CN114870840A - 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 invention discloses a functional modified natural clay nanotube catalyst and a preparation method thereof. The catalyst takes natural clay halloysite nanotubes as a carrier, and is subjected to etching pretreatment of an inner wall structure and then surface deposition of mesoporous CeO 2 An active layer, which is used for functionally grafting a porphyrin structure on the mesoporous CeO through an interface bonding reaction 2 On the surface, Au precursors are adsorbed by utilizing the conjugation symmetry four-coordinate amino site coordination, Au nanoparticles with better dispersity are directionally anchored through organic phase closed thermal reaction and ultraviolet radiation reduction, and finally the guiding action of the interface oxidation-reduction reaction is utilizedWith CeO 2 Ce in the active layer 3+ Is dissolved and coated by Mn 7+ Oxidation to form a lamellar array of CeO 2 ‑MnO 2 And the composite oxide is used as a shell structure to solidify and encapsulate Au nano particles to obtain the catalyst. The catalyst has high catalytic reaction activity, selectivity and stability, and shows good application prospect in the field of nano catalysis.
Description
Technical Field
The invention relates to the technical field of nano catalyst preparation, in particular to a function modified natural clay nanotube catalyst and a preparation method thereof.
Background
Nitrobenzene substances play an important role in chemical industries such as printing and dyeing, textile, papermaking, explosives, petrochemical industry, medicine and the like, but are typical pollutants in toxic and harmful wastewater generated by the industries, and the nitrobenzene substances are increased along with the rapid development of the industries. The nitrobenzene substances have 'three-cause' effect, strong toxicity, difficult biodegradation and high solubility and stability in water. Therefore, extensive attention is paid to the research on how to effectively remove the nitrobenzene pollutants. The common process methods for treating the pollutants comprise solid adsorption, solvent extraction, membrane separation and other technologies of a physical method, microbial 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 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, nitrobenzene substances can be completely converted into amine substances through selective reduction reaction without generating byproducts, and the amine substances have extremely low toxicity and high utilization value and are important raw materials or intermediates in the fields of corrosion inhibitors, lubricants, antipyretic and analgesic drugs and the like. The key point of the process lies in the integral structural design of the catalyst, and many researchers find that the active metal immobilized nano catalyst based on the porous carrier structure limited domain can show better catalytic reduction performance and can reduce the highly toxic nitrobenzene pollutants into low-toxicity amine substances with high added values under mild conditions. Among them, Au nanoparticles have been widely studied and applied because of their high surface activity, large specific surface area, excellent catalytic performance, and good selectivity. However, in the process of material preparation and catalytic application, the nano Au particles have poor stability due to excessively high surface free energy, and are prone to agglomeration, loss and other phenomena, so that the catalytic performance of the nano Au particles is remarkably reduced, and the application of the nano Au particles is limited. Researches show that the stability of the immobilized Au nanoparticles can be further improved by packaging and curing the immobilized Au nanoparticles through a structural confinement or a specific anchoring mechanism, and the catalytic performance of the Au nanoparticles is enhanced by exerting the synergistic effect of the overall structure of the catalyst.
Patent CN106694039B discloses a preparation method of a carbon sphere/Au nano composite material, which comprises the steps of firstly preparing carbon spheres, modifying the surfaces of the carbon spheres by poly (diallyldimethylammonium chloride) and carrying positive charges, and utilizing electrostatic attraction to lead AuCl to be 4 - Uniformly and quickly adsorbing the Au particles onto the surface of a carbon sphere, and finally, under the protection of polyvinylpyrrolidone, taking N, N-dimethylformamide as a reducing agent to enable the reduced Au particles to grow along a specific crystal face, thereby preparing the nano composite material; however, the loaded Au nanoparticles are generally dispersed and easily come off the support. Patent CN112916021A reports a Fe 3 O 4 @Cu 2 The preparation method of O-Au composite nano material uses acetylacetone iron, acetylacetone copper, reducing agent and organic solvent as raw materials to obtain Fe by thermal decomposition method 3 O 4 @Cu 2 O composite material, subsequently with HAuCl 4 Reacting to obtain Fe 3 O 4 @Cu 2 An O-Au composite nanomaterial; however, when the composite material is used as a catalyst, Au nanoparticles are easy to deform and lose, and the stability of the catalytic reaction of the composite material is reduced. Patent CN112916021A proposes an SnS 2 /g-C 3 N 4 The preparation method of the Au composite photocatalyst comprises the steps of firstly preparing g-C 3 N 4 Precursor of SnS 2 The precursor is subjected to hydrothermal reaction to prepare SnS 2 /g-C 3 N 4 Composite material, then dispersed in HAuCl 4 In a dilute solution, obtaining SnS by ultraviolet lamp irradiation 2 /Au/g-C 3 N 4 A composite photocatalyst; however, the Au nanoparticles prepared by the method have the defects of difficult control of shape and size and easy agglomerationA phenomenon.
Disclosure of Invention
The invention aims to provide a function modified natural clay nanotube catalyst and a preparation method thereof. The catalyst takes natural clay halloysite nanotubes as a carrier, the inner wall structure is firstly subjected to etching pretreatment to increase the specific surface area and enrich the pore structure, and then mesoporous CeO is constructed on the surface 2 Active layer, functional modification porphyrin functional group, Au precursor solid-carried by rich amino attachment site through coordination adsorption and in-situ reduction to Au nano-particle, effective anchoring and dispersing Au particle, controlling distribution form, crystal structure and shape and size, and finally constructing sheet array CeO by using interface redox reaction guide effect 2 -MnO 2 Packaging and curing Au nano particles by a composite oxide shell layer to obtain the functionally modified natural clay nano tube catalyst (THNTs @ CeO) 2 -Au@CeO 2 -MnO 2 Composite materials). The preparation method can reduce the phenomena of Au nano-particle agglomeration, loss and the like to a greater extent, improve the reaction activity, selectivity and thermal stability of the nano Au catalyst, and has good application prospect in the field of nano catalysis.
