CN112191275A - Fiber chelated TiO based on LMCT effect and N doping2Visible light catalyst and preparation method thereof - Google Patents
Fiber chelated TiO based on LMCT effect and N doping2Visible light catalyst and preparation method thereof Download PDFInfo
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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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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- 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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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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Abstract
The invention relates to fiber chelated TiO based on LMCT effect and N doping2The visible light catalyst and the preparation method thereof are characterized in that: modified polyacrylonitrile fiber containing amidoxime chelating group and nano TiO2The TiO containing anatase crystal form and N doping is obtained by coordination combination between crystal sols2A catalyst. The preparation method comprises the following steps: the preparation method of the titanium-containing nano TiO compound takes tetrabutyl titanate as a titanium source and acetic acid and absolute ethyl alcohol as hydrolysis inhibitors2The sol of the crystal is reacted with amidoxime modified polyacrylonitrile fiber to obtain fiber chelated TiO based on LMCT effect and N doping2A visible light photocatalyst. The method has the advantages of simple equipment, simple and convenient process, easy operation and the like, and compared with the prior art, the method has the advantages of simple equipment, simple and convenient process, easy operation and the likeThe catalyst can realize visible light photocatalysis through LMCT and N doping, so that higher photocatalytic activity is shown in the oxidative degradation of organic pollutants.
Description
Technical Field
The invention belongs to the technical field of photocatalysis and wastewater treatment, and particularly relates to fiber chelated TiO based on LMCT effect and N doping in the field of oxidative degradation of organic pollutants such as dye in wastewater2Visible light catalyst and its preparation method.
Background
With the increasing global environmental problems and the increasing environmental standards, the attention on the treatment technology of the refractory organic pollutants is increasing. Among them, the solar-driven photocatalytic technology has the characteristics of low energy consumption, mild reaction conditions, high reaction rate and the like, and can effectively treat hundreds of refractory organic pollutants which should be considered preferentially, so that the technology becomes one of the most promising methods for solving the problem of environmental pollution. Among the numerous photocatalytic materials, titanium dioxide (TiO)2) The material has the advantages of high photocatalytic activity, long service life, good thermal stability, strong corrosion resistance, good photochemical stability, low cost, no toxicity, no harm and the like, and is the most favored material in photocatalytic research. However, TiO is limited by a wider bandgap (3.0-3.2eV)2The reactive agent only shows reactivity under ultraviolet light with the wavelength of 387nm, and the content of the ultraviolet light in sunlight only accounts for 3-5%, which seriously limits the utilization efficiency of the sunlight. Therefore, how to extend TiO2The spectral response range of the photocatalyst enables the photocatalyst to efficiently utilize visible light with the content of about 50% in natural light to treat organic pollutants, which becomes a core problem of the photocatalytic technology.
To mix TiO with2The utilization of (b) is extended to the visible region, and doping of non-metals or transition metals to narrow the band gap is a common strategy. The atomic radius of N is equivalent to that of O, so that the N is doped with TiO2Can effectively reduce the forbidden bandwidth and show certain visible light catalytic activity in environmental application. Researchers have been doping TiO with N2Lots of research is carried out on the aspect, and the batch research results are obtained, but the TiO doped with N is singly used2The two bottleneck problems of narrow absorption band in the visible region and low photocatalytic reaction rate still exist. Conditioning TiO2Another strategy for the photoresponse range is to use ligands on TiO2The surface is coordinately modified and is endowed with visible light catalytic activity through charge transfer (LMCT) of a ligand to a metal center. This LMCT-mediated visible photosensitization can directly excite the ground state electrons of the ligand to TiO2Then activating molecular oxygen in the solutionThe generation of active species and the oxidative degradation of organic contaminants. However, most ligands are accompanied by auto-oxidative degradation and desorption of the ligand during visible LMCT sensitization, resulting in TiO2The ability to absorb visible light is lost, and it is difficult to obtain stable visible light catalytic activity.
Disclosure of Invention
The invention aims to provide fiber chelated TiO based on an LMCT (local mean molecular computed tomography) effect and N doping, which belongs to the technical field of photocatalysis and wastewater treatment and can be used for oxidative degradation of organic pollutants such as dyes and the like in wastewater2The visible light catalyst has the characteristics of simple preparation method, low cost, high photocatalytic efficiency, strong use stability and the like.
The technical scheme adopted by the invention is that amidoxime modified polyacrylonitrile fiber with the weight gain rate of 13-32% is used as a carrier to be mixed with nano TiO2The crystal sol is coordinated and combined to construct a high-efficiency TiO which can be activated by visible light through LMCT and N doping double ways2A photocatalyst. The method comprises the following specific steps:
1) butyl titanate, glacial acetic acid and absolute ethyl alcohol are weighed according to the mol ratio of 1: 2: 5, are uniformly mixed by magnetic stirring, and are dripped into the deionized water solution of the glacial acetic acid with the volume ratio of 1: 40 at the speed of 0.25 mL/s. Continuously and violently stirring the obtained solution in the period, continuously stirring for 1-2h after the mixed solution is dripped, standing and aging for 12-84h under the conditions of normal temperature and dark state to obtain the nano TiO-containing2A sol of crystals.
