CN112774656A - Preparation method and application of titanium pillared montmorillonite composite catalyst - Google Patents

Preparation method and application of titanium pillared montmorillonite composite catalyst Download PDF

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CN112774656A
CN112774656A CN202110108541.6A CN202110108541A CN112774656A CN 112774656 A CN112774656 A CN 112774656A CN 202110108541 A CN202110108541 A CN 202110108541A CN 112774656 A CN112774656 A CN 112774656A
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titanium
composite catalyst
suspension
titanium pillared
pillared montmorillonite
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吴宏海
卢鹏澄
魏燕富
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South China Normal University
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Abstract

The invention relates to the field of catalysts, in particular to a preparation method and application of a titanium pillared montmorillonite composite catalyst, which comprises the following steps: s1, preparing a sodium-based montmorillonite suspension A; s2, preparing titanium pillared agent liquid B; s3, preparing a titanium pillared montmorillonite suspension C; s4, aging the suspension C for 20-30 h at room temperature, and stirring at a rotating speed of 20-35 r/min; s5, centrifuging the aged suspension C obtained in the step S4 at a rotating speed of 3800-4500 r/min for 3-10 min, washing the suspension C to be neutral by using deionized water, and drying filter residues at the temperature of 70-90 ℃; s6, grinding the product dried in the step S5, sieving the product with a 200-mesh sieve, and calcining the product at the temperature of 100-500 ℃ for 1-3 hours to obtain the catalyst. The composite catalyst obtained by the invention has high catalytic activity and can be applied to catalytic decomposition and conversion of refractory organic compounds.

Description

Preparation method and application of titanium pillared montmorillonite composite catalyst
Technical Field
The invention relates to the field of catalysts, and in particular relates to a preparation method and application of a titanium pillared montmorillonite composite catalyst.
Background
Nitrophenols are a typical class of nonbiodegradable organic compounds which have been widely used as intermediates for various synthetic compounds such as pesticides, herbicides, dyes and the like, containing the nitro group (-NO)2) In the fragranceThe biochemical stability of the compound is enhanced because electrons can be strongly attracted in the ring. The dye is mainly various dyes released to the environment by industrial wastewater discharged by textile industry and dye house, and can bring non-wear damage to living environment of human and animals and plants.
Titanium dioxide (TiO)2) Is a semiconductor material which is very important in the field of environmental catalysis, and has the environmental protection characteristics of abundant reserves, no toxicity and low cost, so that the semiconductor material is widely applied to the oxidation-reduction conversion of various pollutants in environmental management, and particularly the application of the photocatalytic decomposition conversion of organic pollutants is greatly developed. Although titanium dioxide powder has a large specific surface area and excellent catalytic activity, there still exist practical problems such as difficulty in recycling and easy agglomeration. However, TiO is mixed with2Fixed on montmorillonite (Mt) but can retain TiO to some extent2The property of the crystalline phase semiconductor can solve the problems of difficult recovery and easy agglomeration.
An effective method for modifying clay structure and strategy for developing catalyst, such as using metal cation as pillared ion modifier, can design different pillared layered clay. Among the pillared layered clays, Titanium Pillared Clay (TPC) has various advantages as a potential catalyst, including high stability, huge specific surface area and large pores with adjustable pore size, thus attracting a wide interest. Therefore, TPC mineral materials have been an important research hotspot for decades. The surface properties (including surface charge, acidity, structure and the like) of the clay mineral are greatly influenced by treatment modes such as acid activation, heating, cation fixation and the like, so that the practical application potential of the clay mineral is changed. In particular, the heat treatment not only changes the lamellar structure and surface properties of the montmorillonite, but also on TiO2Crystal growth can also have an effect. Excessive temperature treatment may not only destroy the lamellar structure and surface functional groups of the montmorillonite, but may also cause TiO2The anatase phase is changed into the rutile type. Rutile type TiO2The structure is more stable, however, the electron transfer rate is not as good as anatase.
The existing methods for preparing titanium pillared montmorillonite (TPMt) are many, the hydrothermal method and the sol method are the two most common methods, and the titanium pillared montmorillonite powder prepared in the past almost has no detailed analysis on a thermal modification product. The invention finds that a plurality of acid sites exist on the surface of the titanium pillared montmorillonite which is not subjected to heat treatment, and the acid sites compete for electrons with nitrophenol pollutants together, so that the method is obviously not beneficial to catalytic reduction conversion removal of the pollutants.
