CN108816234B - Preparation method and application of derivative catalyst based on LDH (layered double hydroxide) immobilized transition metal MOF (Metal organic framework) - Google Patents
Preparation method and application of derivative catalyst based on LDH (layered double hydroxide) immobilized transition metal MOF (Metal organic framework) Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
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- B01J35/393—
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/70—Treatment of water, waste water, or sewage by reduction
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
Abstract
The invention belongs to the technical field of catalysts, and relates to a preparation method and application of a derivative catalyst based on Layered Double Hydroxide (LDH) immobilized transition Metal Organic Framework (MOF). Firstly, soaking biomass fibers into an aluminum salt aqueous solution, drying and calcining at high temperature to obtain Al2O3Fibers; then the first divalent metal salt (M)1 2+) And hexamethylenetetramine in deionized water, adding Al2O3Fiber and hydrothermal method for preparing M with fibrous micro-nano hierarchical structure1 2+An Al-LDH support; dispersing in methanol solution of trimesic acid, and adding second divalent metal salt (M)2 2+) Drying to obtain M2+Al‑LDH/M2 2+-MOF complexes, finally at H2Calcining at high temperature in the atmosphere, and cooling to obtain the catalyst. The prepared catalyst is applied to hydrogenation reduction of nitro compounds in wastewater. The prepared catalyst active center is uniformly dispersed on the surface of the carrier, has high specific surface area and high catalytic activity, and solves the problems of easy agglomeration, difficult recovery and the like of the traditional catalyst. The preparation method is simple and the cost is low.
Description
Technical Field
The invention belongs to the technical field of catalysts, relates to a Layered Double Hydroxide (LDH) nanosheet fixed Metal Organic Framework (MOF) catalyst, and particularly relates to a derivative catalyst (M) based on LDH fixed transition metal MOF1 2+Al-LDO/ M2) The preparation method and the application thereof.
Background
In industrial production, a large amount of waste water containing nitro compounds is directly discharged into an ecological system without treatment, so that serious water pollution is caused, and various diseases such as poisoning, blood diseases, cancers and the like are caused. The state has strict regulation on the discharge concentration of the nitro compounds (less than or equal to 5 mg/L), and the nitro compounds are listed in the blacklist of the environmental priority pollutants in China. The nitro compounds currently used for treating wastewater are mainly biochemical, chemical oxidation, adsorption and catalytic hydrogenation reduction. In recent years, with the development of technology and the improvement of environmental awareness, the catalytic hydrogenation reduction method has attracted more and more attention due to its advantages of simple post-treatment, low catalyst consumption, recyclability, etc. The method has no other by-products in the reaction process, the catalyst can be recycled, and the method has great development and utilization prospects in the aspect of treating wastewater containing nitro compounds.
Currently, the research on the catalytic reduction technology of nitro compounds mainly focuses on the nano catalysis of noble metals, but the noble metals are scarce and expensive, and are not beneficial to wide application. In contrast, the transition metal is cheap and easy to obtain, and has wide application in the field of catalysis. However, the unprotected and bare transition metal nanoparticles have high catalytic activity and high surface energy, so that the nanoparticles are easy to agglomerate and deactivate in the catalytic process, thereby causing the rapid reduction of catalytic efficiency and greatly shortening the cycle period. In recent years, various porous supports and corresponding synthesis methods (template method, in-situ growth, etc.) have been used for the preparation of metal nanoparticle catalyst supports. However, the carrier preparation steps are complicated, so that the carrier preparation has the defects of poor reproducibility, high cost, low ordered degree of void distribution and the like. In addition, when active centers are introduced into the ordered pore channels, the introduced compounds are often agglomerated in the pore channels of the carrier or only react on the outer surface due to the chemical action with low selectivity, the active centers are not uniformly dispersed and are easy to fall off, the specific surface area of the catalyst is reduced, and the utilization rate of the catalytic active centers is greatly reduced.
The metal-organic framework (MOF) material has excellent structural characteristics, the active centers are uniformly dispersed, the gaps are adjustable, and the preparation of the high-efficiency functional catalyst by using the MOF as a self-sacrifice template is widely researched. However, the MOF crystals studied at present have the problems of large size, low active center exposure, large mass transfer resistance and the like, and the catalytic activity is severely limited.
Disclosure of Invention
In view of the above-mentioned deficiencies of the prior art, it is an object of the present invention to disclose a method for preparing a derivatized non-noble metal nanoparticle catalyst using a hierarchical structure LDH support for the immobilization of MOFs.
