silicon oxide, promotes the improvement of the photocatalytic activity, and simultaneously the ordered hierarchical pore structure also provides a good channel for the diffusion and transmission of guest molecules, so that the prepared photocatalyst has good catalytic degradation activity on organic pollutants such as phenol, sulfadiazine and the like and actual antibiotic wastewater.
Disclosure of Invention
The invention adopts an in-situ loading method to prepare the carbon nitride quantum dot modified hierarchical porous TiO2-SiO2 photocatalyst by a one-step method. In the process of preparing the composite photocatalyst, acetylacetone is added as a titanium source hydrolysis inhibitor to relieve the over-fast hydrolysis of a titanium source, and simultaneously, a silicon source (tetrabutyl silicate), prepared carbon nitride quantum dots and a titanium source (isopropyl titanate) are added and poured into a polystyrene microsphere template, and the three are synchronously hydrolyzed on micelles formed by a nonionic surfactant in an acid system to synthesize the catalyst simply and conveniently. And removing the template by high-temperature calcination to obtain the carbon nitride quantum dot modified hierarchical pore structure TiO2-SiO2 photocatalyst, which has a good photocatalytic degradation effect on organic pollutants such as sulfadiazine and phenol and actual antibiotic wastewater.
The invention prepares the photocatalyst, and the adopted process steps are as follows:
preparing a carbon nitride quantum dot solution by using sodium citrate and urea as raw materials through a solid-phase hydrothermal method; dissolving a pore-forming agent in an ethanol solution, stirring vigorously for a certain time, then reducing the stirring speed, adding tetrabutyl silicate, hydrochloric acid, acetylacetone, isopropyl titanate and a carbon nitride quantum dot solution to obtain a mixed solution, stirring, pouring into a polystyrene template, hydrolyzing and drying at a certain temperature and humidity for a certain time, and then calcining at a certain temperature in the air for a certain time to remove the template, thereby obtaining the carbon nitride quantum dot modified hierarchical pore structure TiO2-SiO2 photonic crystal photocatalyst.
The reaction system is an acidic solution, promotes the hydrolysis of ethyl orthosilicate, controls the hydrolysis speed of isopropyl titanate at the same time, and avoids titanium from being monodisperse in the mesoporous framework due to the excessively fast hydrolysis of isopropyl titanate;
the concentration of the hydrochloric acid solution is 2-6 mol/L; the pore-forming agent comprises F127, P123 and the like; the stirring time is 0.5-2 h; the hydrolysis temperature is 30-60 ℃, and the humidity is 40-60%; the calcination temperature is 400-600 ℃; the calcination time is 2h-6 h.
The advantages of the invention are as follows:
1) according to the method, the multi-level pore structure with ordered mesoporous pore channels and an inverse opal structure is obtained through the combined action of a pore-forming agent and a template agent which are subjected to hydrolysis drying at a certain temperature and humidity, so that titanium oxide and carbon nitride quantum dots obtained through dialysis are compounded in the framework of the multi-level pore, and the titanium oxide, the carbon nitride quantum dots and the hierarchical pore structure generate a synergistic effect to improve the photocatalytic activity;
2) the carbon nitride quantum dots and the titanium are synchronously introduced, so that the carbon nitride quantum dots and the titanium can interact and are co-doped in the pore walls of the hierarchical pore silicon oxide, and ordered and smooth pore channels and higher specific surface area are ensured;
3) the ordered mesoporous pore canal and the inverse opal structure provide good channels for the diffusion and transmission of guest molecules, and are favorable for improving the photocatalytic activity;
4) the prepared carbon nitride quantum dot modified hierarchical pore structure TiO2-SiO2 photocatalyst has good catalytic degradation activity on organic pollutants such as sulfadiazine, phenol and the like and high-concentration actual antibiotic wastewater;
5) the carbon nitride quantum dots and the hierarchical pore structure generate a synergistic effect to promote the improvement of the photocatalytic activity;
6) compared with the traditional modification methods such as doping, compounding and the like, the in-situ synthesis method has the advantages of simple equipment, convenient operation, high-efficiency utilization of raw materials, great reduction of production cost and contribution to industrial popularization.