2) According to the weight ratio of 1: 50, amidoxime modified polyacrylonitrile fiber with the weight gain ratio of 13-32 percent is placed in the nano TiO prepared in the step 12Stirring and reacting the crystal sol for 2 to 6 hours at 90 to 100 ℃ under a closed condition, taking out the crystal sol, repeatedly cleaning and drying the crystal sol by using distilled water to obtain the fiber chelated TiO based on the LMCT effect and the N doping2A visible light photocatalyst.
The Ti precursor is butyl titanate, and the hydrolysis inhibitor is a mixed solution of glacial acetic acid and absolute ethyl alcohol. The nano TiO2TiO in crystal sol2The concentration is 0.05-0.50 mol/L. The amidoximeThe literature "coordination structure of modified PAN fiber and iron ion and its catalytic action on dye degradation, the report of physical chemistry, 2008, 24 (11): 2114-2121 ".
CN102527440A, Nano TiO2Research on amidoxime fiber preparation, novel chemical materials 2014, 42 (4): 53-54 'and' Nano TiO2Photocatalytic performance of amidoxime fibers, high molecular report, 2013, 12: 71-76 reports that Ti is coordinated by taking amidoxime modified polyacrylonitrile fiber as a carrier and titanium tetrachloride as a precursor4+Loaded on the surface of the fiber and then passed through Ti4+Fiber-loaded nano TiO prepared by in-situ hydrolysis reaction under acidic condition2A catalyst. The catalyst has certain photocatalytic activity on a plurality of dyes under the condition of ultraviolet-visible light, but the main activity of the catalyst still comes from TiO2The utilization efficiency of visible light is not outstanding, and TiO in the catalyst2All are amorphous states and do not relate to visible light catalysis process caused by N doping.
With the existing fiber loaded with TiO2Compared with the catalyst, the invention has the beneficial effects that:
1) using a catalyst containing nano TiO2The sol of the crystal and amidoxime modified polyacrylonitrile fiber react at a higher temperature, and the prepared catalyst has TiO with anatase crystal form2The activity of the catalyst is obviously higher than that of amorphous TiO in the existing fiber catalyst2Photocatalytic activity of (1).
2) Amidoxime modified polyacrylonitrile fiber and nano TiO-containing fiber2In the sol reaction process of the crystal, amino in amidoxime group can be in nano TiO2The crystal growth process reacts with the crystal growth process, thereby realizing that N atoms are on TiO2Effective doping in the crystal lattice provides another visible light activation path for the obtained fiber catalyst.
3) Chelating ligands with nano TiO through amidoxime2The crystal is coordinated and combined, and an LMCT sensitization system which can be continuously applied to the degradation of organic pollutants is realized by means of the chemical stability of the fiber polymer. This uniqueness isCan impart structural design to TiO2Higher visible light catalytic activity and excellent long-term cycling stability.
The invention has the advantages of convenient material source, low price, simple process and easy implementation and control of operation conditions, and is suitable for industrial application.
Drawings
FIG. 1 is a graph showing the UV-VIS diffuse reflectance absorption spectra of catalysts obtained in examples one to four of the catalysts of the present invention.
FIG. 2 is an X-ray diffraction (XRD) pattern comparison of the catalyst obtained in the first example of the catalyst of the present invention and amidoxime-modified polyacrylonitrile fiber.
FIG. 3 shows the catalyst obtained in one embodiment of the present invention and the existing amidoxime fiber/TiO2Catalyst (sample one, prepared according to the method in CN102527440A, TiO)2In amorphous state) and amidoxime fibers supporting commercial TiO2Catalyst (sample two, using commercial P25 dispersion instead of containing nano TiO in the present invention2Sol of crystals, prepared by reaction with amidoxime-modified polyacrylonitrile fiber according to step 2 in example one), was compared for photocatalytic activity (test conditions: dye concentration: 0.02mmol/L, catalyst: 10.0g/L, temperature: 25 ℃, visible light: wavelength is more than 420nm, and intensity is 7.075mW/cm2)。
FIG. 4 shows the reusability of the catalyst obtained in the first example of the catalyst of the present invention in the degradation of dyes (test conditions: dye concentration: 0.02mmol/L, catalyst: 10.0g/L, temperature: 25 ℃, visible light: wavelength > 420nm, intensity 7.075mW/cm2)。
FIG. 5 shows the degradation rate of the catalyst obtained in the first embodiment of the present invention after 90min oxidative degradation of dyes with different structures and formaldehyde solution (test conditions: dye concentration: 0.02mmol/L, formaldehyde concentration: 2ug/mL, catalyst: 10.0g/L, temperature: 25 ℃, visible light: wavelength > 420nm, intensity of 7.075mW/cm2)。
Detailed Description
The present invention will be further explained with reference to the following examples and the accompanying drawings, but these examples do not limit the scope of the present invention.