Technical scheme
Derivative catalyst (M) based on LDH (layered double hydroxide) immobilized transition metal MOF (Metal organic framework)1 2+Al-LDO/ M2) The preparation method comprises the following steps:
a) 、Al2O3preparing fibers: soaking biomass fibers in an aluminum salt aqueous solution with the concentration of 0.1-0.2M, performing ultrasonic treatment for 4 hours, taking out, cleaning with deionized water to remove excessive metal ions on the surface, drying at 100 ℃ for 6 hours, calcining at 400-800 ℃ for 1-5 hours in an air atmosphere, preferably calcining at 600 ℃ for 2 hours to obtain Al2O3 The fiber is characterized in that the mass-volume ratio of the biomass fiber to an aluminum salt aqueous solution is 1g: 30-80 mL, and the aluminum salt is Al (NO)3)3∙9H2O or Al2(SO4)3；
b) Fibrous micro-nano hierarchical structure M1 2+Preparing an Al-LDH carrier: adding a first divalent metal salt (M)1 2+) And hexamethylenetetramine in deionized waterAdding Al2O3 Uniformly stirring the fibers at normal temperature, transferring the fibers into a reaction kettle, reacting for 8-24 hours at 70-180 ℃, preferably reacting for 10 hours at 100 ℃, washing the fibers with deionized water and ethanol respectively for three times after centrifugation, drying for 12 hours at 40-100 ℃, preferably drying for 12 hours at 60 ℃ to obtain the M with the hierarchical structure1 2+The Al-LDH carrier is characterized in that the metal of the first divalent metal salt is any one of Zn, Mg, Cu, Ni and Co, the concentration of the metal is 0.05-0.10M, the concentration of hexamethylenetetramine is 0.10-0.20M, and Al is2O3The mass-to-volume ratio of the fibers to the deionized water is 1g: 200-300 mL;
c) 、M2+Al-LDH/ M2 2+-preparation of MOF complexes: the obtained M1 2+Dispersing Al-LDH carrier in methanol solution of trimesic acid, ultrasonically dispersing for 1 h, and slowly adding second divalent metal salt (M)2 2+) The methanol solution is magnetically stirred for 3 hours, after centrifugation, deionized water and methanol are respectively washed for three times, and the mixture is dried in vacuum for 12 hours at the temperature of 40-100 ℃, preferably 60 ℃ to obtain M1 2+Al-LDH/ M2 2+-a MOF complex wherein the concentration of said methanol trimesate solution is 1-2M, M1 2+The mass-volume ratio of the Al-LDH carrier to the methanol solution is 1g: 200-400 mL, the metal of the second divalent metal salt is any one of Cu, Co and Ni, and the concentration is 0.03-0.08 mM;
d) 、M1 2+Al-LDO/ M2preparing a catalyst: the obtained M1 2+Al-LDH/ M2 2+-MOF complex in H2Calcining for 1-4 h at 200-450 ℃ in the atmosphere, preferably calcining for 3 h at 300 ℃, heating at the rate of 1-3 ℃/min, and naturally cooling to room temperature to obtain the catalyst.
In a preferred embodiment of the present invention, the biomass fiber in step a) is a biomass primary fiber, which comprises cotton, plant leaves, plant stems, and hemp, preferably absorbent cotton.
In a preferred embodiment of the present invention, the aluminum salt in step a) is preferably Al (NO)3)3∙9H2O, preferably at a concentration of 0.17M; the amount of biomass fiber (g) and the volume of aluminum salt solution (mL)The numerical ratio of (a) to (b) is preferably 1g: 50 mL.
In a preferred embodiment of the present invention, the concentration of the first divalent metal salt in step b) is preferably 0.08M; the concentration of hexamethylene tetramine is preferably 0.16M; al (Al)2O3The ratio of the amount of fiber (g) to the volume of deionized water (mL) is preferably 1g:250 mL.
In a preferred embodiment of the present invention, the concentration of the methanol trimesate solution in step c) is preferably 1.6M; m1 2 +The numerical ratio of the using amount (g) of the Al-LDH carrier to the volume of the methanol solution is preferably 1g to 300 mL; the concentration of the second divalent metal salt is preferably 0.05 mM, and the vacuum drying temperature is preferably 60 ℃.
In a preferred embodiment of the present invention, the temperature increase rate in step d) is preferably 1 ℃/min.
The derivatized non-noble metal nanoparticle catalyst (M) prepared according to the process of the invention1 2+Al-LDO/ M2) The LDH nanosheet with the fiber morphology and the micro-nano hierarchical structure is used as a carrier, MOF crystals are fixed on the surface of the LDH nanosheet in situ, non-noble metal nanoparticles are uniformly distributed on the surface of the carrier, and the particle size of the nanoparticles is about 15 nm.
The invention also aims to apply the prepared catalyst to the hydrogenation reduction of nitro compounds in wastewater.