Drawings
FIG. 1 SEM photographs of (a) Me-TSCN-IO, (b) Me-TS-IO, (c) Me-TSCN, (d) Me-TS, (e) TSCN-IO, (f) TS-IO, (g) bulk-TSCN, and (h) bulk-TS.
TEM photographs of (a) Me-TSCN-IO, (b) Me-TS-IO, (c) Me-TSCN, (d) Me-TS, (e) TSCN-IO, (f) TS-IO, (g) bulk-TSCN, (h) bulk-TS are shown in FIG. 2.
FIG. 3 HRTEM photograph of Me-TSCN-IO.
FIG. 4 shows an XRD spectrum of a carbon nitride quantum dot modified hierarchical pore structure TiO2-SiO2 photonic crystal photocatalyst (Me-TSCN-IO).
FIG. 5 shows the pore size distribution curve of (a) nitrogen adsorption/desorption isotherms and (b) of samples.
Fig. 6 impedance plot of sample.
FIG. 7 shows the degradation activity of Me-TSCN-IO on 10mg/L (a) phenol (b) sulfadiazine under a 300W xenon lamp with an AM1.5 filter.
FIG. 8 is a graph of the degradation activity of Me-TSCN-IO on actual antibiotic wastewater.
FIG. 9 is a graph of the cycling stability of sample Me-TSCN-IO versus photocatalytic degradation of (a) phenol (b) sulfadiazine.
Detailed Description
The present invention will be described in more detail below with reference to specific examples, but the scope of the present invention is not limited to these examples.
Preparation of Carbon Nitride Quantum Dots (CNQDs):
and (3) taking urea and sodium citrate as precursors, and preparing the water-phase carbon nitride quantum dot by a low-temperature solid hydrothermal method after dialysis treatment. Specifically, 0.081g of sodium citrate and 0.101g of urea are ground and uniformly mixed, and then transferred into the inner liner of a polytetrafluoroethylene reaction kettle. The stainless steel jacket is tightly screwed and sealed, and is kept for 2 hours at 180 ℃ in an electric heating constant-temperature air blast drying oven. And taking out the high-pressure reaction kettle, naturally cooling at room temperature, ultrasonically washing the obtained brown solid with absolute ethyl alcohol for three times, filling the washed brown solid into an MWCO3500 specification dialysis bag, and dialyzing in 20mL of deionized water at room temperature for 24 hours to obtain the yellowish carbon nitride quantum dot aqueous solution.
Example 1
Synthesizing Me-TSCN-IO, simultaneously adding carbon nitride quantum dots, pore-forming agents such as P123, tetrabutyl silicate and isopropyl titanate in the preparation process, and taking polystyrene as a template, specifically:
after 30mL of EtOH was added to a 50mL beaker, 2g of P123 was added and stirred for 30min to dissolve completely. To the clear solution was added 0.89mL of tetrabutyl silicate (TEOS), 1mL of HCl (4mol/L), 1mL of the inhibitor acetylacetone, 4.8mL of isopropyl titanate (TTIP), and 5mL of an aqueous solution of CNQDs. After stirring for 2h at room temperature, the precursor solution was poured into a 355nm PS template. Hydrolyzing the titanium oxide in a constant temperature and humidity box at 40 ℃ and 55% for 3 days, drying the hydrolyzed titanium oxide in a 70 ℃ drying oven for 3 days, calcining the hydrolyzed titanium oxide in a muffle furnace at 500 ℃ for 4 hours in the air atmosphere (the heating rate is 1 ℃/min), and compounding the titanium oxide and the carbon nitride quantum dots in a framework to obtain the carbon nitride quantum dot modified hierarchical-pore titanium oxide-silicon oxide composite photocatalyst.