The invention provides a functional modified natural clay nanotube catalyst, which comprises the following components: halloysite nanotubes; mesoporous CeO modified with porphyrin unit 2 An active layer of the mesoporous CeO 2 Depositing an active layer onto the surface of the halloysite nanotubes; au nanoparticles immobilized on the amino site of the porphyrin functional group; and flake array CeO 2 -MnO 2 Composite oxide shell layer, said sheet array CeO 2 -MnO 2 And a 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 tetracarboxylporphyrin ligand.
Optionally, the mass percentage of the Au nanoparticles is 0.5-5% of the total mass of the functionally modified natural clay nanotube catalyst.
The catalyst takes natural clay halloysite nanotubes as a carrier, the inner wall structure is firstly subjected to etching pretreatment to increase the specific surface area and enrich the pore structure, and then mesoporous CeO is deposited on the surface 2 Functionally grafting a porphyrin structure, immobilizing an Au precursor on an amino site of the porphyrin structure through coordination adsorption, reducing the Au precursor into nano Au particles in situ, and finally constructing a sheet-shaped array CeO through the guiding action of an interfacial redox reaction 2 -MnO 2 Packaging and curing the nano Au particles by the shell layer of the composite oxide to obtain the functionally modified natural clay nano tube (THNTs @ CeO) 2 -Au@CeO 2 -MnO 2 Composite materials). The catalyst has high reaction activity, selectivity and thermal stability, and has good application prospect in the field of nano catalysis, wherein the catalyst is beneficial to promoting the conversion and utilization of industrial wastewater resources in the application practice of nitrobenzene substance 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 Placing the solution at a temperature of 50-90 ℃ according to a certain mass ratio, refluxing and stirring for 0.5-3 h, cooling to room temperature, centrifuging, removing supernate, washing the solid with distilled water, and drying in vacuum at 40-60 ℃ for 8-15 h 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 the THNTs @ CeO 2 A composite material;
(3) dissolving methyl p-formylbenzoate in propionic acid, heating to 140-160 ℃ for refluxing, dripping a certain amount of pyrrole within 0.5-1 h, reacting for 2-6 h, naturally cooling to room temperature, and washing and drying to obtain a purple porphyrin ester precursor; dissolving the purple porphyrin ester precursor in a mixed solution of tetrahydrofuran and methanol, adjusting an alkaline condition to hydrolyze, performing heating reaction and acidification treatment at 140-160 ℃, centrifuging, and purifying to obtain a tetracarboxylporphyrin ligand;
optionally, dissolving methyl p-formylbenzoate in propionic acid, heating to 140-160 ℃ for refluxing, then dripping a certain amount of pyrrole within 0.5-1 h, and continuing to react for 2-6 h; naturally cooling to room temperature, and sequentially washing with methanol, diethyl ether and tetrahydrofuran, purifying by column chromatography and vacuum drying at room temperature to obtain a purple porphyrin ester precursor; and then dissolving the product in a mixed solution of tetrahydrofuran and methanol, adjusting the alkaline condition to hydrolyze, carrying out heating reaction at 140-160 ℃, carrying out acidification treatment, centrifuging and purifying to obtain the tetracarboxylporphyrin ligand.
(4) Reacting the THNTs @ CeO 2 Dispersing the composite material, zirconium salt, tetracarboxylporphyrin ligand, benzoic acid and distilled water in an N, N-dimethylformamide solvent according to a certain mass ratio, and stirring at room temperature for 0.5-1 h to obtain a mixture; transferring the mixture into a polytetrafluoroethylene lining of a reaction kettle, reacting for 18-24 h at a constant temperature of 100-150 ℃, centrifuging, washing with methanol, and drying for 8-15 h at a temperature of 40-60 ℃ in vacuum to obtain the porphyrin unit modified halloysite nanotube THNTs @ CeO 2 -Py composite material;
(5) mixing Au precursor and the THNTs @ CeO 2 Dispersing a-Py composite material in an N, N-dimethylformamide solvent according to a certain mass ratio, stirring at room temperature for 6-10 h, transferring to a polytetrafluoroethylene lining of a reaction kettle, carrying out organic phase closed thermal reaction at 80-120 ℃ for 4-10 h, centrifuging, dispersing in 50-100 mL of isopropanol solution containing 5% of volume ratio, keeping a circulating cooling water at a constant temperature, irradiating by using an ultraviolet high-pressure mercury lamp for 0.5-1 h under a dark box environment, centrifuging, and drying at 40-60 ℃ for 8-15 h to obtain THNTs @ CeO 2 -Py-Au composite;
(6) taking the THNTs @ CeO in a certain mass ratio 2 Ultrasonically mixing a-Py-Au composite material and potassium permanganate in 50-150 mL of distilled water, heating to 70-90 ℃ in an oil bath for refluxing, stirring for reacting for 8-16 h, centrifuging, washing with ethanol, drying at 40-60 ℃ for 8-15 h, then placing in an inert gas atmosphere, heating to 200-400 ℃ at a heating rate of 5-10 ℃/min, and keeping at the constant temperature for 2-5 h to obtain the functionally modified natural clay nanotube catalyst.