Experiment for catalytic hydrogenation reduction of 4-nitrophenol
The invention uses 4-nitrophenol to simulate nitro compounds in wastewater: 30 μ L of 4-nitrophenol (10 mM), 1.0 mL of freshly prepared NaBH4(0.12M) and 2 mL of deionized water were added to a quartz cuvette and stirred for 3min, followed by 20. mu.L of the prepared M1 2+Al-LDO/ M2Aqueous catalyst solution (0.5 mg/mL). An ultraviolet-visible spectrophotometer (Agilent Cary 8454) was used to monitor the reaction process, with a scanning wavelength range of 200 and 800 nm. The absorbance is converted into concentration according to a standard curve, and then the catalytic efficiency D% is calculated according to the formula (1).
In the formulaC 0AndC trespectively, the initial and the time of the 4-nitrophenol solutiont(min) concentration.
The invention has the characteristics that:
(1) the hierarchical structure LDH nanosheet is based on biomass fibers, has a stable micro-nano hierarchical structure, is simple and controllable in synthesis steps and low in cost, and is difficult to achieve by a traditional physical chemical method.
(2) The MOF crystal is constructed on the surface of the LDH nanosheet in situ, so that the dispersibility of the MOF crystal on the surface of the substrate is effectively improved, the crystal size is controlled, the problem of crystal agglomeration is solved, and the activity of the catalyst can be effectively promoted.
(3) The MOF-derived high-efficiency catalyst prepared by calcining the catalyst precursor in a reducing gas has the advantages that the transition metal nanoparticles fixed on the surfaces of the nanosheets have high specific surface area and high active center exposure ratio, have high catalytic activity in catalytic hydrogenation reduction nitro-compound reaction, and have high catalytic stability.
Advantageous effects
The invention provides a preparation method for preparing a derived non-noble metal nanoparticle catalyst by fixing an MOF (metal organic framework) by using an LDH (layered double hydroxide) carrier with a hierarchical structure, wherein the MOF crystal grows in situ on the surface of an LDH nanosheet, so that the uniform dispersity of transition metal nanoparticles with catalytic performance is improved, the fixed transition metal nanoparticles show high catalytic hydrogenation reduction nitro compound activity, and the stability is remarkably improved. The prepared catalyst active center is uniformly dispersed on the surface of the carrier, has high specific surface area, has high catalytic activity in the aspect of catalytic hydrogenation reduction of nitro compound, and simultaneously solves the problems of easy agglomeration, difficult recovery and the like of the traditional catalyst. The preparation method is simple, has low cost, is beneficial to large-scale industrial production, and has remarkable economic and social benefits.
Drawings
FIG. 1 is an electron micrograph of ZnAl-LDH wherein (a) is SEM and (b) is TEM;
FIG. 2 is an electron micrograph of ZnAl-LDH-Cu-MOF wherein (a) is SEM and (b) is TEM;
FIG. 3 is an electron micrograph of a ZnAl-LDO-Cu catalyst, wherein (a) is SEM and (b) is TEM.
Detailed Description
The present invention will be described in detail below with reference to examples to enable those skilled in the art to better understand the present invention, but the present invention is not limited to the following examples.
Example 1
a) Al2O3Preparing fibers: soaking 1.88 g absorbent cotton fiber in 150 mL of 0.1M Al2(SO4)3And (4) ultrasonically treating the water solution for 4 hours, and then washing the soaked absorbent cotton fibers with deionized water to remove excessive metal ions on the surface. Drying at 100 ℃ for 6 hours, calcining at 400 ℃ for 1 hour in air atmosphere to obtain Al2O3 A fiber.
b) Preparing a ZnAl-LDH carrier with a fibrous micro-nano hierarchical structure: adding Zn (NO)3)2∙6H2O (0.05M) and hexamethylenetetramine (0.10M) were dissolved in 25 mL of deionized water. Then 0.083 g of Al prepared in step a)2O3 Adding the fiber into the solution, stirring at normal temperature for 30 min, transferring into a reaction kettle, reacting at 70 ℃ for 8 h, centrifuging, washing with water and ethanol for three times respectively, and drying at 40 ℃ for 12 h to obtain the ZnAl-LDH carrier with the hierarchical structure.
c) Preparation of ZnAl-LDH/Co-MOF composite: dispersing 0.075 g of ZnAl-LDH carrier prepared in the step b) in 30 mL of trimesic acid (1.0M) methanol solution, ultrasonically dispersing for 1 h, and slowly adding Co (NO)3)2·6H2Magnetically stirring O (0.03M) in methanol for 3 h, centrifuging, washing with deionized water and methanol for 3 times respectively, and vacuum drying at 40 ℃ for 12 h to obtain the ZnAl-LDH/Co-MOF compound.
d) Preparation of ZnAl-LDO/Co catalyst: the ZnAl-LDH/Co-MOF compound prepared in the step c) is put in H2Calcining for 1 h at 200 ℃ in the atmosphere, wherein the heating rate is 1 ℃/min. Cooling to room temperature, and collecting the product to obtain the ZnAl-LDO/Co catalyst.
