CN114870840B - Functional modified natural clay nanotube catalyst and preparation method thereof - Google Patents
Functional modified natural clay nanotube catalyst and preparation method thereof Download PDFInfo
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Abstract
The application discloses a functional modified natural clay nanotube catalyst and a preparation method thereof. The catalyst takes natural clay halloysite nanotubes as a carrier, is subjected to inner wall structure etching pretreatment, and then is deposited with mesoporous CeO on the surface 2 An active layer for functionally grafting Yu Jiekong CeO to porphyrin structure through interface bonding reaction 2 The surface utilizes the conjugated symmetrical four-coordinate amino locus to coordinate and adsorb Au precursor, through organic phase closed thermal reaction and ultraviolet radiation reduction, au nano particles with better dispersity are directionally anchored, and finally CeO is led by means of interfacial oxidation reduction reaction guiding effect 2 Ce in active layer 3+ Dissolve out and become coated with Mn 7+ Oxidation to form a platelet array CeO 2 ‑MnO 2 And the composite oxide is used as a shell structure to solidify and encapsulate Au nano particles, so that the catalyst is obtained. The catalyst has higher catalytic reaction activity, selectivity and stability, and has good application prospect in the field of nano catalysis.
Description
Technical Field
The application relates to the technical field of nano catalyst preparation, in particular to a functional modified natural clay nano tube catalyst and a preparation method thereof.
Background
Nitrobenzene substances play an important role in the chemical industries of printing and dyeing, textile, papermaking, explosive, petrochemical industry, medicine and the like, but are typical pollutants in poisonous and harmful wastewater produced by the industries at the same time, and are rapidly increased along with the rapid development of the industries. Nitrobenzene substances have a three-effect, strong toxicity, difficult biodegradation and high solubility and stability in water. Therefore, research on how to effectively remove nitrobenzene contaminants has been widely focused. Common process methods for treating such pollutants include solid adsorption, solvent extraction, membrane separation and other technologies of a physical method, microorganism metabolism, aerobic/anaerobic organisms, activated sludge and other technologies of a biological method, and electrochemical oxidation, fenton oxidation, photocatalytic oxidation and other technologies of a chemical method, however, the above-mentioned technical methods have certain limitations, such as complicated operation process, secondary pollution generation, high subsequent treatment cost and the like.
The catalytic reduction process is a relatively efficient and environment-friendly catalytic technology, can completely convert nitrobenzene substances into amine substances through selective reduction reaction without generating byproducts, has extremely low toxicity and relatively high utilization value, and is an important raw material or intermediate in the fields of corrosion inhibitors, lubricants, antipyretic analgesic drugs and the like. The key point of the technology is the structural design of the catalyst, and many researchers find that the active metal immobilized nano catalyst based on the porous carrier structure limit domain can show better catalytic reduction performance, and can reduce high-toxicity nitrobenzene pollutants into low-toxicity high-added-value amine substances under mild conditions. Among them, au nanoparticles are widely studied and applied because of their high surface activity, large specific surface area, excellent catalytic performance and good selectivity. However, during the preparation and catalytic application processes of the material, the nano Au particles have poor stability due to the excessively high surface free energy, and are easy to agglomerate, run off and the like, so that the catalytic performance of the nano Au particles is obviously reduced, and the application of the nano Au particles is limited. The research shows that the encapsulation and solidification of the immobilized Au nano-particles by a structure limit domain or a specific anchoring mechanism can further improve the stability of the Au nano-particles, and the synergistic effect of the whole structure of the catalyst is exerted to strengthen the catalytic performance of the Au nano-particles.
Patent CN106694039B discloses a preparation method of carbon sphere/Au nanocomposite, which comprises preparing carbon sphere, modifying its surface with polydiallyl dimethyl ammonium chloride and carrying positive reactionCharge, use electrostatic attraction to make AuCl 4 - Uniformly and rapidly adsorbing the Au particles on the surface of the carbon sphere, and finally using N, N-dimethylformamide as a reducing agent under the protection of polyvinylpyrrolidone to enable the reduced Au particles to grow along a specific crystal face so as to prepare the nanocomposite; however, the supported Au nanoparticles are generally dispersed and easily separated from the carrier. Patent CN112916021a reports an Fe 3 O 4 @Cu 2 The O-Au composite nano material is prepared from ferric acetylacetonate, copper acetylacetonate, a reducing agent and an organic solvent by a thermal decomposition method 3 O 4 @Cu 2 O-composite material, followed by HAuCl 4 Reacting to obtain Fe 3 O 4 @Cu 2 O-Au composite nano-material; however, the Au nano-particles are easy to deform and run off when the composite material is used as a catalyst, so that the stability of the catalytic reaction is reduced. Patent CN112916021A proposes a SnS 2 /g-C 3 N 4 Preparation method of Au composite photocatalyst, and the catalyst is used for preparing g-C firstly 3 N 4 Precursor, and SnS 2 The precursor is subjected to hydrothermal reaction to prepare SnS 2 /g-C 3 N 4 Composite material, then disperse in HAuCl 4 Irradiating the diluted solution with ultraviolet lamp to obtain SnS 2 /Au/g-C 3 N 4 A composite photocatalyst; however, the morphology and the size of the Au nano-particles prepared by the method are difficult to control, and the agglomeration phenomenon is easy to occur.