Alternatively, the above preparation is catalyzedReacting the halloysite nanotube, concentrated sulfuric acid and H in step (1) 2 O 2 The mass ratio of the solution is 1: 10-20: 4-10; 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 catalyst preparation step (2) is 1: 2-8: 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.
Alternatively, the mass ratio of pyrrole, methyl p-formylbenzoate and propionic acid in the catalyst preparation step (3) is 1: 2-3: 55-60 parts; the pH value under the alkaline condition is 8-10, and the used adjusting solution is one of KOH solution (10 wt%) or NaOH solution (10 wt%); the pH value of the acidification treatment is 4-7, and the used adjusting solution is HCl solution (5 wt%).
Alternatively, the tetracarboxylporphyrin ligand as described in step (4) above for preparing the catalyst is THNTs @ CeO 2 The composite material comprises, by mass, 10-30% of a zirconium salt, a tetracarboxylporphyrin ligand, benzoic acid, N-dimethylformamide and distilled water, wherein the mass ratio of the zirconium salt to the tetracarboxylporphyrin ligand to the N, N-dimethylformamide to the distilled water is 1: 0.2-2.5: 5-15: 50-90: 2-15; the zirconium salt is selected from any one of zirconium oxychloride, zirconium chloride, zirconium sulfate and zirconium nitrate.
Alternatively, the THNTs @ CeO described in step (5) of preparing the catalyst above 2 The mass ratio of the-Py composite material to the Au precursor to the N, N-dimethylformamide solvent is 1: 0.015-0.2: 50-200 parts of; the Au precursor is selected from any one of tetrachloroauric acid, gold acetate, ammonium tetrachloroaurate and sodium tetrachloroaurate; the power of the ultraviolet high-pressure mercury lamp is 250W, the main radiation wavelength is 365nm, and the circulating cooling water is kept at a constant temperature; the mass percentage of the Au nano particles is 0.5-5% of the whole mass of the catalyst.
Alternatively, the THNTs @ CeO described in the catalyst preparation step (6) above 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 high-purity nitrogen and high-purity heliumGas and high purity argon gas.
Has the advantages that: the invention provides a functional modified natural clay nanotube catalyst and a preparation method thereof. The catalyst has high catalytic reaction activity, selectivity and stability in the selective reduction reaction of nitrobenzene substances, and shows good application prospect in the field of industrial wastewater resource conversion.
The invention has the characteristics that:
(1) the specific surface area and the rich pore structure are increased by etching the inner wall structure of the halloysite nanotube, the micro-reaction environment of the porous carrier interface is improved, the subsequent interface modification of metal oxide and the functional grafting of porphyrin functional groups are facilitated, and the catalyst shows a better carrier synergistic effect;
(2) an amino group in the porphyrin structure is deprotonated under a specific condition to form a more stable metal-porphyrin structure with coordinated metal ions, so that the metal cluster can be more stably immobilized; by applying the pair THNTs @ CeO 2 An interface bonding reaction is carried out to graft porphyrin functional groups, effective metal attachment sites on the interface of the carrier are increased, Au nanoparticles can be firmly anchored in the carrier structure, and the dispersion degree and the thermal stability of the Au nanoparticles are improved;
(3) the sealed thermal reaction of the organic phase promotes the Au ions to be reduced into Au nanoclusters in situ, the remaining free Au ions are adsorbed on the Au crystal, meanwhile, the porphyrin functional group loses protons to form a stable metal-porphyrin structure, and then the Au nanoclusters are converted into Au nanoparticles with good dispersity through the ultraviolet radiation reduction reaction, so that the directional anchoring of the spatial positions of the Au nanoparticles is realized;
(4) utilizing interfacial redox reaction guide effect to react on THNTs @ CeO 2 High-valence Mn with shell structure packaged by-Py-Au composite material 7+ Ion induced CeO 2 Ce in the active layer 3+ Dissolved and oxidized to form a sheet-shaped array CeO 2 -MnO 2 The composite oxide further encapsulates and solidifies Au nano particles, thereby not only enhancing the synergistic effect between Au active sites and an interlayer carrier structure, promoting the formation of a special interlayer cross-linked pore channel structure of a body system, improving the catalytic reaction performance of the nano catalyst, and simultaneously exerting the sheet array laminated mesoporous oxide pairThe structural confinement effect of the Au active site reduces the agglomeration and loss of Au nanoparticles, thereby improving the thermal stability and catalytic activity of the Au nanoparticles.
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 element distribution diagram of the functionally modified natural clay nanotube catalyst prepared in example 1;
Detailed Description
The present invention is further illustrated by the following specific examples, which are intended to be purely exemplary of the invention and are not intended to limit its scope, as various equivalent modifications of the invention will become apparent to those skilled in the art after reading the present invention and fall within the scope of the appended claims.