The prepared catalyst can be used for reducing the 4-nitro compound by catalytic hydrogenation within 15 min, and the efficiency reaches 100%.
Example 2
a) Al2O3Preparing fibers: soaking 2.50 g of absorbent cotton fiber in 150 mL of 0.13M Al (NO)3)3∙9H2And (4) carrying out ultrasonic treatment on the O aqueous solution for 4 hours, and then washing the soaked absorbent cotton fibers with deionized water to remove excessive metal ions on the surfaces. Drying at 100 ℃ for 6 hours, calcining at 500 ℃ for 2 hours in air atmosphere to obtain Al2O3 A fiber.
b) Preparing a CuAl-LDH carrier with a fibrous micro-nano hierarchical structure: adding Cu (NO)3)2∙3H2O (0.06M) and hexamethylenetetramine (0.12M) were dissolved in 25 mL of deionized water. Then 0.089 g of Al prepared in step a) are added2O3 Adding the fibers into the solution, stirring at normal temperature for 30 min, transferring into a reaction kettle, reacting at 120 ℃ for 10 h, centrifuging, washing with water and ethanol for three times respectively, and drying at 60 ℃ for 12 h to obtain the CuAl-LDH carrier with the hierarchical structure.
c) Preparation of CuAl-LDH/Co-MOF complexes: dispersing 0.086 g of CuAl-LDH carrier prepared in the step b) in 30 mL of trimesic acid (1.2M) methanol solution, ultrasonically dispersing for 1 h, and slowly adding Co (NO)3)2·6H2Magnetically stirring a methanol solution of O (0.04M) for 3 hours, centrifuging, washing with deionized water and methanol for 3 times respectively, and vacuum drying at 50 ℃ for 12 hours to obtain the CuAl-LDH/Co-MOF compound.
d) Preparation of CuAl-LDO/Co catalyst: the CuAl-LDH/Co-MOF compound prepared in the step c) is put in H2Calcining for 2 h at 200 ℃ in the atmosphere, wherein the heating rate is 2 ℃/min. Cooling to room temperature, and collecting the product to obtain the CuAl-LDO/Co catalyst.
The prepared catalyst can be used for reducing the 4-nitro compound by catalytic hydrogenation within 10min, and the efficiency reaches 100%.
Example 3
a) Al2O3Preparing fibers: 3.75 g of absorbent cotton fiber was soaked in 150 mL of 0.15M Al (NO)3)3∙9H2In O aqueous solution, sonication 4And h, washing the soaked absorbent cotton fibers with deionized water to remove excessive metal ions on the surface. Drying at 100 deg.C for 6 hr, calcining at 500 deg.C in air atmosphere for 3 hr to obtain Al2O3 A fiber.
b) Preparing a NiAl-LDH carrier with a fibrous micro-nano hierarchical structure: mixing Ni (CH)3COO)2・4H2O (0.07M) and hexamethylenetetramine (0.14M) were dissolved in 25 mL of deionized water. Then 0.096 g of Al prepared in step a)2O3 Adding the fiber into the solution, stirring at normal temperature for 30 min, transferring into a reaction kettle, reacting at 110 ℃ for 10 h, centrifuging, washing with water and ethanol for three times respectively, and drying at 80 ℃ for 12 h to obtain the NiAl-LDH carrier with the hierarchical structure.
c) Preparation of NiAl-LDH/Ni-MOF complexes: dispersing 0.12 g of the NiAl-LDH carrier prepared in the step b) in 30 mL of trimesic acid (1.4M) methanol solution, ultrasonically dispersing for 1 h, and slowly adding Ni (NO)3)2·6H2Magnetically stirring the methanol solution of O (0.06M) for 3 h, centrifuging, washing with deionized water and methanol for 3 times respectively, and vacuum drying at 80 ℃ for 12 h to obtain the NiAl-LDH/Ni-MOF compound.
d) Preparation of NiAl-LDO/Ni catalyst: subjecting the NiAl-LDH/Ni-MOF complex prepared in step c) to H2Calcining at 200 deg.C for 3 h in atmosphere, and heating rate of 2 deg.C/min. Cooling to room temperature, and collecting the product to obtain the NiAl-LDO/Ni catalyst.
The efficiency of the prepared catalyst for catalytic hydrogenation reduction of 4-nitro compounds within 8 min reaches 100%.