Comparative example 1
Synthesizing Me-TS-IO, only adding pore-forming agents such as P123, tetrabutyl silicate and isopropyl titanate in the preparation process, namely, the adding amount of the carbon nitride quantum dots is 0, and taking polystyrene as a template:
after 30mL of EtOH was added to a 50mL beaker, 2g P123 was added and stirred for 30min to dissolve completely. To the clear solution was added 0.89mL of tetrabutyl silicate (TEOS), 1mL of HCl, 1mL of the inhibitor acetylacetone, 4.8mL of isopropyl titanate (TTIP), and 5mL of deionized water. After stirring for 2h at room temperature, the precursor solution was poured into a 355nm PS template. Hydrolyzing the mixture in a constant temperature and humidity box at 40 ℃ and 55% for 3 days, drying the hydrolyzed mixture in a 70 ℃ oven for 3 days, and calcining the dried mixture in a muffle furnace at 500 ℃ for 4 hours in the air atmosphere (the heating rate is 1 ℃/min), thus obtaining the hierarchical pore titanium oxide and silicon oxide composite photocatalyst.
Comparative example 2
Synthesizing Me-TSCN, adding carbon nitride quantum dots, pore-forming agents such as P123, tetrabutyl silicate and isopropyl titanate in the preparation process, and taking polystyrene-free pellets as a template:
after 30mL of EtOH was added to a 50mL beaker, 2g P123 was added and stirred for 30min to dissolve completely. Adding 0.89mL of tetrabutyl silicate (TEOS), 1mL of HCl, 1mL of inhibitor acetylacetone, 4.8mL of isopropyl titanate (TTIP) and 5mL of CNQDs aqueous solution into the transparent solution, stirring for 2h at room temperature, putting into a constant temperature and humidity box, hydrolyzing for 3 days at 40 ℃ and 55% of humidity, drying in a 70 ℃ oven for 3 days, calcining for 4h at 500 ℃ in a muffle furnace under air atmosphere (the temperature rise speed is 1 ℃/min), and thus obtaining the carbon nitride quantum dot modified mesoporous titanium oxide and silicon oxide composite photocatalyst.
Comparative example 3
Synthesizing TSCN-IO, adding carbon nitride quantum dots, tetrabutyl silicate and isopropyl titanate only in the preparation process, namely when the adding amount of a pore-forming agent such as P123 is 0, taking polystyrene spheres as a template to obtain the catalyst:
after 30mL of EtOH was added to a 50mL beaker, the mixture was stirred for 30min until completely dissolved. To the clear solution was added 0.89mL of tetrabutyl silicate (TEOS), 1mL of HCl, 1mL of the inhibitor acetylacetone, 4.8mL of isopropyl titanate (TTIP), and 5mL of an aqueous solution of CNQDs. After stirring for 2h at room temperature, the precursor solution was poured into a 355nm PS template. Hydrolyzing the titanium oxide in a constant temperature and humidity box at 40 ℃ and 55% for 3 days, drying the hydrolyzed titanium oxide in a 70 ℃ drying oven for 3 days, calcining the hydrolyzed titanium oxide in a muffle furnace at 500 ℃ for 4 hours in the air atmosphere (the heating rate is 1 ℃/min), and compounding titanium oxide and carbon nitride quantum dots in a framework to obtain the carbon nitride quantum dot modified titanium oxide and silicon oxide composite photocatalyst with the macroporous structure.
Comparative example 4
Only tetrabutyl silicate and isopropyl titanate are added in the preparation process of synthesizing bulk-TS, namely when the addition amount of pore-forming agents such as P123 and carbon nitride quantum dots is 0, no polystyrene pellet is used as a template to obtain the catalyst:
adding 30mL of absolute ethyl alcohol, 0.89mL of tetrabutyl silicate (TEOS), 1mL of HCl, 1mL of inhibitor acetylacetone, 4.8mL of isopropyl titanate (TTIP) and 5mL of deionized water into a 50mL beaker, stirring for 2h at room temperature, putting into a constant temperature and humidity box, hydrolyzing at 40 ℃ and 55% humidity for 3 days, transferring into a 70 ℃ oven, drying for 3 days, and calcining for 4h at 500 ℃ in a muffle furnace under air atmosphere (the temperature rise speed is 1 ℃/min), thus obtaining the blocky titanium oxide and silicon oxide composite photocatalyst.