Example 1:
1g of halloysite nanotubes, 14mL of concentrated sulfuric acid, and 6mL of H at room temperature 2 O 2 Ultrasonically mixing the solution in a three-neck round-bottom flask, carrying out reflux reaction for 3h at 60 ℃, naturally cooling to room temperature, centrifuging, washing with distilled water until the pH of the supernatant is neutral, and carrying out vacuum drying for 12h at 50 ℃ to obtain THNTs solid;
at room temperature, 0.5g of THNTs solid and 2g of hexamethylenetetramine are dispersed in 90mL of ethanol and stirred for 0.5h, 0.75g of cerous nitrate hexahydrate and 70mL of distilled water are added dropwise during the stirring, the mixture is placed in an oil bath at 80 ℃ for heating and reflux reaction for 5h, the mixture is cooled to room temperature, centrifuged, washed by ethanol and dried for 12h at 50 ℃, and the THNTs @ CeO is prepared 2 A composite material;
taking 0.5g THNTs @ CeO at room temperature 2 The composite material, 0.33g of zirconium sulfate tetrahydrate, 0.15g of tetracarboxylporphyrin ligand (prepared in advance and stored in a refrigerator), 3.8g of benzoic acid and 3.4mL of distilled water are dispersed in 30mL of N, N-dimethylformamide solvent, and stirred for 1h at room temperature; transferring the solution to a reaction kettle for poly-tetraReacting in a vinyl fluoride lining at constant temperature of 100 ℃ for 24h, centrifuging, washing with methanol, and vacuum drying at 50 ℃ for 12h to obtain THNTs @ CeO 2 -Py composite material;
at room temperature, 0.5g of THNTs @ CeO was taken 2 -Py composite material, 1.5mL of tetrachloroauric acid solution (10mg Au/mL) and 55mL of N, N-dimethylformamide solvent are ultrasonically mixed, stirred at room temperature for 8h, transferred to a polytetrafluoroethylene lining of a reaction kettle for organic phase closed thermal reaction, the constant temperature reaction temperature is 85 ℃, the reaction time is 7h, centrifugation is carried out, then the mixture is dispersed in 50mL of isopropanol solution containing 5% volume ratio, the circulating cooling water is kept at the constant temperature, the ultraviolet high-pressure mercury lamp is irradiated for 0.5h under the dark box environment, centrifugation is carried out, drying is carried out at 60 ℃ for 8h, and THNTs @ CeO is obtained 2 -Py-Au composite;
taking 0.5g THNTs @ CeO at room temperature 2 Ultrasonically dispersing a-Py-Au composite material and 0.45g of potassium permanganate in 80mL of distilled water, heating in an oil bath at 80 ℃ to perform reflux reaction for 12 hours, cooling to room temperature, centrifuging, washing with ethanol, and drying at 50 ℃ for 10 hours; then, carrying out high-purity nitrogen atmosphere surrounding heat treatment, taking 5 ℃/min as the heating rate, heating to 300 ℃, keeping the constant temperature for 3h, and obtaining THNTs @ CeO 2 -Au@CeO 2 -MnO 2 A composite material. The obtained composite material is characterized, and the characterization results are shown in fig. 1 to 4, which show that the composite material has a specific sheet array outer layer structure, corresponding element distribution characteristics and rich pore channel structures.
Evaluation conditions were as follows: 50mL of NaBH were taken separately 4 The solution (0.5mol/L) and 50mL of 4-nitrophenol solution (20mg/L) were mixed, magnetic stirring was maintained, and 5mL of a catalyst dispersion (2g/L) was added to the above mixed solution, and the catalytic reaction was timed. After a small amount of reaction solution is taken at different reaction time and filtered by a filter head, the conversion rate and selectivity of the 4-nitrophenol are analyzed by using a UV-Vis absorption spectrometer.
The results show that: within 4min, the catalyst catalyzes and reduces 4-nitrophenol to 95 percent, and the selectivity of 4-aminophenol is 100 percent.
Example 2:
at room temperature, 1g halloysite nanotube, 15mL concentrated sulfuric acid and 6.5mL H 2 O 2 Solution in three-mouth round bottomCarrying out ultrasonic mixing in a flask, carrying out reflux reaction for 1h at 80 ℃, naturally cooling to room temperature, centrifuging, washing with distilled water until the pH of the supernatant is neutral, and carrying out vacuum drying for 10h at 55 ℃ to obtain THNTs solid;
at room temperature, 0.5g of THNTs solid and 2.5g of hexamethylenetetramine are dispersed in 85mL of ethanol and stirred for 0.5h, 0.7g of cerous nitrate hexahydrate and 60mL of distilled water are dropwise added during stirring, the mixture is placed in an oil bath at the temperature of 75 ℃ for heating and reflux reaction for 6h, the mixture is cooled to the room temperature, centrifuged, washed by ethanol and dried for 10h at the temperature of 50 ℃, and the THNTs @ CeO @ is prepared 2 A composite material;
taking 0.45g THNTs @ CeO at room temperature 2 The composite material, 0.21g of zirconium oxychloride octahydrate, 0.12g of tetracarboxylporphyrin ligand (prepared in advance and stored in a refrigerator), 2.4g of benzoic acid and 2.1mL of distilled water are dispersed in 22mL of N, N-dimethylformamide solvent, and stirred at room temperature for 0.5 h; transferring the solution into a polytetrafluoroethylene lining of a reaction kettle, reacting for 20h at a constant temperature of 120 ℃, centrifuging, washing with methanol, and drying for 8h in vacuum at 60 ℃ to obtain THNTs @ CeO 2 -Py composite material;
at room temperature, 0.3g of THNTs @ CeO was taken 2 -Py composite material and 1.3mL ammonium tetrachloroaurate solution (10mg Au/mL) are ultrasonically mixed in 50mL N, N-dimethylformamide solvent, stirred at room temperature for 8h, transferred into a polytetrafluoroethylene lining of a high-pressure reaction kettle for organic phase closed thermal reaction, the constant temperature reaction temperature is 100 ℃, the reaction time is 5h, centrifugation is carried out, then the mixture is dispersed in 50mL isopropanol solution containing 5% of volume ratio, the circulating cooling water is kept at the constant temperature condition, and the mixture is irradiated by an ultraviolet high-pressure mercury lamp under a dark box environment for 0.5h, centrifuged, dried at 50 ℃ for 10h, so that THNTs @ CeO 2 -Py-Au composite;
taking 0.3g of THNTs @ CeO at room temperature 2 Ultrasonically dispersing a-Py-Au composite material and 0.3g of potassium permanganate in 65mL of distilled water, heating in an oil bath at 90 ℃ to perform reflux reaction for 10 hours, cooling to room temperature, centrifuging, washing with ethanol, and drying at 50 ℃ for 10 hours; then carrying out high-purity argon atmosphere surrounding heat treatment, taking 6 ℃/min as the heating rate, heating to 350 ℃, keeping the constant temperature for 3h, and obtaining THNTs @ CeO 2 -Au@CeO 2 -MnO 2 A composite material.