Example 4
a) Al2O3Preparing fibers: soaking 3.0 g absorbent cotton fiber in 150 mL of 0.17M Al (NO)3)3∙9H2And (4) carrying out ultrasonic treatment on the O aqueous solution for 4 hours, and then washing the soaked absorbent cotton fibers with deionized water to remove excessive metal ions on the surfaces. Drying at 100 ℃ for 6 hours, calcining at 600 ℃ for 2 hours in air atmosphere to obtain Al2O3 A fiber.
b) Preparing a ZnAl-LDH carrier with a fibrous micro-nano hierarchical structure: adding Zn (NO)3)2∙6H2O (0.08M) and hexamethylenetetramine (0.16M) were dissolved in 25 mL of deionized water. Then 0.10 g of Al prepared in step a)2O3 Adding the fiber into the solution, stirring at normal temperature for 30 min, transferring into a reaction kettle, reacting at 75 ℃ for 10 h, centrifuging, washing with water and ethanol for three times respectively, and drying at 60 ℃ for 12 h to obtain the ZnAl-LDH carrier with a hierarchical structure (see figure 1).
c) Preparation of ZnAl-LDH/Cu-MOF complex: dispersing 0.10 g of ZnAl-LDH carrier prepared in the step b) in 30 mL of trimesic acid (1.6M) methanol solution, ultrasonically dispersing for 1 h, and slowly adding Cu (NO)3)2·6H2Magnetically stirring O (0.05M) in methanol for 3 h, centrifuging, washing with deionized water and methanol for 3 times, and vacuum drying at 60 deg.C for 12 h to obtain ZnAl-LDH/Cu-MOF complex (see FIG. 2).
d) Preparation of ZnAl-LDO/Cu catalyst: the ZnAl-LDH/Cu-MOF composite prepared in the step c) is put in H2Calcining at 300 deg.C for 3 h in the atmosphere, and heating rate of 1 deg.C/min. Cooling to room temperature, and collecting the product to obtain the ZnAl-LDO/Cu catalyst (see figure 3).
The prepared catalyst can be used for reducing the 4-nitro compound by catalytic hydrogenation within 2 min, and the efficiency reaches 100%.
Example 5
a) Al2O3Preparing fibers: 5.0 g of absorbent cotton fibers were soaked in 150 mL of 0.2M Al2(SO4)3And (4) ultrasonically treating the water solution for 4 hours, and then washing the soaked absorbent cotton fibers with deionized water to remove excessive metal ions on the surface. Drying at 100 deg.C for 6 hr, calcining at 800 deg.C in air atmosphere for 5 hr to obtain Al2O3 A fiber.
b) Preparing a ZnAl-LDH carrier with a fibrous micro-nano hierarchical structure: adding Zn (NO)3)2∙6H2O (0.05M) and hexamethylenetetramine (0.20M) were dissolved in 25 mL of deionized water. Then 0.125 g of Al prepared in step a)2O3 Adding fiber into the above solution, stirring at room temperature for 30 min, transferring into a reaction kettle, reacting at 180 deg.C for 24 hr, centrifuging, washing with water and ethanol for three times, and drying at 100 deg.C for 12 hr to obtain the final productZnAl-LDH carrier with a hierarchical structure.
c) Preparation of ZnAl-LDH/Cu-MOF complex: dispersing 0.15 g of ZnAl-LDH carrier prepared in the step b) in 30 mL of trimesic acid (2.0M) methanol solution, ultrasonically dispersing for 1 h, and slowly adding Cu (NO)3)2·3H2Magnetically stirring an O (0.08M) methanol solution for 3 hours, centrifuging, washing with deionized water and methanol for 3 times respectively, and vacuum drying at 100 ℃ for 12 hours to obtain the ZnAl-LDH/Cu-MOF compound.
d) Preparation of ZnAl-LDO/Cu catalyst: the ZnAl-LDH/Cu-MOF composite prepared in the step c) is put in H2Calcining for 4 h at 450 ℃ in the atmosphere, wherein the heating rate is 3 ℃/min. Cooling to room temperature, and collecting the product to obtain the ZnAl-LDO/Cu catalyst.
The prepared catalyst can be used for reducing the 4-nitro compound by catalytic hydrogenation within 7 min, and the efficiency reaches 100%.