Disclosure of Invention
The application aims to provide a functional modified natural clay nanotube catalyst and a preparation method thereof. The catalyst takes natural clay halloysite nanotubes as a carrier, firstly carries out etching pretreatment on an inner wall structure so as to increase the specific surface area and enrich pore structures, and then builds mesoporous CeO on the surface 2 The active layer is used for functionally modifying porphyrin functional groups, rich amino attachment sites of the active layer are used for immobilizing an Au precursor through coordination adsorption and reducing the Au precursor into Au nano-particles in situ, so that the Au nano-particles can be effectively anchored and dispersed, the distribution form, the crystal structure and the morphology and the size of the Au nano-particles are controlled, and finally, the interface oxidation-reduction reaction guiding effect is utilized for constructing a lamellar array CeO 2 -MnO 2 The composite oxide shell encapsulates and cures Au nano-particles to obtain the functional modified natural clay nanotube catalyst (THNTs@CeO) 2 -Au@CeO 2 -MnO 2 Composite material). The preparation method can reduce the aggregation, the loss and other phenomena of the Au nano-particles to a large extent, improves the reactivity, the selectivity and the thermal stability of the nano-Au catalyst, and has good application prospect in the field of nano-catalysis.
The application provides a functional modified natural clay nanotube catalyst, which comprises the following components: halloysite nanotubes; mesoporous CeO modified with porphyrin units 2 An active layer of mesoporous CeO 2 An active layer is deposited on the surface of the halloysite nanotube; au nanoparticles immobilized on amino sites of the porphyrin functional groups; ceO in sheet array 2 -MnO 2 A composite oxide shell layer, the flaky arrays of CeO 2 -MnO 2 The complex oxide shell layer is deposited on the surface of the Au nano-particles.
Optionally, the functional modified natural clay nanotube catalyst, wherein the porphyrin unit is a tetracarboxylic porphyrin ligand.
Optionally, the weight percentage of the Au nano particles in the functionally modified natural clay nanotube catalyst is 0.5-5% of the total weight of the functionally modified natural clay nanotube catalyst.
The catalyst takes natural clay halloysite nanotubes as a carrier, firstly carries out etching pretreatment on an inner wall structure so as to increase the specific surface area and enrich pore structures, and then deposits mesoporous CeO on the surface 2 And the functional grafting porphyrin structure has amino site with Au precursor immobilized through coordination adsorption and reduced to nanometer Au particle in situ, and finally through interface oxidation-reduction reaction guiding effect, flaky array CeO is constructed 2 -MnO 2 The composite oxide shell encapsulates and cures nano Au particles to obtain the functional modified natural clay nanotube (THNTs@CeO) 2 -Au@CeO 2 -MnO 2 Composite material). The catalyst has higher reactivity, selectivity and thermal stability, and has good application prospect in the field of nano catalysis, whereinThe method is helpful to promote the conversion and utilization of industrial wastewater resources in the application practice of nitrobenzene selective reduction reaction.
The preparation method of the functional modified natural clay nanotube catalyst comprises the following steps:
(1) Taking halloysite nanotubes, concentrated sulfuric acid and H 2 O 2 The solution is placed at 50-90 ℃ according to a certain mass ratio, and is subjected to reflux stirring for 0.5-3 hours, cooled to room temperature, centrifuged, the supernatant is discarded, the solid is washed by distilled water, and vacuum drying is carried out at 40-60 ℃ for 8-15 hours, thus obtaining the modified halloysite nanotube THNTs;
(2) Dispersing the modified halloysite nanotube THNTs and hexamethyltetramine in ethanol according to a certain mass ratio, stirring for 0.5-1 h, dropwise adding a certain amount of cerium salt solution, heating in an oil bath at 70-100 ℃ for reflux reaction for 4-8 h, cooling to room temperature, centrifuging, washing with ethanol, and drying at 40-60 ℃ for 8-15 h to obtain THNTs@CeO 2 A composite material;
(3) Dissolving methyl p-formylbenzoate in propionic acid, heating to 140-160 ℃ for reflux, dripping a certain amount of pyrrole in 0.5-1 h, reacting for 2-6 h, naturally cooling to room temperature, and obtaining a purple porphyrin ester precursor after cleaning and drying operations; dissolving the purple porphyrin ester precursor in a mixed solution of tetrahydrofuran and methanol, regulating alkaline conditions to hydrolyze, heating to react at 140-160 ℃ and acidizing, centrifuging and purifying to obtain a tetracarboxylic porphyrin ligand;
optionally, dissolving methyl paraformylbenzoate in propionic acid, heating to 140-160 ℃ for reflux, then dripping a certain amount of pyrrole in 0.5-1 h, and continuing to react for 2-6 h; naturally cooling to room temperature, washing with methanol, diethyl ether and tetrahydrofuran, purifying by column chromatography, and vacuum drying at room temperature to obtain purple porphyrin ester precursor; then dissolving in tetrahydrofuran and methanol mixed solution, regulating alkaline condition to hydrolyze, heating to 140-160 deg.c for reaction, acidifying, centrifuging and purifying to obtain tetracarboxy porphyrin ligand.
(4) The THNTs@CeO is added to 2 The composite material, zirconium salt, tetracarboxy porphyrin ligand, benzoic acid and distilled water are mixed according to a certain proportionDispersing the mixture in N, N-dimethylformamide solvent in a mass ratio, and stirring the mixture for 0.5 to 1 hour at room temperature to obtain a mixture; transferring the mixture into a polytetrafluoroethylene lining of a reaction kettle, reacting for 18-24 hours at the constant temperature of 100-150 ℃, centrifuging, washing with methanol, and vacuum drying for 8-15 hours at the temperature of 40-60 ℃ to obtain porphyrin unit modified halloysite nanotube THNTs@CeO 2 -Py composite material;
(5) Au precursor and THNTs@CeO are prepared 2 Dispersing the-Py composite material in N, N-dimethylformamide solvent according to a certain mass ratio, stirring for 6-10 h at room temperature, transferring into a polytetrafluoroethylene lining of a reaction kettle, performing airtight thermal reaction at 80-120 ℃ for 4-10 h, centrifuging, dispersing in 50-100 mL isopropanol solution containing 5% volume ratio, maintaining circulating cooling water at constant temperature and irradiating with an ultraviolet high-pressure mercury lamp for 0.5-1 h in a dark box environment, centrifuging, drying at 40-60 ℃ for 8-15 h to obtain THNTs@CeO 2 -Py-Au composite;
(6) Taking the THNTs@CeO with a certain mass ratio 2 And (3) ultrasonically mixing the Py-Au composite material and potassium permanganate in 50-150 mL of distilled water, heating to 70-90 ℃ in an oil bath for reflux, stirring for reaction for 8-16 h, centrifuging, washing with ethanol, drying at 40-60 ℃ for 8-15 h, then placing an inert gas atmosphere, heating to 200-400 ℃ at a constant temperature with a heating rate of 5-10 ℃/min, and maintaining for 2-5 h to obtain the functional modified natural clay nanotube catalyst.