Evaluation conditions were as follows: evaluation conditions were as follows: 50mL of NaBH were taken separately 4 The solution (0.5mol/L) and 50mL of 2-nitrophenol solution (20mg/L) were mixed, magnetic stirring was maintained, and 5mL of a catalyst dispersion (2g/L) was added to the above mixed solution, and the catalytic reaction was timed. After a small amount of reaction solution is taken at different reaction time and filtered by a filter head, a UV-Vis absorption spectrometer is used for analyzing the conversion rate and the selectivity of the 2-nitrophenol.
The results show that: within 4min, the catalyst is used for catalytic reduction of 2-nitrophenol with the conversion rate of 97% and the selectivity of 2-aminophenol of 100%.
Example 3:
at room temperature, 1.5g halloysite nanotube, 21mL concentrated sulfuric acid and 9mL H 2 O 2 Ultrasonically mixing the solution in a three-neck round-bottom flask, carrying out reflux reaction for 2h at 70 ℃, naturally cooling to room temperature, centrifuging, washing with distilled water until the pH of the supernatant is neutral, and carrying out vacuum drying for 12h at 50 ℃ to obtain THNTs solid;
at room temperature, 0.8g of THNTs solid and 3.2g of hexamethylenetetramine are dispersed in 95mL of ethanol and stirred for 1h, 1g of cerium chloride heptahydrate and 80mL of distilled water are added dropwise during the stirring, the mixture is placed in an oil bath at 85 ℃ for heating and reflux reaction for 4h, the mixture is cooled to room temperature, centrifuged, washed by ethanol and dried for 10h at 50 ℃, and the THNTs @ CeO is prepared 2 A composite material;
taking 0.6g THNTs @ CeO at room temperature 2 The composite material, 0.35g of zirconium sulfate tetrahydrate, 0.16g of tetracarboxylporphyrin ligand (prepared in advance and stored in a refrigerator), 3.8g of benzoic acid and 2.9mL of distilled water are dispersed in 32mL of 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 115 ℃ for 21h, centrifuging, washing with methanol, and vacuum drying at the temperature of 45 ℃ for 12h to obtain THNTs @ CeO 2 -Py composite material;
taking 0.45g THNTs @ CeO at room temperature 2 Ultrasonically mixing the-Py composite material and 1.9mL of sodium tetrachloroaurate solution (10mg Au/mL) in 60mL of N, N-dimethylformamide solvent, stirring for 6h at room temperature, transferring to a polytetrafluoroethylene lining of a high-pressure reaction kettle for carrying out organic phase closed thermal reaction at the constant temperature of 90 ℃ for 6h, centrifuging, then dispersing in 60mL of isopropanol solution containing 5% of volume ratio, and circularly coolingKeeping water at constant temperature, irradiating with ultraviolet high-pressure mercury lamp for 1 hr in dark box environment, centrifuging, and drying at 45 deg.C for 14 hr to obtain THNTs @ CeO 2 -Py-Au composite;
taking 0.4g THNTs @ CeO at room temperature 2 Ultrasonically dispersing a-Py-Au composite material and 0.42g of potassium permanganate in 70mL of distilled water, heating in an oil bath at 85 ℃ for reflux reaction for 12 hours, cooling to room temperature, centrifuging, washing with ethanol, and drying at 50 ℃ for 8 hours; then, carrying out high-purity nitrogen atmosphere surrounding heat treatment, taking 5 ℃/min as the heating rate, heating to 350 ℃, keeping the constant temperature for 3h, and obtaining THNTs @ CeO 2 -Au@CeO 2 -MnO 2 A composite material.
Evaluation conditions were as follows: 50mL of NaBH were taken separately 4 The solution (0.5mol/L) and 50mL of 3-nitrophenol solution (20mg/L) were mixed, magnetic stirring was maintained, and 5mL of a catalyst dispersion (2g/L) was added to the above mixed solution, and the catalytic reaction was timed. After a small amount of reaction solution is taken at different reaction time and filtered by a filter head, the conversion rate and selectivity of the 3-nitrophenol are analyzed by using a UV-Vis absorption spectrometer.
The results show that: within 8min, the catalyst catalyzes and reduces the conversion rate of 3-nitrophenol to 96 percent, and the selectivity of 3-aminophenol to 100 percent.