Disclosure of Invention
The invention aims to provide a preparation method and application of a titanium pillared montmorillonite composite catalyst, aiming at the problems that in the prior art, a plurality of acid sites exist on the surface of the titanium pillared montmorillonite, and the catalytic reduction conversion effect on nitrophenol pollutants is not good.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a titanium pillared montmorillonite composite catalyst comprises the following steps:
s1, dispersing sodium-based montmorillonite in deionized water, and stirring for 2-4 hours at room temperature to obtain a sodium-based montmorillonite suspension A with the mass percentage of 3% -6%;
s2, according to Ti and H+The molar ratio of the titanium oxide to the titanium oxide is 1 (1.5-2.5), and tetrabutyl titanate and an HCl solution are mixed to obtain a titanium pillared agent solution B;
s3, mixing the suspension A and the titanium pillared agent liquid B according to the ratio of [ Ti ]/Mt of 5-20 mmoL/g, and stirring for 0.5-1.5 h to obtain a titanium pillared montmorillonite suspension C;
s4, aging the suspension C for 20-30 h at room temperature, and stirring at a rotating speed of 20-35 r/min;
s5, centrifuging the aged suspension C obtained in the step S4 at a rotating speed of 3800-4500 r/min for 3-10 min, washing the suspension C with deionized water to be neutral, and drying filter residues at 70-90 ℃; stirring in the aging process to increase the fluidity of the turbid liquid, and enabling most of titanium cations to complete intercalation behavior to enter the interlayer region of montmorillonite to avoid layered precipitation and accumulation of montmorillonite and titanium dioxide.
S6, grinding the product dried in the step S5, sieving the product with a 200-mesh sieve, and calcining the product for 1-3 hours at the temperature of 100-500 ℃ to obtain the catalyst.
[ Ti ]/Mt represents the ratio of the concentration of titanium to the mass of montmorillonite.
Preferably, in the step S1, the sodium-based montmorillonite suspension a is 5% by mass.
Preferably, in the step S2, Ti and H+In a molar ratio of 1: 2.
Preferably, in the step S4, the aging time is 24 h.
Preferably, in the step S5, the centrifugal separator is centrifuged at 4000r/min for 6 min.
Preferably, in the step S5, the calcination is performed at a temperature of 200 ℃.
The titanium pillared montmorillonite composite catalyst is obtained by the preparation method of the titanium pillared montmorillonite composite catalyst.
The titanium pillared montmorillonite composite catalyst is applied to the degradation of organic pollutants.
The titanium pillared montmorillonite composite catalyst is applied to degrading nitrophenol.
Compared with the prior art, the invention has the following technical characteristics:
(1) the slow stirring is adopted in the aging time instead of standing aging, so that most of polymeric titanium cations can enter montmorillonite interlayers and are uniformly distributed on the surface of montmorillonite, and the generation of pure titanium dioxide colloidal particles which are not easy to precipitate is reduced;
(2) calcination makes the polymeric titanium cations more robust between or on the surface of the montmorillonite layer, while promoting the formation of anatase crystals;
(3) the anatase phase is the core of the catalytic reduction reaction, and the higher the exposure rate is, the better the catalytic reduction effect is, so the proper temperature needs to be controlled to ensure that the calcination can not damage the layered structure of the montmorillonite phase in the titanium pillared montmorillonite, and the improvement of the catalytic reduction conversion effect is facilitated;
(4) the surface of the montmorillonite has a plurality of solid acid sites which are not beneficial to the catalytic reduction and conversion of pollutants, and the acid sites on the surface are irreversibly reduced through calcination, but the structural integrity of the montmorillonite is ensured to improve the catalytic effect.
Drawings
FIG. 1 is an XRD pattern of sodium montmorillonite and titanium pillared montmorillonite;
FIG. 2 is an SEM image of titanium pillared montmorillonite;
FIG. 3 is a diagram showing the effect of titanium pillared montmorillonite on catalytic reduction of o-nitrophenol (2-NP);
FIG. 4 is the adsorption diagram of sodium montmorillonite and titanium pillared montmorillonite for o-nitrophenol;
FIG. 5 is a graph of pyridine FTIR of titanium pillared montmorillonite.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below with reference to specific examples and comparative examples. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the examples given herein without any inventive step, are within the scope of the present invention.