Example 6
a) Al2O3Preparing fibers: 3.0 g of dehydrated sisal fibers were soaked in 150 mL of 0.17M Al (NO)3)3∙9H2And (4) carrying out ultrasonic treatment in an O aqueous solution for 4 hours, and then washing the soaked sisal fiber with deionized water to remove excessive metal ions on the surface. Drying at 100 ℃ for 6 hours, calcining at 600 ℃ for 2 hours in air atmosphere to obtain Al2O3 A fiber.
b) Preparing a ZnAl-LDH carrier with a fibrous micro-nano hierarchical structure: adding Zn (NO)3)2∙6H2O (0.08M) and hexamethylenetetramine (0.16M) were dissolved in 25 mL of deionized water. Then 0.10 g of Al prepared in step a)2O3 Adding the fiber into the solution, stirring at normal temperature for 30 min, transferring into a reaction kettle, reacting at 75 ℃ for 10 h, centrifuging, washing with water and ethanol for three times respectively, and drying at 60 ℃ for 12 h to obtain the ZnAl-LDH carrier with the hierarchical structure.
c) Preparation of ZnAl-LDH/Cu-MOF complex: dispersing 0.10 g of ZnAl-LDH carrier prepared in the step b) in 30 mL of trimesic acid (1.6M) methanol solution, ultrasonically dispersing for 1 h, and slowly adding Co (NO)3)2·6H2O (0.03M) in methanol, magnetically stirring for 3 hCentrifuging, washing 3 times respectively by deionized water and methanol, and drying in vacuum at 60 ℃ for 12 h to obtain the ZnAl-LDH/Cu-MOF compound.
d) Preparation of ZnAl-LDO/Cu catalyst: the ZnAl-LDH/Cu-MOF composite prepared in the step c) is put in H2Calcining at 300 deg.C for 3 h in the atmosphere, and heating rate of 1 deg.C/min. Cooling to room temperature, and collecting the product to obtain the ZnAl-LDO/Cu catalyst.
The efficiency of the prepared catalyst for catalytic hydrogenation reduction of 4-nitro compounds within 8 min reaches 100%.
Example 7
a) Al2O3Preparing fibers: soaking 3.0 g dehydrated bamboo filament fiber in 150 mL Al (NO) solution with concentration of 0.17M3)3∙9H2And (4) carrying out ultrasonic treatment on the bamboo filament fibers in an O aqueous solution for 4 hours, and then washing the soaked bamboo filament fibers with deionized water to remove excessive metal ions on the surfaces. Drying at 100 ℃ for 6 hours, calcining at 600 ℃ for 2 hours in air atmosphere to obtain Al2O3 A fiber.
b) Preparing a ZnAl-LDH carrier with a fibrous micro-nano hierarchical structure: adding Zn (NO)3)2∙6H2O (0.08M) and hexamethylenetetramine (0.16M) were dissolved in 25 mL of deionized water. Then 0.10 g of Al prepared in step a)2O3 Adding the fiber into the solution, stirring at normal temperature for 30 min, transferring into a reaction kettle, reacting at 75 ℃ for 10 h, centrifuging, washing with water and ethanol for three times respectively, and drying at 60 ℃ for 12 h to obtain the ZnAl-LDH carrier with the hierarchical structure.
c) Preparation of ZnAl-LDH/Cu-MOF complex: dispersing 0.10 g of ZnAl-LDH carrier prepared in the step b) in 30 mL of trimesic acid (1.6M) methanol solution, ultrasonically dispersing for 1 h, and slowly adding Co (NO)3)2·6H2Magnetically stirring an O (0.03M) methanol solution for 3 hours, centrifuging, washing with deionized water and methanol for 3 times respectively, and vacuum drying at 60 ℃ for 12 hours to obtain the ZnAl-LDH/Cu-MOF compound.
d) Preparation of ZnAl-LDO/Cu catalyst: the ZnAl-LDH/Cu-MOF composite prepared in the step c) is put in H2Calcining at 300 deg.C for 3 h in the atmosphere, and heating rate of 1 deg.C/min. Cooling to room temperature, and collecting the product to obtain the ZnAl-LDO/Cu catalyst.
The prepared catalyst can be used for reducing the 4-nitro compound by catalytic hydrogenation within 5 min, and the efficiency reaches 100%.
Example 8
a) Al2O3Preparing fibers: soaking 3.0 g dehydrated radix Ophiopogonis Japonici fiber in 150 mL Al (NO) with concentration of 0.17M3)3∙9H2And (4) carrying out ultrasonic treatment on the O aqueous solution for 4 hours, and then cleaning the soaked broadleaf radix ophiopogonis fibers with deionized water to remove excessive metal ions on the surfaces. Drying at 100 ℃ for 6 hours, calcining at 600 ℃ for 2 hours in air atmosphere to obtain Al2O3 A fiber.