Example 4:
at room temperature, 1.3g halloysite nanotube, 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 2h at 80 ℃, naturally cooling to room temperature, centrifuging, washing with distilled water until the pH of the supernatant is neutral, and carrying out vacuum drying for 12h at 45 ℃ to obtain THNTs solid;
at room temperature, 0.7g of THNTs solid and 3.5g of hexamethylenetetramine are dispersed in 85mL of ethanol and stirred for 40min, during which 0.8g of cerium acetate hydrate and 70mL of distilled water are dropwise added, the mixture is placed in an oil bath at 80 ℃ and heated for reflux reaction for 6h, cooled to room temperature, centrifuged, washed by ethanol and dried for 12h at 50 ℃ to obtain THNTs @ CeO 2 A composite material;
taking 0.65g THNTs @ CeO at room temperature 2 Composite, 0.41g zirconium nitrate pentahydrate, 0.17g tetracarboxylporphyrin ligand (prepared in advance and stored in a refrigerator), 4.6g benzoic acid and 4mL distilled water dispersedStirring the mixture for 1 hour at room temperature in 37mL of N, N-dimethylformamide solvent; transferring the solution into a polytetrafluoroethylene lining of a reaction kettle, reacting for 18h at a constant temperature of 130 ℃, centrifuging, washing with methanol, and vacuum drying for 9h at 55 ℃ to obtain THNTs @ CeO 2 -Py composite material;
taking 0.6g THNTs @ CeO at room temperature 2 -Py composite material and 2.5mL tetrachloroauric acid solution (10mg/mL) are ultrasonically mixed in 80mL N, N-dimethylformamide solvent, stirred for 5h at room temperature, transferred into a polytetrafluoroethylene lining of a reaction kettle for organic phase closed thermal reaction, the constant temperature reaction temperature is 85 ℃, the reaction time is 8h, centrifuged, dispersed in 80mL isopropanol solution containing 5% volume ratio, circulated cooling water is kept at the constant temperature, an ultraviolet high-pressure mercury lamp is irradiated for 1h under the dark box environment, centrifuged, dried at 55 ℃ for 10h, and THNTs @ CeO is obtained 2 -Py-Au composite;
taking 0.6g THNTs @ CeO at room temperature 2 Ultrasonically dispersing a-Py-Au composite material and 0.55g of potassium permanganate in 80mL of distilled water, heating in an oil bath at 80 ℃ to perform reflux reaction for 15h, cooling to room temperature, centrifuging, washing with ethanol, and drying at 50 ℃ for 10 h; then, carrying out surrounding heat treatment in a high-purity argon atmosphere at a heating rate of 6 ℃/min to 300 ℃, keeping the temperature for 4h to obtain THNTs @ CeO 2 -Au@CeO 2 -MnO 2 A composite material.
Evaluation conditions were as follows: 50mL of NaBH were taken separately 4 The solution (0.5mol/L) and 50mL of 2-chloro-4-nitrophenol solution (20mg/L) were mixed, magnetic stirring was maintained, and 5mL of a catalyst dispersion (2g/L) was added to the above mixed solution, and the catalytic reaction was timed. After a small amount of reaction solution is taken at different reaction time and filtered by a filter head, a UV-Vis absorption spectrometer is used for analyzing the conversion rate and the selectivity of the 2-chloro-4-nitrophenol.
The results show that: within 6min, the catalyst catalyzes and reduces the 2-chloro-4-nitrophenol conversion rate to 95 percent and the 2-chloro-4-aminophenol selectivity to 100 percent.
Example 5:
at room temperature, 1.6g halloysite nanotube, 23mL concentrated sulfuric acid and 9.8mL H 2 O 2 The solution is stirred and mixed by magnetic force in a three-mouth round-bottom flask, and is refluxed and reacted for 1 hour at the temperature of 85 ℃, and the reaction is carried out naturallyCooling to room temperature, centrifuging, washing with distilled water until the pH of the supernatant is neutral, and vacuum drying at 55 deg.C for 10h to obtain THNTs solid;
at room temperature, 0.8g of THNTs solid and 4g of hexamethylenetetramine are dispersed in 80mL of ethanol and stirred for 1h, 1.2g of ammonium ceric nitrate and 90mL of distilled water are added dropwise during the stirring, the mixture is placed in an oil bath at 80 ℃ for heating and reflux reaction for 5.5h, the mixture is cooled to room temperature, centrifuged, washed by ethanol and dried for 10h at 50 ℃, and the THNTs @ CeO is prepared 2 A composite material;
weighing 0.75g THNTs @ CeO at room temperature 2 The composite material, 0.35g of zirconium chloride, 0.14g of tetracarboxylporphyrin ligand (prepared in advance and stored in a refrigerator), 5.7g of benzoic acid and 4mL of distilled water are dispersed in 37mL of N, N-dimethylformamide solvent, and stirred for 1h at room temperature; transferring the solution into a polytetrafluoroethylene lining of a reaction kettle, reacting for 20h at a constant temperature of 120 ℃, centrifuging, washing with methanol, and vacuum drying for 10h at a temperature of 50 ℃ to obtain THNTs @ CeO 2 -Py composite material;
taking 0.7g THNTs @ CeO at room temperature 2 Ultrasonically mixing a-Py composite material and 3mL of gold acetate solution (10mg Au/mL) in 75mL of N, N-dimethylformamide solvent, stirring at room temperature for 4.5h, transferring the mixture into a polytetrafluoroethylene lining of a reaction kettle to perform organic phase closed thermal reaction, keeping the constant temperature reaction at 110 ℃, keeping the reaction time at 4h, centrifuging, dispersing the mixture in 80mL of isopropanol solution containing 5% of volume ratio, keeping the circulating cooling water at the constant temperature, irradiating by using an ultraviolet high-pressure mercury lamp for 40min in a dark box environment, centrifuging, and drying at 45 ℃ for 12h to obtain THNTs @ CeO 2 -Py-Au composite;
taking 0.55g THNTs @ CeO at room temperature 2 Ultrasonically dispersing a-Py-Au composite material and 0.65g of potassium permanganate in 90mL of distilled water, heating in an oil bath at 90 ℃ for reflux reaction for 12 hours, cooling to room temperature, centrifuging, washing with ethanol, drying at 50 ℃ for 10 hours, centrifuging, washing with ethanol, and drying at 55 ℃ for 10 hours; then carrying out high-purity nitrogen atmosphere surrounding heat treatment, taking 8 ℃/min as the heating rate, heating to 350 ℃, keeping the constant temperature for 2.5h, and obtaining THNTs @ CeO 2 -Py@CeO 2 -MnO 2 A composite material.