The invention provides fiber chelated TiO based on LMCT effect and N doping2Visible light catalyst containing anatase crystal form and N-doped TiO2And the Ti content is 3.9-11.5 mg/g.
The invention also provides fiber chelated TiO based on the LMCT effect and N doping2The preparation method of the visible light photocatalyst comprises the following specific steps:
1) butyl titanate, glacial acetic acid and absolute ethyl alcohol are weighed according to the mol ratio of 1: 2: 5, are uniformly mixed by magnetic stirring, and are dripped into the deionized water solution of the glacial acetic acid with the volume ratio of 1: 40 at the speed of 0.25 mL/s. Continuously and violently stirring the obtained solution in the period, continuously stirring for 1-2h after the mixed solution is dripped, standing and aging for 12-84h under the conditions of normal temperature and dark state to obtain the nano TiO-containing2A sol of crystals.
2) According to the weight ratio of 1: 50, amidoxime modified polyacrylonitrile fiber with the weight gain ratio of 13-32 percent is placed in the nano TiO prepared in the step 12Stirring and reacting the crystal sol for 2 to 6 hours at 90 to 100 ℃ under a closed condition, taking out the crystal sol, repeatedly cleaning and drying the crystal sol by using distilled water to obtain the fiber chelated TiO based on the LMCT effect and the N doping2A visible light photocatalyst.
The nano TiO2TiO in crystal sol2The concentration is 0.05-0.50 mol/L.
The first embodiment is as follows:
1) weighing tetrabutyl titanate, glacial acetic acid and absolute ethyl alcohol according to the mol ratio of 1: 2: 5, uniformly mixing the tetrabutyl titanate, the glacial acetic acid and the absolute ethyl alcohol through magnetic stirring, and then dropwise adding the mixture into a glacial acetic acid deionized water solution with the volume ratio of 1: 40 at the speed of 0.25mL/s to enable TiO2The concentration was 0.12 mol/L. Continuously and violently stirring the obtained solution in the period, continuously stirring for 2 hours after the mixed solution is dripped, and then standing and aging for 36 hours under the conditions of normal temperature and dark state to obtain the nano TiO2A crystalline sol.
2) 1.0g of amidoxime-modified polyacrylonitrile fiber having a weight gain of 32% was weighed and placed in 50mL of the fiber prepared in step 1TiO rice2Stirring and reacting the crystal sol for 3 hours at 90 ℃ under a closed condition, taking out the crystal sol, and repeatedly cleaning and drying the crystal sol by using distilled water to obtain first fiber chelated TiO based on LMCT effect and N doping2A visible light photocatalyst.
Determination of titanium content of catalyst: accurately weighing 0.05g of catalyst, dissolving Ti ions in 15mL of mixed solution of sulfuric acid, hydrofluoric acid and nitric acid by an acid digestion method, measuring the titanium concentration in the solution by using an inductively coupled plasma emission spectrometer (ICP-OES), and calculating the titanium content on the catalyst to be 6.1mg/g according to the concentration.
Examples two, three, four:
respectively adjusting the weight gain rates of amidoxime-modified polyacrylonitrile in step 2 of the first step of the embodiment to 13%, 23% and 27%, and obtaining a second, a third and a fourth fibre-chelated TiO based on the LMCT effect and N doping in the same way as the first step of the first embodiment2A visible light photocatalyst. The titanium content on the catalyst was determined and calculated to be 4.9mg/g, 5.7mg/g and 5.9mg/g, respectively.
Example five, six:
Examples seven, eight:
Fig. 1 is an ultraviolet-visible diffuse reflection absorption spectrum of the catalysts obtained in the first to fourth examples, and it can be seen that all four catalysts have obvious absorption in the visible light region, which provides conditions for the catalysts to effectively utilize visible light to catalyze and oxidize organic pollutants. Through comparison, the light absorption of the four catalysts in the visible region is foundThe strength is in positive correlation with the weight gain ratio of the amidoxime modified polyacrylonitrile fiber, which shows that the amidoxime group in the fiber is a necessary condition for causing the catalyst to absorb visible light, and the reason is that the amidoxime ligand is converted into TiO2LMCT effect of metal centre and amidoxime amino N atom on TiO2The N doping formed during crystal growth.