Alternatively, the halloysite nanotubes described in the above step (1) of preparing the catalyst, concentrated sulfuric acid and H 2 O 2 The mass ratio of the solution is 1: 10-20: 4 to 10; wherein the concentrated sulfuric acid and H 2 O 2 The volume ratio of the solution is 7:3.
optionally, the mass ratio of the modified halloysite nanotubes THNTs, hexamethylenetetramine and cerium salt in the step (2) of preparing the catalyst is 1:2 to 8:0.3 to 2; the dosage of the cerium salt solution is 50-150 mL; the cerium salt is selected from any one of cerium nitrate, ammonium cerium nitrate, cerium sulfate, cerium chloride and cerium acetate.
Optionally, the mass ratio of pyrrole, methyl p-formyl benzoate and propionic acid in the step (3) of preparing the catalyst is 1: 2-3: 55-60; the pH of the alkaline condition is 8-10, and the used regulating solution is one of KOH solution (10wt%) or NaOH solution (10wt%); the pH value of the acidification treatment is 4-7, and the used regulating solution is HCl solution (5 wt%).
Optionally, the tetracarboxylporphyrin ligand described in the step (4) of preparing the catalyst occupies THNTs@CeO 2 The mass percentage of the composite material is 10-30%, wherein the mass ratio of the zirconium salt, the tetra-carboxyl porphyrin ligand, the benzoic acid, the N, N-dimethylformamide and the distilled water is 1:0.2 to 2.5: 5-15: 50-90: 2 to 15; the zirconium salt is selected from any one of zirconium oxychloride, zirconium chloride, zirconium sulfate and zirconium nitrate.
Alternatively, THNTs@CeO as described in the above step (5) of preparing a catalyst 2 The mass ratio of the Py composite material, the Au precursor and the N, N-dimethylformamide solvent is 1:0.015 to 0.2: 50-200 parts; the Au precursor is selected from any one of tetrachloroauric acid, gold acetate, ammonium tetrachloroauric acid and sodium tetrachloroauric acid; the power of the ultraviolet high-pressure mercury lamp is 250W, the main radiation wavelength is 365nm, and circulating cooling water maintains a constant temperature condition; the mass percentage of the Au nano-particles is 0.5-5% of the total mass of the catalyst.
Optionally, the THNTs@CeO in the step (6) of preparing the catalyst is 2 The mass ratio of the Py-Au composite material to the manganese element in the potassium permanganate is 1:0.05 to 0.5; the inert gas is selected from any one of high-purity nitrogen, high-purity helium and high-purity argon.
The beneficial effects are that: the application provides a functional modified natural clay nanotube catalyst and a preparation method thereof. The catalyst has higher catalytic activity, selectivity and stability in the nitrobenzene selective reduction reaction, and has good application prospect in the field of industrial wastewater resource conversion.
The application is characterized in that:
(1) The inner wall structure of the halloysite nanotube is etched to increase the specific surface area and enrich the pore structure, so that the interface micro-reaction environment of the porous carrier is improved, the interface modification of the subsequent metal oxide and the functional grafting of the porphyrin functional group are facilitated, and the catalyst shows better carrier synergistic effect;
(2) The amino group in the porphyrin structure is deprotonated under specific conditions and coordinated metal ions form a more stable metal-porphyrin structure, so that the immobilized metal cluster can be more stable; by reacting THNTs@CeO 2 Grafting porphyrin functional groups through interface bonding reaction, increasing effective metal attachment sites of a carrier interface, enabling Au nano-particles to be firmly anchored in a carrier structure, and improving dispersity and thermal stability of the Au nano-particles;
(3) The organic phase airtight thermal reaction promotes Au ions to be reduced into Au nanoclusters in situ, the rest free Au ions are adsorbed on Au crystals, meanwhile, porphyrin functional groups lose protons to form a stable metal-porphyrin structure, and then the Au nano particles with good dispersity are converted into Au nano particles through ultraviolet radiation reduction reaction, so that the directional anchoring of the space positions of the Au nano particles is realized;
(4) THNTs@CeO by utilizing interfacial redox reaction guiding effect 2 Packaging the Py-Au composite material in a shell structure, and high-valence Mn 7+ Ion-induced CeO formation 2 Ce in active layer 3+ Is dissolved out and oxidized to form a flake array CeO 2 -MnO 2 The composite oxide further encapsulates and cures Au nano-particles, not only enhances the synergistic effect between Au active sites and an interlayer carrier structure, promotes the formation of a special interlayer cross-linked pore structure of the system, improves the catalytic reaction performance of the nano-catalyst, and simultaneously plays the structural limiting effect of the lamellar array laminated mesoporous oxide on the Au active sites, reduces the aggregation and loss of the Au nano-particles, and further improves the thermal stability and catalytic activity of the Au nano-particles.