Evaluation conditions were as follows: 50mL of NaBH were taken separately 4 Solution (0.5mol/L) and 50mL of 2-bromo-4-nitrophenol solution (20mg/L) were addedThe mixture was stirred magnetically, and 5mL of the catalyst dispersion (2g/L) was added to the mixed solution, and the catalytic reaction was timed. After a small amount of reaction solution is taken at different reaction time and filtered by a filter head, a UV-Vis absorption spectrometer is used for analyzing the conversion rate and the selectivity of the 2-bromo-4-nitrophenol.
The results show that: within 8min, the catalyst catalyzes and reduces the 2-bromo-4-nitrophenol conversion rate to 93 percent, and the 2-bromo-4-aminophenol selectivity to 100 percent.
Example 6:
at room temperature, 2.4g halloysite nanotubes, 28mL concentrated sulfuric acid and 12mL H were taken 2 O 2 Ultrasonically mixing the solution in a three-neck round-bottom flask, carrying out reflux reaction for 2h at 85 ℃, naturally cooling to room temperature, centrifuging, washing with distilled water until the pH of the supernatant is neutral, and carrying out vacuum drying for 12h at 50 ℃ to obtain THNTs solid;
at room temperature, 1g of THNTs solid and 5g of hexamethylenetetramine are dispersed in 95mL of ethanol and stirred for 1h, 1.5g of cerium sulfate tetrahydrate and 100mL of distilled water are added dropwise during stirring, the mixture is placed in a 75 ℃ oil bath and heated for reflux reaction for 6h, the mixture is cooled to room temperature, centrifuged, washed by ethanol and dried at 50 ℃ for 12h to obtain THNTs @ CeO 2 A composite material;
taking 0.8g THNTs @ CeO at room temperature 2 The composite material, 0.48g of zirconium nitrate pentahydrate, 0.21g of tetracarboxylporphyrin ligand (prepared in advance and stored in a refrigerator), 5.2g of benzoic acid and 4mL of distilled water are dispersed in 40mL of N, N-dimethylformamide solvent, and stirred for 1h at room temperature; transferring the solution into a polytetrafluoroethylene lining of a reaction kettle, reacting for 22h at a constant temperature of 110 ℃, centrifuging, washing with methanol, and vacuum drying for 10h at a temperature of 55 ℃ to obtain THNTs @ CeO 2 -Py composite material;
taking 0.75g of THNTs @ CeO at room temperature 2 Mixing and ultrasonically treating a-Py composite material and 3.2mL of ammonium tetrachloroaurate solution (10mg Au/mL) in 80mL of N, N-dimethylformamide solvent, stirring at room temperature for 6h, transferring the mixture into a polytetrafluoroethylene lining of a reaction kettle to perform organic phase closed thermal reaction, carrying out centrifugation at the constant temperature of 110 ℃ for 4h, then dispersing the mixture in 60mL of isopropanol solution containing 5% of volume ratio, keeping the constant temperature condition of circulating cooling water and carrying out ultraviolet high-temperature reaction in a dark box environmentIrradiating with mercury lamp for 0.5h, centrifuging, and drying at 50 deg.C for 10h to obtain THNTs @ CeO 2 -Py-Au composite;
weighing 0.7g THNTs @ CeO at room temperature 2 Ultrasonically dispersing a-Py-Au composite material and 0.9g of potassium permanganate in 100mL of distilled water, heating in an oil bath at 85 ℃ for reflux reaction for 13h, cooling to room temperature, centrifuging, washing with ethanol, and drying at 50 ℃ for 12 h; then, carrying out high-purity nitrogen atmosphere surrounding heat treatment, taking 8 ℃/min as the heating rate, heating to 320 ℃, keeping the constant temperature for 3h, and obtaining THNTs @ CeO 2 -Au@CeO 2 -MnO 2 A composite material.
Evaluation conditions were as follows: 50mL of NaBH were taken separately 4 The solution (0.5mol/L) and 50mL of 2-methyl-4-nitrophenol solution (20mg/L) were mixed, magnetic stirring was maintained, and 5mL of a catalyst dispersion (2g/L) was added to the above mixed solution, and the catalytic reaction was timed. After a small amount of reaction solution is taken at different reaction time and filtered by a filter head, a UV-Vis absorption spectrometer is used for analyzing the conversion rate and the selectivity of the 2-methyl-4-nitrophenol.
The results show that: within 15min, the catalyst catalyzes and reduces the 2-methyl-4-nitrophenol conversion rate to 92 percent and the 2-methyl-4-aminophenol selectivity to 100 percent.
Claims (10)
1. A functional modified natural clay nanotube catalyst, comprising: halloysite nanotubes; mesoporous CeO modified with porphyrin unit 2 An active layer of the mesoporous CeO 2 An active layer is deposited on the surface of the halloysite nanotube; au nanoparticles immobilized on the amino sites of the porphyrin functional groups; and flake array CeO 2 -MnO 2 Composite oxide shell layer, said sheet array CeO 2 -MnO 2 And a complex oxide shell layer is deposited on the surface of the Au nano-particles.