Unless otherwise specified, the devices used in this example are all conventional experimental devices, the materials and reagents used are commercially available, and the experimental methods without specific descriptions are also conventional experimental methods.
The purity of the sodium montmorillonite reaches 90%, and the particle size is 100-200 meshes. All other reagents used were analytical grade, with tetrabutyl titanate from Tianjin Daloco chemical reagent works.
Example 1
S1. preparation of montmorillonite suspension
Weighing 12.5g of sodium-based montmorillonite, dispersing in 238mL of deionized water, and vigorously stirring at room temperature (about 25 ℃) for 3 hours to obtain a sodium-based montmorillonite suspension with the solid mass concentration of 5%;
s2. preparation of titanium pillared agent solution
Taking 21.3mL of tetrabutyl titanate, dropwise adding the tetrabutyl titanate into 63mL of 2M HCl solution, and vigorously stirring for 1h to obtain [ Ti]/[H+]Titanium pillared agent solution with the molar ratio of 1: 2;
s3. preparation of pillared montmorillonite
Mixing the sodium-based montmorillonite suspension and the titanium pillared agent solution according to the ratio of [ Ti ]/Mt of 5mmoL/g, and violently stirring for 1h to ensure that the mixture is fully and uniformly mixed to obtain the titanium pillared montmorillonite suspension;
s4, aging
The titanium pillared montmorillonite suspension was aged at room temperature (about 25 ℃) for 24 hours while being slowly stirred at a rotation speed of about 30 r/min. And centrifuging the suspension, washing the suspension with deionized water until the pH is neutral, and centrifuging the suspension for 6min at the rotating speed of 4000r/min to obtain a wet cake.
S5, drying
Drying the wet cake obtained in S4 in an oven at 80 deg.C;
s6, grinding and calcining
And grinding the dried sample and passing through a 200-mesh sieve, then placing the powder sample in a covered crucible and putting the crucible into a 200 ℃ muffle furnace for calcining for 2h to obtain the titanium pillared montmorillonite composite catalyst.
Example 2
S1. preparation of montmorillonite suspension
Weighing 12.5g of sodium-based montmorillonite, dispersing in 238mL of deionized water, and stirring vigorously at room temperature (about 25 ℃) for 3 hours to obtain a sodium-based montmorillonite suspension with a solid concentration of 5%;
s2. preparation of titanium pillared agent solution
42.5mL of tetrabutyl titanate was added dropwise to 125mL of 2M HCl solution, [ Ti ]]/[H+]The molar ratio is 1:2, and the mixture is stirred vigorously for 1h to obtain a titanium pillared agent solution;
s3. preparation of pillared montmorillonite
Mixing the sodium-based montmorillonite suspension and the titanium pillared agent solution according to the ratio of [ Ti ]/Mt of 10mmoL/g, and violently stirring for 1h to ensure that the mixture is fully and uniformly mixed to obtain the titanium pillared montmorillonite suspension;
s4, aging
The titanium pillared montmorillonite suspension was aged at room temperature (about 25 ℃) for 24 hours while being slowly stirred at a rotation speed of about 30 r/min. And then centrifuging the solution and washing the solution by deionized water, wherein the pH of the solution is neutral, the rotating speed is 4000r/min, and the centrifuging time is 6min to obtain a wet cake.
S5, drying
Drying the wet cake obtained in S4 in an oven at 80 deg.C;
s6, grinding and calcining
After grinding and passing through a 200-mesh sieve, the powder was placed in a covered crucible and calcined in a 200 ℃ muffle furnace for 2 hours to obtain a titanium pillared montmorillonite composite catalyst.