Drawings
FIG. 1 is a TEM image of the functionally modified natural clay nanotube catalyst prepared in example 1;
FIG. 2 is an SEM image of the functionally modified natural clay nanotube catalyst prepared in example 1;
FIG. 3 is an XRD pattern of the functionally modified natural clay nanotube catalyst prepared in example 1;
FIG. 4 is an elemental distribution diagram of the functionally modified natural clay nanotube catalyst prepared in example 1;
Detailed Description
The present application is further illustrated below with reference to specific examples, which are intended to be illustrative of the application and not to be limiting of the scope of the application, since modifications of the application in its various equivalents will fall within the scope of the application as defined by the appended claims after reading the application.
Example 1:
taking 1g halloysite nanotube, 14mL concentrated sulfuric acid and 6mL H at room temperature 2 O 2 Ultrasonically mixing the solution in a three-neck round bottom flask, carrying out reflux reaction for 3 hours at 60 ℃, naturally cooling to room temperature, centrifuging, washing with distilled water until the pH value of the supernatant is neutral, and carrying out vacuum drying at 50 ℃ for 12 hours to obtain THNTs solid;
dispersing 0.5g THNTs solid and 2g hexamethylenetetramine in 90mL ethanol at room temperature, stirring for 0.5h, dropwise adding 0.75g cerium nitrate hexahydrate and 70mL distilled water during the period, placing in an oil bath at 80 ℃ for heating for reflux reaction for 5h, cooling to room temperature, centrifuging, washing with ethanol, and drying at 50 ℃ for 12h to obtain THNTs@CeO 2 A composite material;
at room temperature, 0.5g of THNTs@CeO is taken 2 The composite material, 0.33g zirconium sulfate tetrahydrate, 0.15g tetra-carboxyl porphyrin ligand (prepared in advance and stored in a refrigerator), 3.8g benzoic acid and 3.4mL distilled water are dispersed in 30mL N, N-dimethylformamide solvent, and stirred for 1h at room temperature; transferring the solution into a polytetrafluoroethylene lining of a reaction kettle, reacting for 24 hours at the constant temperature of 100 ℃, centrifuging, washing with methanol, and drying for 12 hours at the temperature of 50 ℃ in vacuum to obtain THNTs@CeO 2 -Py composite material;
at room temperature, 0.5g of THNTs@CeO is taken 2 Py composite material, 1.5mL of tetrachloroauric acid solution (10 mg Au/mL), ultrasonic mixing in 55mL of N, N-dimethylformamide solvent, stirring for 8h at room temperature, transferring into a polytetrafluoroethylene lining of a reaction kettle to perform organic phase closed thermal reaction, keeping the constant temperature at 85 ℃, keeping the reaction time at 7h, centrifuging, dispersing in 50mL of isopropanol solution containing 5% volume ratio, keeping the constant temperature of circulating cooling water, irradiating with ultraviolet high-pressure mercury lamp for 0.5h in a dark box environment, centrifuging, drying at 60 ℃ for 8h to obtain THNTs@CeO 2 -Py-Au composite;
at room temperature, 0.5g of THNTs@CeO is taken 2 -Py-Au composite material and 0.45g potassium permanganate are dispersed in 80mL distilled water by ultrasonic, reflux reaction is carried out for 12h at 80 ℃ by heating in an oil bath, cooling to room temperature, centrifuging, washing with ethanol, and drying for 10h at 50 ℃; then heat treatment is carried out in a high-purity nitrogen atmosphere, the temperature is raised to 300 ℃ at a heating rate of 5 ℃/min, and the temperature is kept for 3 hours to obtain THNTs@CeO 2 -Au@CeO 2 -MnO 2 A composite material. The obtained composite material is characterized, and the characterization result is shown in figures 1 to 4, and the composite material is provided with a specific lamellar array outer layer structure, corresponding element distribution characteristics and rich pore channel structures.
Evaluation conditions: respectively taking 50mL NaBH 4 The solution (0.5 mol/L) and 50mL of 4-nitrophenol solution (20 mg/L) were mixed, magnetic stirring was maintained, 5mL of a catalyst dispersion (2 g/L) was added to the mixed solution, and the catalytic reaction was timed. After a small amount of reaction solution was filtered through a filter head at different reaction times, the 4-nitrophenol conversion and selectivity were analyzed by means of a UV-Vis absorption spectrometer.
The results show that: the conversion rate of the catalytic reduction of the 4-nitrophenol by the catalyst is 95% within 4min, and the selectivity of the 4-aminophenol is 100%.