b) Preparing a ZnAl-LDH carrier with a fibrous micro-nano hierarchical structure: adding Zn (NO)3)2∙6H2O (0.08M) and hexamethylenetetramine (0.16M) were dissolved in 25 mL of deionized water. Then 0.10 g of Al prepared in step a)2O3 Adding the fiber into the solution, stirring at normal temperature for 30 min, transferring into a reaction kettle, reacting at 75 ℃ for 10 h, centrifuging, washing with water and ethanol for three times respectively, and drying at 60 ℃ for 12 h to obtain the ZnAl-LDH carrier with the hierarchical structure.
c) Preparation of ZnAl-LDH/Cu-MOF complex: dispersing 0.10 g of ZnAl-LDH carrier prepared in the step b) in 30 mL of trimesic acid (1.6M) methanol solution, ultrasonically dispersing for 1 h, and slowly adding Co (NO)3)2·6H2Magnetically stirring an O (0.03M) methanol solution for 3 hours, centrifuging, washing with deionized water and methanol for 3 times respectively, and vacuum drying at 60 ℃ for 12 hours to obtain the ZnAl-LDH/Cu-MOF compound.
d) Preparation of ZnAl-LDO/Cu catalyst: the ZnAl-LDH/Cu-MOF composite prepared in the step c) is put in H2Calcining at 300 deg.C for 3 h in the atmosphere, and heating rate of 1 deg.C/min. Cooling to room temperature, and collecting the product to obtain the ZnAl-LDO/Cu catalyst.
The efficiency of the prepared catalyst for catalytic hydrogenation reduction of 4-nitro compounds within 9 min reaches 100%.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes performed by the present invention or directly or indirectly applied to other related technical fields are included in the scope of the present invention.
Claims (15)
1. Derivative catalyst M based on LDH (layered double hydroxide) immobilized transition metal MOF (Metal organic framework)1 2+Al-LDO/ M2The preparation method is characterized by comprising the following steps:
a)、Al2O3preparing fibers: soaking biomass fibers in an aluminum salt aqueous solution with the concentration of 0.1-0.2M, performing ultrasonic treatment for 4 hours, taking out, cleaning with deionized water to remove excessive metal ions on the surface, drying at 100 ℃ for 6 hours, and calcining at 400-800 ℃ in an air atmosphere for 1-5 hours to obtain Al2O3 The fiber is characterized in that the mass-volume ratio of the biomass fiber to an aluminum salt aqueous solution is 1g: 30-80 mL, and the aluminum salt is Al (NO)3)3∙9H2O or Al2(SO4)3；
b) Fibrous micro-nano hierarchical structure M1 2+Preparing an Al-LDH carrier: the first divalent metal salt M1 2+And hexamethylenetetramine in deionized water, adding Al2O3 Uniformly stirring the fibers at normal temperature, transferring the fibers into a reaction kettle, reacting for 8-24 hours at 70-180 ℃, washing the fibers with deionized water and ethanol respectively for three times after centrifugation, and drying for 12 hours at 40-100 ℃ to obtain the M with the hierarchical structure1 2+The Al-LDH carrier is characterized in that the metal of the first divalent metal salt is any one of Zn, Mg, Cu, Ni and Co, the concentration of the metal is 0.05-0.10M, the concentration of hexamethylenetetramine is 0.10-0.20M, and Al is2O3The mass-to-volume ratio of the fibers to the deionized water is 1g: 200-300 mL;
c)、M1 2+Al-LDH/ M2 2+-preparation of MOF complexes: the obtained M1 2+Dispersing Al-LDH carrier in methanol solution of trimesic acid, ultrasonically dispersing for 1 h, slowly adding second divalent metal salt M2 2+Magnetically stirring the methanol solution for 3 hours, respectively washing the methanol solution with deionized water for three times after centrifugation, and drying the methanol solution for 12 hours in vacuum at the temperature of 40-100 ℃ to obtain M1 2+Al-LDH/ M2 2+-a MOF complex wherein the concentration of said methanol trimesate solution is 1-2M, M1 2+The mass-volume ratio of the Al-LDH carrier to the methanol solution is 1g: 200-400 mL, the metal of the second divalent metal salt is any one of Cu, Co and Ni, and the concentration is 0.03-0.08 mM;
d)、M1 2+Al-LDO/ M2preparing a catalyst: the obtained M1 2+Al-LDH/ M2 2+-MOF complex in H2Calcining for 1-4 h at 200-450 ℃ in the atmosphere, heating at the rate of 1-3 ℃/min, and naturally cooling to room temperature to obtain the catalyst.
2. The LDH-immobilized transition metal MOF-based derivative catalyst M of claim 11 2+Al-LDO/ M2The preparation method is characterized by comprising the following steps: the biomass fiber in the step a) is a biomass protofiber which comprises cotton, plant leaves, plant stems and hemp.