As can be seen from FIG. 2, the XRD pattern of the catalyst obtained in the first example of the present invention shows new absorption peaks compared to the amidoxime-modified polyacrylonitrile fiber, and these peaks are similar to those of typical anatase TiO2The absorption peak positions are matched, which shows that the catalyst of the invention contains anatase TiO2This is in contrast to the prior amidoxime fibres/TiO2In the catalyst TiO2The results are clearly different for both amorphous states.
The photocatalytic activity of the catalyst of the present invention is determined by the rate of oxidative degradation of contaminants such as dyes. The specific method for investigating the activity of the catalyst comprises the following steps: selecting rhodamine B as a main dye pollutant, placing a catalyst in a dye aqueous solution, carrying out photocatalytic degradation reaction under the condition of visible light, calculating the degradation rate according to the change of the dye concentration, and evaluating the catalytic activity of the catalyst according to the dye degradation rate value. The catalyst prepared in the first example is selected for catalytic activity investigation and is compared with the existing amidoxime fiber/TiO2Catalyst and amidoxime fiber-supported commercial TiO2The catalysts were compared and the results are shown in FIG. 3. It can be seen that the catalyst obtained in example one of the present invention exhibits a significantly higher photocatalytic activity than the other two catalyst samples. With existing amidoxime fibres/TiO2Compared with the catalyst, the catalyst of the invention contains anatase crystal form and N-doped TiO2The photocatalytic activity of the photocatalyst is far higher than that of amorphous TiO2Activity of (2). Loading of commercial TiO with amidoxime fibers2Compared with the prior art, the P25 has a good anatase/rutile mixed crystal form, so that an amidoxime amino N atom is difficult to dope into P25 in the preparation process of the catalyst, and the amidoxime amino N atom can be oxidized and degraded on the dye under visible light only through an LMCT effect, so that the catalyst has lower photocatalytic activity. In summary, the catalysis of the present inventionThe visible light catalytic activity of the agent mainly comes from LMCT effect of amidoxime group and Ti and TiO2The N doping formed during crystal growth.
FIG. 4 shows that the catalytic activity of the catalyst obtained in the first embodiment of the present invention is not reduced in the process of continuously oxidizing and degrading dye rhodamine B for 5 times, which indicates that the catalyst can be applied to the oxidation and degradation treatment of dye wastewater for multiple times, i.e., the catalyst is not inactivated due to the auto-oxidation degradation and desorption of the ligand in the reaction process, and confirms that the fiber chelating ligand in the catalyst can be deactivated with TiO due to the auto-oxidation degradation and desorption of the ligand2Forming a stable LMCT visible light photosensitization system. Fig. 5 shows that the catalyst obtained in the first embodiment of the present invention has good photocatalytic oxidation activity for various dyes with different structures and formaldehyde as a colorless pollutant, which shows that the catalyst has good versatility and practicability in organic pollutant treatment, and has obvious economic benefits in industrial application.
Claims (4)
1. Fiber chelated TiO based on LMCT effect and N doping2The visible light catalyst is characterized in that: the catalyst contains anatase crystal form and N-doped TiO2Ti content of 3.9-11.5mg/g, is made of amidoxime modified polyacrylonitrile fiber and nano TiO2The crystal sol is obtained by reaction.
2. Fiber chelated TiO based on LMCT effect and N doping according to claim 12The visible light catalyst is characterized in that the fiber carrier can be amidoxime modified polyacrylonitrile short fiber, yarn and fabric, including woven fabric, knitted fabric, non-woven fabric and other materials.
3. The fiber chelated TiO based on LMCT effect and N doping as claimed in claim 12The preparation method of the visible light photocatalyst comprises the following specific steps:
1) butyl titanate, glacial acetic acid and absolute ethyl alcohol are weighed according to the mol ratio of 1: 2: 5, are uniformly mixed by magnetic stirring, and are dripped into the deionized water solution of the glacial acetic acid with the volume ratio of 1: 40 at the speed of 0.25 mL/s. Period of timeContinuously and violently stirring the obtained solution, continuously stirring for 1-2h after the mixed solution is dripped, standing and aging for 12-84h under the conditions of normal temperature and dark state to obtain the nano TiO-containing solution2A sol of crystals.
2) Amidoxime modified polyacrylonitrile fiber with the weight gain ratio of 13-32% is placed in the nano TiO-containing nano-polyacrylonitrile fiber prepared in the step 1 according to the weight ratio of 1: 502Stirring and reacting the crystal in sol of the crystal for 2 to 6 hours at 90 to 100 ℃ under a closed condition, then taking out the crystal, repeatedly cleaning the crystal by using distilled water and drying the crystal to obtain the fiber chelated TiO based on the LMCT effect and the N doping2A visible light photocatalyst.
4. Fiber chelated TiO based on LMCT effect and N doping according to claim 12The preparation method of the visible light catalyst is characterized in that the titanium precursor is tetrabutyl titanate containing nano TiO2TiO in crystalline sol2The concentration is 0.05-0.50 mol/L.
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