Example 2:
at room temperature, 1g halloysite nanotube, 15mL concentrated sulfuric acid and 6.5mL H were taken 2 O 2 Ultrasonically mixing the solution in a three-neck round bottom flask, carrying out reflux reaction for 1h at 80 ℃, naturally cooling to room temperature, centrifuging, washing with distilled water until the pH value of the supernatant is neutral, and carrying out vacuum drying at 55 ℃ for 10h to obtain THNTs solid;
dispersing 0.5g THNTs solid and 2.5g hexamethylenetetramine in 85mL ethanol at room temperature, stirring for 0.5h, dropwise adding 0.7g cerium nitrate hexahydrate and 60mL distilled water during the period, placing in 75 ℃ oil bath, heating for reflux reaction for 6h, cooling to room temperature, centrifuging, washing with ethanol, drying at 50 ℃ for 10h to obtain THNTs@CeO 2 A composite material;
taking 0.45g of THNTs@CeO at room temperature 2 Composite material, 0.21g of zirconium oxychloride octahydrate and 0.12g of tetracarboxy porphyrin ligand (prepared in advance and placed in a refrigerator for preservation)) 2.4g benzoic acid and 2.1mL distilled water were dispersed in 22mL N, N-dimethylformamide solvent and stirred at room temperature for 0.5h; transferring the solution into a polytetrafluoroethylene lining of a reaction kettle, reacting for 20 hours at the constant temperature of 120 ℃, centrifuging, washing with methanol, and vacuum drying for 8 hours at the temperature of 60 ℃ to obtain THNTs@CeO 2 -Py composite material;
taking 0.3g of THNTs@CeO at room temperature 2 Mixing Py composite material and 1.3mL of ammonium tetrachloroaurate solution (10 mg Au/mL) with 50mL of N, N-dimethylformamide solvent by ultrasonic, stirring for 8h at room temperature, transferring into a polytetrafluoroethylene lining of a high-pressure reaction kettle for organic phase closed thermal reaction, keeping the constant temperature at 100 ℃, keeping the reaction time at 5h, centrifuging, dispersing in 50mL of isopropanol solution containing 5% volume ratio, keeping the constant temperature condition by circulating cooling water, irradiating with an ultraviolet high-pressure mercury lamp for 0.5h in a dark box environment, centrifuging, drying at 50 ℃ for 10h to obtain THNTs@CeO 2 -Py-Au composite;
taking 0.3g of THNTs@CeO at room temperature 2 -Py-Au composite material and 0.3g potassium permanganate are dispersed in 65mL distilled water by ultrasonic, reflux reaction is carried out for 10h at 90 ℃ by heating in an oil bath, cooling to room temperature, centrifuging, washing by ethanol, and drying for 10h at 50 ℃; then heat-treating in high-purity argon atmosphere, heating to 350 ℃ at a heating rate of 6 ℃/min, and keeping at constant temperature for 3 hours to obtain THNTs@CeO 2 -Au@CeO 2 -MnO 2 A composite material.
Evaluation conditions: evaluation conditions: respectively taking 50mL NaBH 4 The solution (0.5 mol/L) and 50mL of 2-nitrophenol solution (20 mg/L) were mixed, magnetic stirring was maintained, 5mL of a catalyst dispersion (2 g/L) was added to the mixed solution, and the catalytic reaction was timed. After a small amount of reaction solution was filtered through a filter head at different reaction times, the conversion and selectivity of 2-nitrophenol were analyzed by means of a UV-Vis absorption spectrometer.
The results show that: the conversion rate of the catalytic reduction of the 2-nitrophenol by the catalyst is 97% within 4min, and the selectivity of the 2-aminophenol is 100%.
Example 3:
at room temperature, 1.5g halloysite nanotube, 21mL concentrated sulfuric acid and 9mL H were taken 2 O 2 Ultrasonic mixing of the solution in a three-neck round bottom flaskReflux-reacting at 70deg.C for 2h, naturally cooling to room temperature, centrifuging, washing with distilled water until the pH of the supernatant is neutral, and vacuum-drying at 50deg.C for 12h to obtain THNTs solid;
dispersing 0.8g THNTs solid and 3.2g hexamethylenetetramine in 95mL ethanol at room temperature, stirring for 1h, dropwise adding 1g cerium chloride heptahydrate and 80mL distilled water during the period, placing in an oil bath at 85 ℃ for heating for reflux reaction for 4h, cooling to room temperature, centrifuging, washing with ethanol, and drying at 50 ℃ for 10h to obtain THNTs@CeO 2 A composite material;
at room temperature, 0.6g of THNTs@CeO is taken 2 The composite material, 0.35g zirconium sulfate tetrahydrate, 0.16g tetra-carboxyl porphyrin ligand (prepared in advance and stored in a refrigerator), 3.8g benzoic acid and 2.9mL distilled water are dispersed in 32mL N, N-dimethylformamide solvent, and stirred for 1h at room temperature; transferring the solution into a polytetrafluoroethylene lining of a reaction kettle, reacting at a constant temperature of 115 ℃ for 21 hours, centrifuging, washing with methanol, and vacuum drying at 45 ℃ for 12 hours to obtain THNTs@CeO 2 -Py composite material;
taking 0.45g of THNTs@CeO at room temperature 2 Mixing Py composite material and 1.9mL of sodium tetrachloroaurate solution (10 mg Au/mL) with 60mL of N, N-dimethylformamide solvent by ultrasonic, stirring for 6h at room temperature, transferring into a polytetrafluoroethylene lining of a high-pressure reaction kettle for organic phase closed thermal reaction, keeping the constant temperature at 90 ℃, keeping the reaction time at 6h, centrifuging, dispersing in 60mL of isopropanol solution containing 5% volume ratio, keeping the constant temperature by circulating cooling water, irradiating with an ultraviolet high-pressure mercury lamp for 1h in a dark box environment, centrifuging, drying at 45 ℃ for 14h to obtain THNTs@CeO 2 -Py-Au composite;
taking 0.4g of THNTs@CeO at room temperature 2 -Py-Au composite material and 0.42g potassium permanganate are dispersed in 70mL distilled water by ultrasonic, reflux reaction is carried out for 12h at 85 ℃ by heating in an oil bath, cooling to room temperature, centrifuging, washing with ethanol, and drying for 8h at 50 ℃; then heat treatment is carried out in a high-purity nitrogen atmosphere, the temperature is raised to 350 ℃ at a heating rate of 5 ℃/min, and the temperature is kept for 3 hours to obtain THNTs@CeO 2 -Au@CeO 2 -MnO 2 A composite material.
Evaluation conditions: respectively taking 50mL NaBH 4 Solution (0.5 mol/L) and 50mL of 3-nitrophenol solution (20 mg)/L) was mixed, magnetic stirring was maintained, 5mL of a catalyst dispersion (2 g/L) was added to the above mixed solution, and the catalytic reaction was timed. After a small amount of reaction solution was filtered through a filter head at different reaction times, the conversion and selectivity of 3-nitrophenol were analyzed by means of a UV-Vis absorption spectrometer.