3. The LDH-immobilized transition metal MOF-based derivative catalyst M of claim 11 2+Al-LDO/ M2The preparation method is characterized by comprising the following steps: the biomass fiber in the step a) is absorbent cotton.
4. The LDH-immobilized transition metal MOF-based derivative catalyst M of claim 11 2+Al-LDO/ M2The preparation method is characterized by comprising the following steps: drying at 100 ℃ for 6h, and calcining at 600 ℃ for 2 h in an air atmosphere.
5. The LDH-immobilized transition metal MOF-based derivative catalyst M of claim 11 2+Al-LDO/ M2The preparation method is characterized by comprising the following steps: the aluminum salt in the step a) is Al (NO)3)3∙9H2O, concentration 0.17M; the mass-volume ratio of the biomass fibers to the aluminum salt aqueous solution is 1g: 50 mL.
6. According to claimThe LDH-immobilized transition metal MOF-based derivative catalyst M of claim 11 2+Al-LDO/ M2The preparation method is characterized by comprising the following steps: subjecting the first divalent metal salt M to the step b)1 2+And hexamethylenetetramine in deionized water, adding Al2O3 The fiber is stirred evenly at normal temperature and then transferred into a reaction kettle to react for 10 hours at 100 ℃.
7. The LDH-immobilized transition metal MOF-based derivative catalyst M of claim 11 2+Al-LDO/ M2The preparation method is characterized by comprising the following steps: washing with deionized water and ethanol for three times respectively after centrifugation in the step b), and drying at 60 ℃ for 12 h to obtain M with a hierarchical structure1 2+An Al-LDH carrier.
8. The LDH-immobilized transition metal MOF-based derivative catalyst M of claim 11 2+Al-LDO/ M2The preparation method is characterized by comprising the following steps: the concentration of the first divalent metal salt in the step b) is 0.08M; the concentration of hexamethylene tetramine is 0.16M; al (Al)2O3The mass-to-volume ratio of the fibers to the deionized water was 1g:250 mL.
9. The LDH-immobilized transition metal MOF-based derivative catalyst M of claim 11 2+Al-LDO/ M2The preparation method is characterized by comprising the following steps: washing the centrifuged deionized water and methanol for three times respectively in the step c), and carrying out vacuum drying for 12 h at 60 ℃.
10. The LDH-immobilized transition metal MOF-based derivative catalyst M of claim 11 2+Al-LDO/ M2The preparation method is characterized by comprising the following steps: the concentration of the methanol trimesate solution in the step c) is 1.6M; m1 2+The mass-volume ratio of the Al-LDH carrier to the methanol solution is 1g:300 mL; the concentration of the second divalent metal salt was 0.05 mM, and the vacuum drying temperature was 60 ℃.
11. The LDH-immobilized transition metal MOF-based derivative catalyst M of claim 11 2+Al-LDO/ M2The preparation method is characterized by comprising the following steps: m to be prepared as described in step d)1 2+Al-LDH/ M2 2+-MOF complex in H2Calcining for 3 h at 300 ℃ in the atmosphere, heating at the rate of 1-3 ℃/min, and naturally cooling to room temperature to obtain the catalyst.
12. The LDH-immobilized transition metal MOF-based derivative catalyst M of claim 11 2+Al-LDO/ M2The preparation method is characterized by comprising the following steps: the temperature rise rate in step d) is 1 ℃/min.
13. LDH-immobilized transition metal MOF-based derivative catalyst M prepared by the method of any one of claims 1 to 121 2+Al-LDO/ M2。
14. The LDH-immobilized transition metal MOF-based derivative catalyst M of claim 131 2+Al-LDO/ M2The method is characterized in that: the catalyst takes LDH nanosheets with fiber morphology and micro-nano hierarchical structures as carriers, MOF crystals are fixed on the surfaces of the LDH nanosheets in situ, non-noble metal nanoparticles are uniformly distributed on the surfaces of the carriers, and the particle size of the nanoparticles is 15 nm.
15. An LDH-immobilized transition metal MOF-based derivative catalyst M of claim 131 2+Al-LDO/ M2The application of (2), which is characterized in that: the catalyst is applied to hydrogenation reduction of nitro compounds in wastewater.
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| CN112341631B (en) * | 2020-10-30 | 2022-06-10 | 陕西科技大学 | Method for synthesizing ZnAl-MOF-LDH nano material based on template-oriented method |
| CN113184921B (en) * | 2021-04-23 | 2023-10-13 | 江苏大学 | LDH-based composite material based on nickel-containing sludge and preparation method thereof |
| CN113926430B (en) * | 2021-11-19 | 2023-10-20 | 太原理工大学 | Preparation method and application of MOF derivative/LDH double-site adsorption membrane |
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