Example 3
S1. preparation of montmorillonite suspension
Weighing 12.5g of sodium-based montmorillonite, dispersing in 238ml of deionized water, and stirring vigorously at room temperature (about 25 ℃) for 3 hours to obtain a sodium-based montmorillonite suspension with the solid mass concentration of 5%;
s2, preparing titanium pillared agent solution
85mL of tetrabutyl titanate is taken and dripped into 250mL of 2M HCl solution, and the mixture is stirred vigorously for 1h to obtain [ Ti]/[H+]Titanium pillared agent solution with the molar ratio of 1: 2;
s3, preparation of pillared montmorillonite
Mixing the sodium-based montmorillonite suspension and the titanium pillared agent solution according to the ratio of [ Ti ]/Mt of 20mmoL/g, and violently stirring for 1h to ensure that the mixture is fully and uniformly mixed to obtain the titanium pillared montmorillonite suspension;
s4, aging
The titanium pillared montmorillonite suspension was aged at room temperature (about 25 ℃) for 24 hours while being slowly stirred at a rotation speed of about 30 r/min. And then centrifuging the solution, washing the solution by deionized water until the pH value is neutral, and centrifuging the solution for 6min at the rotating speed of 4000r/min to obtain a wet cake.
S5, drying
Drying the wet cake obtained in S4 in an oven at 80 deg.C;
s6, grinding and calcining
Grinding a sample, sieving the ground sample by a 200-mesh sieve, putting the powder sample into a covered crucible, and calcining the crucible in a muffle furnace at the temperature of 100-500 ℃ for 2 hours to obtain 6 titanium pillared montmorillonite composite catalysts (TPMt 100-TPMt 500) with different calcination temperatures.
Examples of the experiments
The catalytic reduction reaction is all in N2The method is carried out under the atmosphere condition and is free from light irradiation. The reaction device comprises a glass conical flask, a rubber plug, a magnetic stirrer, tinfoil and the like. Reaction vesselHigh purity N is used before adding ferrous sulfate and o-nitrophenol (2-NP) before starting2Removing dissolved oxygen, setting aeration N2The gas lasts for about 30 min. The reaction solution contained 0.2mol/L NaCl, 28mmol/L buffer (MES), 22. mu. mol/L2-NP, and 3.0mmol/L FeSO4And 4.0g/L catalyst. However, before the 2-NP is added into the reaction system, the Fe (II) pre-adsorption needs to be carried out for 2h to ensure that the Fe (II) can reach the adsorption equilibrium. Once the 2-NP was added to the catalytic reaction system, the catalytic reduction experiment was started. The reaction temperature for each experiment was controlled at room temperature (about 25 ℃). At regular intervals, 1.5mL aliquots of the suspension were sampled and stopped with 2.0mol/L HCl (20. mu.L).
All liquid samples were filtered using 0.22 μm PTFE membrane filters prior to determination of 2-NP concentration. The sample was analyzed by reversed-phase High Performance Liquid Chromatography (HPLC) using Shimadzu LC-10AT Shimadzu, Japan, and using Syncronis-C18 reversed-phase column (250 mm. times.4.6 mm, 5 μm). The mobile phase composition was 80% methanol and 20% ultrapure water (which was acidified with hydrochloric acid and adjusted to pH 2.8). The flow rate of the mobile phase is 1mL/min, the column temperature is 25 ℃, the sample injection amount is 20 mu L, and the detection wavelength is 265 nm.
To explain the catalytic reduction effect of the titanium pillared montmorillonite p-o-nitrophenol of the present invention, the main data obtained by the test, characterization, etc. are specifically described as follows:
XRD analysis
At the XRD pattern 2 theta 6 degrees (FIG. 1), the characteristic diffraction peak of the original sodium-based montmorillonite (Na-Mt) (001) crystal face can be clearly observed, but the characteristic peak is weakened in 6 TPMt. The d001 value of the montmorillonite phase is changed between 1.24 nm and 1.59nm, which indicates that the polymeric titanium ions enter the interlayer of the montmorillonite and are hydrolyzed to form an anatase titanium dioxide column. In addition to the diffraction peak at 2 θ ≈ 6 °, a strong new diffraction peak corresponding to the (101) crystal plane of anatase can be clearly observed at 2 θ ≈ 25.3 °.
When the calcination temperature is 150 ℃ or higher, the above-mentioned (001) diffraction peak becomes broader and weaker, indicating that the (001) crystal face is destroyed, while the (101) crystal face strong diffraction peak corresponding to anatase becomes gradually sharper with an increase in calcination temperature, indicating that the heat treatment promotes the crystal growth of anatase.