The results show that: the conversion rate of the 3-nitrophenol by catalytic reduction of the catalyst is 96% within 8min, and the selectivity of the 3-aminophenol is 100%.
Example 4:
at room temperature, 1.3g halloysite nanotubes, 18mL concentrated sulfuric acid and 7.7mL H were taken 2 O 2 Ultrasonically mixing the solution in a three-neck round bottom flask, carrying out reflux reaction for 2 hours at 80 ℃, naturally cooling to room temperature, centrifuging, washing with distilled water until the pH value of the supernatant is neutral, and carrying out vacuum drying at 45 ℃ for 12 hours to obtain THNTs solid;
dispersing 0.7g THNTs solid and 3.5g hexamethylenetetramine in 85mL ethanol at room temperature, stirring for 40min, dropwise adding 0.8g cerium acetate hydrate and 70mL distilled water during the period, placing in an oil bath at 80 ℃ for heating for reflux reaction for 6h, cooling to room temperature, centrifuging, washing with ethanol, and drying at 50 ℃ for 12h to obtain THNTs@CeO 2 A composite material;
taking 0.65g of THNTs@CeO at room temperature 2 The composite material, 0.41g zirconium nitrate pentahydrate, 0.17g tetra-carboxyl porphyrin ligand (prepared in advance and stored in a refrigerator), 4.6g benzoic acid and 4mL distilled water are dispersed in 37mL N, N-dimethylformamide solvent, and stirred for 1h at room temperature; transferring the solution into a polytetrafluoroethylene lining of a reaction kettle, reacting at the constant temperature of 130 ℃ for 18 hours, centrifuging, washing with methanol, and vacuum drying at 55 ℃ for 9 hours to obtain THNTs@CeO 2 -Py composite material;
at room temperature, 0.6g of THNTs@CeO is taken 2 Mixing Py composite material and 2.5mL of tetrachloroauric acid solution (10 mg/mL) with 80mL of N, N-dimethylformamide solvent by ultrasonic, stirring for 5h at room temperature, transferring into a polytetrafluoroethylene lining of a reaction kettle to perform organic phase closed thermal reaction, keeping the constant temperature at 85 ℃ and the reaction time at 8h, centrifuging, dispersing in 80mL of isopropanol solution containing 5% volume ratio, keeping the constant temperature condition by circulating cooling water, and irradiating with ultraviolet high-pressure mercury lamp in dark box environmentInjecting for 1h, centrifuging, drying at 55 ℃ for 10h to obtain THNTs@CeO 2 -Py-Au composite;
at room temperature, 0.6g of THNTs@CeO is taken 2 -Py-Au composite material and 0.55g potassium permanganate are dispersed in 80mL distilled water by ultrasonic, reflux reaction is carried out for 15h at 80 ℃ by heating in an oil bath, cooling to room temperature, centrifuging, washing with ethanol, and drying for 10h at 50 ℃; then heat-treating in high-purity argon atmosphere, heating to 300 ℃ at a heating rate of 6 ℃/min, and keeping the temperature for 4 hours to obtain THNTs@CeO 2 -Au@CeO 2 -MnO 2 A composite material.
Evaluation conditions: respectively taking 50mL NaBH 4 The solution (0.5 mol/L) and 50mL of 2-chloro-4-nitrophenol solution (20 mg/L) were mixed, magnetic stirring was maintained, 5mL of a catalyst dispersion (2 g/L) was added to the mixed solution, and the catalytic reaction was timed. After a small amount of reaction solution was filtered through a filter head at different reaction times, the conversion and selectivity of 2-chloro-4-nitrophenol were analyzed by means of a UV-Vis absorption spectrometer.
The results show that: the conversion rate of the catalyst for catalytic reduction of the 2-chloro-4-nitrophenol is 95% and the selectivity of the 2-chloro-4-aminophenol is 100% within 6 min.
Example 5:
at room temperature, 1.6g halloysite nanotubes, 23mL concentrated sulfuric acid and 9.8mL H were taken 2 O 2 Magnetically stirring and mixing the solution in a three-neck round bottom flask, carrying out reflux reaction for 1h at 85 ℃, naturally cooling to room temperature, centrifuging, washing with distilled water until the pH value of the supernatant is neutral, and carrying out vacuum drying at 55 ℃ for 10h to obtain THNTs solid;
dispersing 0.8g THNTs solid and 4g hexamethylenetetramine in 80mL ethanol at room temperature for 1h, dropwise adding 1.2g ceric ammonium nitrate and 90mL distilled water during the stirring, placing in an 80 ℃ oil bath for heating for reflux reaction for 5.5h, cooling to room temperature, centrifuging, washing with ethanol, and drying at 50 ℃ for 10h to obtain THNTs@CeO 2 A composite material;
weighing 0.75g of THNTs@CeO at room temperature 2 The composite material, 0.35g zirconium chloride, 0.14g tetra-carboxyl porphyrin ligand (prepared in advance and stored in a refrigerator), 5.7g benzoic acid and 4mL distilled water were dispersed in 37mL N, N-dimethylformamide solvent, chamberStirring for 1h at the temperature; transferring the solution into a polytetrafluoroethylene lining of a reaction kettle, reacting for 20 hours at the constant temperature of 120 ℃, centrifuging, washing with methanol, and vacuum drying for 10 hours at 50 ℃ to obtain THNTs@CeO 2 -Py composite material;
taking 0.7g of THNTs@CeO at room temperature 2 Mixing Py composite material and 3mL gold acetate solution (10 mg Au/mL) with 75mL N, N-dimethylformamide solvent by ultrasonic, stirring for 4.5h at room temperature, transferring into a polytetrafluoroethylene lining of a reaction kettle to perform organic phase closed thermal reaction, keeping the constant temperature at 110 ℃ for 4h, centrifuging, dispersing in 80mL isopropanol solution containing 5% volume ratio, keeping the constant temperature by circulating cooling water, irradiating with ultraviolet high-pressure mercury lamp for 40min under dark box environment, centrifuging, drying at 45 ℃ for 12h to obtain THNTs@CeO 2 -Py-Au composite;
taking 0.55g of THNTs@CeO at room temperature 2 -Py-Au composite material and 0.65g potassium permanganate are dispersed in 90mL distilled water by ultrasonic, reflux reaction is carried out for 12h at 90 ℃ by heating in an oil bath, cooling to room temperature, centrifuging, washing with ethanol, drying for 10h at 50 ℃, centrifuging, washing with ethanol, and drying for 10h at 55 ℃; then heat treatment is carried out in high-purity nitrogen atmosphere, the temperature is raised to 350 ℃ at the heating rate of 8 ℃/min, and the temperature is kept for 2.5 hours, thus obtaining THNTs@CeO 2 -Py@CeO 2 -MnO 2 A composite material.