2. The functionally modified natural clay nanotube catalyst of claim 1, wherein the porphyrin unit is a tetracarboxylporphyrin ligand.
3. The functionally modified natural clay nanotube catalyst according to claim 1, wherein the mass percentage of the Au nanoparticles is 0.5-5% of the total mass of the functionally modified natural clay nanotube catalyst.
4. A method for preparing the functionally modified natural clay nanotube catalyst according to any one of claims 1 to 3, wherein the method comprises the steps of:
(1) taking halloysite nanotubes, concentrated sulfuric acid and H 2 O 2 Placing the solution at a temperature of 50-90 ℃ according to a certain mass ratio, refluxing and stirring for 0.5-3 h, cooling to room temperature, centrifuging, removing supernate, washing the solid with distilled water, and drying in vacuum at 40-60 ℃ for 8-15 h 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 the THNTs @ CeO 2 A composite material;
(3) dissolving methyl p-formylbenzoate in propionic acid, heating to 140-160 ℃ for refluxing, dripping a certain amount of pyrrole within 0.5-1 h, reacting for 2-6 h, naturally cooling to room temperature, and washing and drying to obtain a purple porphyrin ester precursor; dissolving the purple porphyrin ester precursor in a mixed solution of tetrahydrofuran and methanol, adjusting an alkaline condition to hydrolyze, performing heating reaction and acidification treatment at 140-160 ℃, centrifuging, and purifying to obtain a tetracarboxylporphyrin ligand;
(4) reacting the THNTs @ CeO 2 Dispersing the composite material, zirconium salt, tetracarboxylporphyrin ligand, benzoic acid and distilled water in an N, N-dimethylformamide solvent according to a certain mass ratio, and stirring at room temperature for 0.5-1 h to obtain a mixture; transferring the mixture into a polytetrafluoroethylene lining of a reaction kettle, reacting for 18-24 h at a constant temperature of 100-150 ℃, centrifuging, washing with methanol, and drying for 8-15 h at a temperature of 40-60 ℃ in vacuum to obtain the porphyrin unit modified halloysite nanotube THNTs @ CeO 2 -Py composite material;
(5) mixing Au precursor and the THNTs @ CeO 2 Dispersing a-Py composite material in an N, N-dimethylformamide solvent according to a certain mass ratio, stirring at room temperature for 6-10 h, transferring to a polytetrafluoroethylene lining of a reaction kettle, carrying out organic phase closed thermal reaction at 80-120 ℃ for 4-10 h, centrifuging, dispersing in 50-100 mL of isopropanol solution containing 5% of volume ratio, keeping a circulating cooling water at a constant temperature, irradiating by using an ultraviolet high-pressure mercury lamp for 0.5-1 h under a dark box environment, centrifuging, and drying at 40-60 ℃ for 8-15 h to obtain THNTs @ CeO 2 -Py-Au composite;
(6) taking the THNTs @ CeO in a certain mass ratio 2 Ultrasonically mixing a-Py-Au composite material and potassium permanganate in 50-150 mL of distilled water, heating to 70-90 ℃ in an oil bath for refluxing, stirring for reacting for 8-16 h, centrifuging, washing with ethanol, drying at 40-60 ℃ for 8-15 h, then placing in an inert gas atmosphere, heating to 200-400 ℃ at a heating rate of 5-10 ℃/min, and keeping at the constant temperature for 2-5 h to obtain the functionally modified natural clay nanotube catalyst.
5. The method for preparing the functionally modified natural clay nanotube catalyst according to claim 4, wherein the halloysite nanotubes, concentrated sulfuric acid and H in the step (1) 2 O 2 The mass ratio of the solution is 1: 10-20: 4 to 10, and concentrated sulfuric acid and H 2 O 2 The volume ratio of the solution is 7: 3.
6. the method for preparing the functionally modified natural clay nanotube catalyst according to claim 4, wherein in the step (2), the mass ratio of the modified halloysite nanotubes THNTs to the hexamethylenetetramine to the cerium salt is 1: 2-8: 0.3 to 2; the cerium salt is selected from any one of cerium nitrate, ammonium cerium nitrate, cerium sulfate, cerium chloride and cerium acetate.
7. The method for preparing the functionally modified natural clay nanotube catalyst according to claim 4, wherein in the step (3), the mass ratio of the pyrrole to the methyl p-formylbenzoate to the propionic acid is 1: 2-3: 55-60 parts; the pH value under the alkaline condition is 8-10.
8. The preparation method of the functional modified natural clay nanotube catalyst according to claim 4, wherein in the step (4), the tetracarboxylporphyrin ligand accounts for the THNTs @ CeO 2 The mass percentage of the composite material is 10-30%; the mass ratio of the zirconium salt to the tetracarboxylporphyrin ligand to the benzoic acid to the N, N-dimethylformamide to the distilled water is 1: 0.2-2.5: 5-15: 50-90: 2-15; the zirconium salt is selected from any one of zirconium oxychloride, zirconium chloride, zirconium sulfate and zirconium nitrate.
9. The method for preparing the functionally modified natural clay nanotube catalyst according to claim 4, wherein the THNTs @ CeO in the step (5) 2 The mass ratio of the-Py composite material to the Au precursor to the N, N-dimethylformamide solvent is 1: 0.015-0.2: 50-200 parts of; the Au precursor is selected from any one of tetrachloroauric acid, gold acetate, ammonium tetrachloroaurate and sodium tetrachloroaurate.
10. The method for preparing the functionally modified natural clay nanotube catalyst according to claim 4, wherein the THNTs @ CeO in the step (6) 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.
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