The (Mt200) sample obtained by calcination of Na-Mt at 200 ℃ still retained a sharp (001) diffraction peak at 2 θ ≈ 6 °, whereas the 150 ℃ heat-treated TPMt sample, in contrast, had a significantly broader and flatter diffraction peak at this point, indicating that the (001) crystal plane was destroyed during the growth of anatase crystals, consistent with the above analysis.
SEM analysis
The particle morphology of the mineral particles changed to ellipsoidal shape after 400 ℃ calcination in TPMt samples from large area continuous to discontinuous with increasing calcination temperature (fig. 2 a-d). The elemental distribution plots show that the distribution of titanium elements is relatively uniform (fig. 2e-f), indicating that the anatase phase is uniformly distributed on the outer surface of the Mt and/or in the interlaminar space. The anatase formed between the layers is beneficial to provide strong support between the Mt layers, but also has a large distribution on the surface. However, the central portion of the structural sheet is the new section that is most likely to crack during firing, thereby uncovering the Mt edge.
3. Catalytic reduction effect diagram and adsorption diagram of p-o-nitrophenol
The mineral material composite catalyst synthesized by the invention has the best catalytic performance on Fe (II), namely TPMt200 with the calcination temperature of 200 ℃, and secondly (TPMt150 ≈ TPMt300)>(TPMt100≈TPMt400)>TPMt500 (fig. 3 b). The titanium content in the titanium pillared montmorillonite has obvious influence on the catalytic reduction reaction, and the removal efficiency of o-nitrophenol reduction is found to be introduced along with the introduction of TiO2The increase in content is significant (FIG. 3c), which is comparable to the initial TPMt, TiO2The results of the tests observed at 200 and Mt200 (fig. 3a) are consistent. In addition, 2-NP is in montmorillonite and TiO2And 6 TPMt samples (fig. 4), so the removal of 2-NP by these mineral material catalysts is mainly catalytic reduction conversion removal. It is noted that TPMt200 rapidly reduced and converted to remove 2-NP, and 2-NP was completely removed at pH 7.0 for 10min (fig. 3 d).
4. FTIR plot of pyridine
Figure BDA0002918438260000091
The acid sites are mainly derived from the interlamination of polarized water molecules (such as Na) in the montmorillonite+、K+、Ca2+Hydration of (b), H adsorbed on Al-O octahedron (main site of structural negative charge)3O+And SiOH species, while the Lewis acid sites originate mainly from unsaturated Al at the edges of the octahedral sheets3+(Mg2+And Fe2+/3+). According to the pyridine adsorption mode, at 1640 and 1540cm-1The infrared absorption bands of (1) correspond to Bpy acid sites and are positioned at 1450-1455 and 1600-620cm-1Has an infrared absorption band belonging to the acid position of Lpy and being close to 1440 and 1590cm-1Corresponding to acid position Hpy. 1490cm-1The strong absorption band of (b) may contain all types of surface acid sites, i.e., Bpy + Lpy + Hpy. Bpy and Hpy relate to solid moisture content and dihydroxylation, respectively, and decrease with increasing heat treatment temperature.
The total amount of acid sites for the 6 TPMt samples decreased with increasing heat treatment temperature. The acid sites of which are mainly derived from the Mt component and not from the incorporated TiO2. The main factors influencing the number of Lewis acid sites are: unsaturated Al with exposed bond3+Interlayer cations and their migration into the layer, and the degree of anatase coverage. In 5 TPMt samples calcined at temperatures above 100 deg.C, 1620cm were not observed-1The Lpy peak at point, may be associated with coverage of the anatase crystalline phase. When the calcination temperature is increased to 200 ℃, the reason for the decrease in the number of Lewis acid sites may be that the temperature increase promotes the permeation of interlayer cations to the bottom of the silicon sheet ring structure inside the Mt crystal structure.