Evaluation conditions: respectively taking 50mL NaBH 4 The solution (0.5 mol/L) and 50mL of 2-bromo-4-nitrophenol solution (20 mg/L) were mixed, magnetic stirring was maintained, 5mL of a catalyst dispersion (2 g/L) was added to the mixed solution, and the catalytic reaction was timed. After a small amount of reaction solution was filtered through a filter head at different reaction times, the conversion and selectivity of 2-bromo-4-nitrophenol were analyzed by means of a UV-Vis absorption spectrometer.
The results show that: the conversion rate of the catalyst for catalytic reduction of 2-bromo-4-nitrophenol is 93% and the selectivity of 2-bromo-4-aminophenol is 100% within 8 min.
Example 6:
at room temperature, 2.4g halloysite nanotubes, 28mL concentrated sulfuric acid and 12mL H were taken 2 O 2 Ultrasonic mixing the solution in a three-neck round bottom flask, reflux reacting at 85deg.C for 2h, and naturally coolingCooling to room temperature, centrifuging, washing with distilled water until the pH of the supernatant is neutral, and vacuum drying at 50deg.C for 12h to obtain THNTs solid;
at room temperature, 1g of THNTs solid and 5g of hexamethylenetetramine are taken to be dispersed in 95mL of ethanol and stirred for 1h, 1.5g of cerium sulfate tetrahydrate and 100mL of distilled water are added dropwise during the period, and the mixture is placed in an oil bath at the temperature of 75 ℃ for heating to carry out reflux reaction for 6h, cooled to room temperature, centrifuged, washed by ethanol and dried for 12h at the temperature of 50 ℃ to prepare THNTs@CeO 2 A composite material;
taking 0.8g of THNTs@CeO at room temperature 2 The composite material, 0.48g zirconium nitrate pentahydrate, 0.21g tetra-carboxyl porphyrin ligand (prepared in advance and stored in a refrigerator), 5.2g benzoic acid and 4mL distilled water are dispersed in 40mL N, N-dimethylformamide solvent, and stirred for 1h at room temperature; transferring the solution into a polytetrafluoroethylene lining of a reaction kettle, reacting for 22 hours at a constant temperature of 110 ℃, centrifuging, washing with methanol, and vacuum drying for 10 hours at 55 ℃ to obtain THNTs@CeO 2 -Py composite material;
at room temperature, 0.75g of THNTs@CeO was taken 2 Mixing Py composite material, 3.2mL ammonium tetrachloroaurate solution (10 mg Au/mL) with 80mL N, N-dimethylformamide solvent, stirring at room temperature for 6h, transferring into a polytetrafluoroethylene lining of a reaction kettle to perform organic phase closed thermal reaction, keeping the constant temperature at 110 ℃, keeping the reaction time at 4h, centrifuging, dispersing in 60mL isopropanol solution containing 5% volume ratio, keeping the constant temperature with circulating cooling water, irradiating with ultraviolet high-pressure mercury lamp for 0.5h under the dark box environment, centrifuging, drying at 50 ℃ for 10h to obtain THNTs@CeO 2 -Py-Au composite;
weighing 0.7g of THNTs@CeO at room temperature 2 -Py-Au composite material and 0.9g potassium permanganate are dispersed in 100mL distilled water by ultrasonic, reflux reaction is carried out for 13h at 85 ℃ by heating in an oil bath, cooling to room temperature, centrifuging, washing with ethanol, and drying for 12h at 50 ℃; then heat treatment is carried out in a high-purity nitrogen atmosphere, the temperature is raised to 320 ℃ at a heating rate of 8 ℃/min, and the temperature is kept for 3 hours to obtain THNTs@CeO 2 -Au@CeO 2 -MnO 2 A composite material.
Evaluation conditions: respectively taking 50mL NaBH 4 The solution (0.5 mol/L) and 50mL of 2-methyl-4-nitrophenol solution (20 mg/L) were mixed and magnetically stirredAfter stirring, 5mL of the catalyst dispersion (2 g/L) was added to the mixed solution, and the catalytic reaction was timed. After a small amount of reaction solution was filtered through a filter head at different reaction times, the conversion and selectivity of 2-methyl-4-nitrophenol were analyzed by means of a UV-Vis absorption spectrometer.
The results show that: the conversion rate of the catalyst for catalytic reduction of the 2-methyl-4-nitrophenol is 92% and the selectivity of the 2-methyl-4-aminophenol is 100% within 15 min.