Experiment and data
The activity investigation method for photocatalytic degradation of simulated pollutants provided by the invention comprises the following steps:
adding 50mg of composite photocatalyst into a quartz glass tube, measuring 50mL of 10mg/L target organic pollutant solution, adding the solution, pre-adsorbing the organic pollutants by the catalyst for 30min under magnetic stirring to achieve adsorption-desorption balance, and sampling to obtain the initial concentration of photodegradation. Then, carrying out photocatalytic degradation reaction on organic pollutants under a 300W xenon lamp, sampling at regular intervals, placing in a centrifugal tube for centrifugation, taking supernatant, filtering out a catalyst by using a filter head, testing the degradation amount by using a high performance liquid chromatography if the target is simulated organic wastewater such as phenol and sulfadiazine, testing Chemical Oxygen Demand (COD) and Total Organic Carbon (TOC) by using a COD tester and a TOC analyzer if the target is actual wastewater such as antibiotic actual wastewater of pharmaceutical group Limited liability company in North China, and then carrying out drawing analysis.
FIG. 1 is a Scanning Electron Microscope (SEM) photograph of samples obtained in example 1 and comparative examples 1 to 4. From SEM photos, it can be seen that the carbon nitride quantum dot modified hierarchical pore structure TiO2-SiO2 photonic crystal (Me-TSCN-IO), the hierarchical pore structure TiO2-SiO2 photonic crystal (Me-TS-IO), and the carbon nitride quantum dot modified macroporous structure TiO2-SiO2 photonic crystal (TSCN-IO) have obvious inverse opal macroporous structures, and the carbon nitride quantum dot modified mesoporous structure TiO2-SiO2(Me-TSCN) and the common TiO2-SiO2(bulk-TS) do not have regular macroporous structures.
FIG. 2 is a Transmission Electron Microscope (TEM) photograph of the samples obtained in example 1 and comparative examples 1 to 4. According to a TEM picture, Me-TSCN-IO, Me-TS-IO and TSCN-IO have obvious inverse opal macroporous structures, and Me-TSCN and bulk-TS do not have regular macroporous structures.
FIG. 3 is a high transmission electron microscope (HRTEM) photograph of the Me-TSCN-IO sample obtained in example 1. Clear mesoporous structure and inverse opal structure can be seen from HRTEM picture, formation of multi-level pore structure is proved, different lattice stripes can be observed, and successful load of the carbon nitride quantum dot is proved corresponding to (002) crystal face and (100) crystal face of carbon nitride and (101) crystal face of titanium oxide respectively.
FIG. 4 is an XRD spectrum of the samples obtained in example 1 and comparative examples 1 to 4. The peak appearance of titanium oxide was observed in the wide-angle XRD pattern because the amount of carbon nitride was too small to observe the peak appearance of carbon nitride.
Fig. 5 is a graph showing nitrogen adsorption-desorption isotherms and pore size distributions of the samples prepared in example 1 and comparative examples 2 to 3. The hysteresis loop of Me-TSCN-IO with macroporous material TSCN-IO and mesoporous material Me-TSCN can be seen from the nitrogen adsorption desorption isotherm diagram, which indicates that Me-TSCN-IO has a hierarchical pore structure. The introduction of mesopores can be illustrated by a pore size distribution curve chart, so that Me-TSCN-IO has larger pore volume than that of a macroporous material TSCN-IO.
FIG. 6 is a graph showing the impedance of the samples obtained in example 1 and comparative examples 1 to 3. As can be seen from the figure, the carbon nitride quantum dot modified hierarchical pore titanium oxide silicon oxide photonic crystal has the smallest radius of resistance, and the carbon nitride quantum dot loading promotes the separation of photogenerated electrons and holes.
FIG. 7 is a graph showing the degradation activity of the photocatalyst obtained in example 1 and comparative examples 1 to 4 on 10mg/L phenol and sulfadiazine under a 300W xenon lamp with an AM1.5 filter. For the degradation of phenol and sulfadiazine, the catalytic activity of the hierarchical pore TiO2-SiO2 photonic crystal Me-TSCN-IO modified by the carbon nitride quantum dots is more excellent than that of the hierarchical pore TiO2-SiO2 photonic crystal Me-TS-IO modified by the non-carbon nitride quantum dots, and the load of the carbon nitride quantum dots is proved to be beneficial to the improvement of the photocatalytic activity; and the carbon nitride quantum dot modified hierarchical pore TiO2-SiO2 photonic crystal Me-TSCN-IO has better catalyst effect than the carbon nitride quantum dot modified TiO2-SiO2 material Me-TSCN with a pure mesoporous structure, the carbon nitride quantum dot modified TiO2-SiO2 photonic crystal TSCN-IO with a pure macroporous structure and the bulk-TS of a blocky TiO2-SiO2 material, and the hierarchical pore structure is proved to have more advantages than the pure mesoporous and macroporous structures. In summary, the synergistic effect of the carbon nitride quantum dots and the hierarchical pore structure improves the activity of the material in photocatalytic degradation of organic pollutants such as phenol, sulfadiazine and the like.