The clay mineral has different types of acid sites distributed on the surface, including (AlOH, Al)2OH，AlOH2+And Al3+) The acidity is different because of different structural forms. In fact, the surface reaction active sites of the catalyst need to have certain surface complexing ability and to be strongly combined with Fe (II) so as to increase the density of electron clouds on the outer layer of Fe (II) ions, thereby enhancing the reduction performance of ferrous iron. Acid sites with appropriate strength can form a high-activity ferrous surface complex. For example,>TiOH、>FeOH in comparison with>AlOH can form a ferrous surface complex with strong reduction activity. In addition, the oreThe surface-mediated properties of the material are also important, and low surface impedance is beneficial to electron transmission. Therefore, the titanium and iron oxides with semiconductor properties have good environmental protection application potential. Therefore, the invention introduces anatase phase titanium dioxide and carries out the optimization design of the material, and finally successfully obtains the TPMt200 mineral material composite catalyst with excellent surface reduction catalytic performance.
The TPMt200 composite catalyst material with excellent reduction catalytic performance is successfully synthesized, and because the surface of a sample of the material is distributed with an anatase phase with good crystallization and a large number of surface titanium hydroxyl sites are more than TiOH, the material can form a Fe (II) surface complex with water-phase ferrous iron (II), and meanwhile, the TPMt200 also shows low surface impedance. These surface properties are all very beneficial for the catalytic reduction of 2-NP. Although the anatase crystallinity and resistivity properties in TPMt300 are similar to those of TPMt200, the structural layer breaks down significantly, while the edge sections of the cleaved montmorillonite lack anatase distribution, resulting in a relatively reduced amount of distribution of > tiofe (ii) over its surface. Thus, the catalytic performance of the surface reduction of TPMt300 is affected to some extent, with a reduced rate of 2-NP reductive conversion occurring on its surface (FIG. 3 b).
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.

Claims (9)

1. The preparation method of the titanium pillared montmorillonite composite catalyst is characterized by comprising the following steps of:
s1, dispersing sodium-based montmorillonite in deionized water, and stirring for 2-4 hours at room temperature to obtain a sodium-based montmorillonite suspension A with the mass percentage of 3% -6%;
s2, according to Ti and H+The molar ratio of the titanium oxide to the titanium oxide is 1 (1.5-2.5), and tetrabutyl titanate and an HCl solution are mixed to obtain a titanium pillared agent solution B;
s3, mixing the suspension A and the titanium pillared agent solution B according to the ratio of [ Ti ]/Mt of 5-20 mmoL/g, and stirring for 0.5-1.5 h to obtain a titanium pillared montmorillonite suspension C;
s4, ageing the suspension C for 20-30 hours at room temperature, and continuously stirring at a rotating speed of 20-35 r/min;
s5, centrifuging the aged suspension C obtained in the step S4 at a rotating speed of 3800-4500 r/min for 3-10 min, washing the suspension C with deionized water to be neutral, and drying filter residues at 70-90 ℃;
s6, grinding the product dried in the step S5, sieving the product with a 200-mesh sieve, and calcining the product at the temperature of 100-500 ℃ for 1-3 hours to obtain the catalyst.
2. The method for producing a titanium pillared montmorillonite composite catalyst according to claim 1, wherein in the step S1, the sodium-based montmorillonite suspension a is 5% by mass.
3. The method for producing the titanium pillared montmorillonite composite catalyst according to claim 1, wherein in the step S2, Ti and H are added+In a molar ratio of 1: 2.
4. The method for producing a titanium pillared montmorillonite composite catalyst according to claim 1, wherein in the step S4, the aging time is 24 hours.
5. The method for preparing a titanium pillared montmorillonite composite catalyst according to claim 1, wherein in the step S5, the titanium pillared montmorillonite composite catalyst is centrifuged at a rotation speed of 4000r/min for 6 min.
6. The method for preparing a titanium pillared montmorillonite composite catalyst according to claim 1, wherein in the step S6, the calcination is performed at a temperature of 200 ℃ for 1 to 3 hours.
7. The titanium pillared montmorillonite composite catalyst obtained by the method for producing a titanium pillared montmorillonite composite catalyst according to any one of claims 1 to 6.
8. Use of the titanium pillared montmorillonite composite catalyst of claim 7 for degrading organic pollutants.
9. Use of the titanium pillared montmorillonite composite catalyst of claim 7 for degrading nitrophenol.
CN202110108541.6A 2021-01-27 2021-01-27 Preparation method and application of titanium pillared montmorillonite composite catalyst Pending CN112774656A (en)

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Application publication date: 20210511