Claims (7)
1. The preparation method of the functional modified natural clay nanotube catalyst is characterized by comprising the following steps of:
(1) Reflux stirring a halloysite nanotube, concentrated sulfuric acid and H2O2 solution for 0.5-3H at 50-90 ℃ according to a certain mass ratio, cooling to room temperature, centrifuging, discarding supernatant, washing a solid with distilled water, and vacuum drying at 40-60 ℃ for 8-15H to obtain modified halloysite nanotube THNTs;
(2) Dispersing the modified halloysite nanotube THNTs and hexamethyltetramine in ethanol according to a certain mass ratio, stirring for 0.5-1 h, dropwise adding a certain amount of cerium salt solution, heating in an oil bath at 70-100 ℃ for reflux reaction for 4-8 h, cooling to room temperature, centrifuging, washing with ethanol, and drying at 40-60 ℃ for 8-15 h to obtain THNTs@CeO2 composite material;
(3) Dissolving methyl paraformylbenzoate in propionic acid, heating to 140-160 ℃ for reflux, dripping a certain amount of pyrrole in 0.5-1 h, reacting for 2-6 h, naturally cooling to room temperature, and obtaining a purple porphyrin ester precursor after cleaning and drying operations; dissolving the purple porphyrin ester precursor in a mixed solution of tetrahydrofuran and methanol, regulating an alkaline condition to hydrolyze, heating to react at 140-160 ℃, acidizing, centrifuging, and purifying to obtain a tetracarboxylic porphyrin ligand;
(4) Dispersing the THNTs@CeO2 composite material, zirconium salt, tetra-carboxyl porphyrin ligand, benzoic acid and distilled water in an N, N-dimethylformamide solvent according to a certain mass ratio, and stirring for 0.5-1 h at room temperature to obtain a mixture; transferring the mixture into a polytetrafluoroethylene lining of a reaction kettle, reacting for 18-24 hours at a constant temperature of 100-150 ℃, centrifuging, washing with methanol, and vacuum drying for 8-15 hours at a temperature of 40-60 ℃ to obtain a porphyrin unit modified halloysite nanotube THNTs@CeO2-Py composite material;
(5) Dispersing an Au precursor and the THNTs@CeO2-Py composite material in an N, N-dimethylformamide solvent according to a certain mass ratio, stirring for 6-10 hours at room temperature, transferring into a polytetrafluoroethylene lining of a reaction kettle, performing airtight thermal reaction on the mixture for 4-10 hours at 80-120 ℃, centrifuging, dispersing the mixture in 50-100 mL of isopropanol solution containing 5% by volume, keeping a constant temperature condition by circulating cooling water, irradiating for 0.5-1 hour by an ultraviolet high-pressure mercury lamp in a dark box environment, centrifuging, and drying for 8-15 hours at 40-60 ℃ to obtain the THNTs@CeO2-Py-Au composite material;
(6) And (3) mixing the THNTs@CeO2-Py-Au composite material and potassium permanganate in 50-150 mL of distilled water in an ultrasonic manner according to a certain mass ratio, heating to 70-90 ℃ in an oil bath, carrying out reflux, stirring and reacting for 8-16 h, centrifuging, washing with ethanol, drying at 40-60 ℃ for 8-15 h, then placing an inert gas atmosphere, heating to 200-400 ℃ at a heating rate of 5-10 ℃/min, and keeping at a constant temperature for 2-5 h to obtain the functional modified natural clay nanotube catalyst.
2. The method for preparing a functionally modified natural clay nanotube catalyst according to claim 1, wherein in the step (1), a mass ratio of the halloysite nanotube, the concentrated sulfuric acid and the H2O2 solution is 1: 10-20: 4-10, wherein the volume ratio of the concentrated sulfuric acid to the H2O2 solution is 7:3.
3. the method for preparing a functionally modified natural clay nanotube catalyst according to claim 1, wherein in the step (2), the mass ratio of the modified halloysite nanotubes THNTs, hexamethylenetetramine and cerium salt is 1: 2-8: 0.3-2; the cerium salt is selected from any one of cerium nitrate, ammonium cerium nitrate, cerium sulfate, cerium chloride and cerium acetate.
4. The method for preparing a functionally modified natural clay nanotube catalyst according to claim 1, wherein in the step (3), the mass ratio of pyrrole, methyl p-formylbenzoate, and propionic acid is 1: 2-3: 55-60 parts; the pH of the alkaline condition is 8-10.
5. The preparation method of the functionally modified natural clay nanotube catalyst according to claim 1, wherein in the step (4), the tetracarboxy porphyrin ligand accounts for 10-30% of the mass of the thnts@ceo2 composite material; the mass ratio of the zirconium salt to the tetracarboxyl porphyrin ligand, the benzoic acid, the N, N-dimethylformamide and distilled water is 1: 0.2-2.5: 5-15: 50-90: 2-15 parts; the zirconium salt is selected from any one of zirconium oxychloride, zirconium chloride, zirconium sulfate and zirconium nitrate.
6. The method for preparing the functionally modified natural clay nanotube catalyst according to claim 1, wherein in the step (5), the mass ratio of the thnts@ceo2-Py composite material, au precursor and N, N-dimethylformamide solvent is 1: 0.015-0.2: 50-200 parts; the Au precursor is selected from any one of tetrachloroauric acid, gold acetate, ammonium tetrachloroauric acid and sodium tetrachloroauric acid.
7. The method for preparing a functionally modified natural clay nanotube catalyst according to claim 1, wherein in the step (6), a mass ratio of the thnts@ceo2-Py-Au composite material to manganese element in the potassium permanganate is 1:0.05 to 0.5.
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