FIG. 8 is a graph showing the degradation activity of the photocatalyst obtained in example 1 under a 300W xenon lamp with an AM1.5 filter on the actual wastewater containing high-concentration antibiotics from North China pharmaceutical group liability company, Inc. (Hebei, Shijiazhuang). As can be seen from the graph, as the light irradiation progresses, the COD and TOC values of the high-concentration antibiotic actual wastewater gradually decrease, and the COD removal rate reaches 33.24% and the TOC removal rate reaches 27.65% after 14h of light irradiation (raw water COD is 206400mg/L, TOC is 63750 mg/L). The prepared catalyst has good photocatalytic degradation effect on the practical high-concentration antibiotic wastewater.
FIG. 9 is a graph showing the cyclic stability of the photocatalyst obtained in example 1 in the photocatalytic degradation of phenol and sulfadiazine under a 300W xenon lamp with an AM1.5 filter. It can be seen from the figure that five times of cycle experiments show that the photocatalytic degradation effect of the catalyst on phenol and sulfadiazine is not obviously reduced, which indicates that the catalyst has good stability and can be repeatedly used.
While the present invention has been described in detail with reference to the preferred embodiments, it should be understood that the above description should not be taken as limiting the invention.
Claims (6)
1. Preparation of carbon nitride quantum dot modified hierarchical porous structure TiO2-SiO2Photonic crystal lightThe method of the catalyst is characterized in that carbon nitride quantum dots of the catalyst are doped in a framework of the hierarchical pore titanium oxide silicon oxide photonic crystal, and the specific experimental steps are as follows:
1) grinding and uniformly mixing sodium citrate and urea, transferring the mixture into a lining of a polytetrafluoroethylene reaction kettle, keeping the mixture at the temperature of 160-200 ℃, cooling, separating to obtain brown solid, ultrasonically washing the brown solid with absolute ethyl alcohol for three times, filling the brown solid into a dialysis bag, and dialyzing the brown solid in deionized water for a certain time at room temperature to obtain yellowish carbon nitride quantum dot aqueous solution;
2) adding EtOH into a container, then adding P123, stirring until the mixture is completely dissolved to obtain a transparent solution, adding tetrabutyl silicate (TEOS), hydrochloric acid, acetylacetone, isopropyl titanate (TTIP) and a carbon nitride quantum dot aqueous solution into the transparent solution, stirring at room temperature, pouring the precursor solution into a 300-plus-400 nm PS template, hydrolyzing for a predetermined time at a predetermined temperature and humidity, transferring into an oven for drying, and calcining in a muffle furnace under an air atmosphere to compound titanium oxide and carbon nitride quantum dots in a framework, thereby obtaining the carbon nitride quantum dot modified hierarchical-pore titanium oxide-silicon oxide photocatalyst.
2. The method of claim 1, wherein: the concentration of the hydrochloric acid is 2-6 mol/L.
3. The process of claim 1, wherein the stirring time is 0.5 to 2 hours.
4. The process of claim 1, wherein the hydrolysis temperature is 30-60 ℃ and the humidity is 40-60%.
5. The method as claimed in any one of claims 1 to 4, wherein the temperature of the calcination is 400-600 ℃; the calcining time is 2-6 h.
6. Carbon nitride quantum dot modified hierarchical porous structure TiO2-SiO2Photonic crystal photocatalyst, characterized in that carbon nitride of said catalystThe quantum dots are doped in the framework of a hierarchical porous titania silica photonic crystal, and the catalyst is prepared by the method of any one of claims 1-5.
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