CN114797848A - Preparation method and application of oxygen-defect-containing rod-shaped core-shell structure catalyst - Google Patents

Preparation method and application of oxygen-defect-containing rod-shaped core-shell structure catalyst Download PDF

Info

Publication number
CN114797848A
CN114797848A CN202210571921.8A CN202210571921A CN114797848A CN 114797848 A CN114797848 A CN 114797848A CN 202210571921 A CN202210571921 A CN 202210571921A CN 114797848 A CN114797848 A CN 114797848A
Authority
CN
China
Prior art keywords
hnts
solution
zro
reaction
oxygen
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202210571921.8A
Other languages
Chinese (zh)
Other versions
CN114797848B (en
Inventor
曹雨
顾美凌
宋忠贤
应钰
翟洪金
张云雷
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jurong Ningwu New Material Co ltd
Jiangsu University
Original Assignee
Jurong Ningwu New Material Co ltd
Jiangsu University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Jurong Ningwu New Material Co ltd, Jiangsu University filed Critical Jurong Ningwu New Material Co ltd
Priority to CN202210571921.8A priority Critical patent/CN114797848B/en
Publication of CN114797848A publication Critical patent/CN114797848A/en
Application granted granted Critical
Publication of CN114797848B publication Critical patent/CN114797848B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/48—Silver or gold
    • B01J23/52—Gold
    • B01J35/393—
    • B01J35/397—
    • B01J35/40—
    • 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
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Nanotechnology (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Dispersion Chemistry (AREA)
  • Composite Materials (AREA)
  • Catalysts (AREA)

Abstract

The invention belongs to the field of preparation of novel heterogeneous catalysts, and discloses a preparation method of an oxygen-containing defect rodlike core-shell structure catalyst, and a method for preparing 2,5-furandicarboxylic acid FDCA by applying the oxygen-containing defect rodlike core-shell structure catalyst to selective oxidation of 5-Hydroxymethylfurfural (HMF) of a high-efficiency catalytic biomass platform molecule. The Au/ZrO thus obtained 2 The catalyst of @ HNTs has oxygen vacancy and Lewis acid site, and the existence of the oxygen vacancy is favorable for reducing the oxidant O in the reaction process 2 Chemical adsorption energy ofO adsorbed on the surface of the agent 2 Can receive delocalized electrons from oxygen vacancy and convert the delocalized electrons into active oxygen, thereby improving the catalytic reaction activity. In addition, the Lewis acid site can capture lone pair electrons of hydroxyl group oxygen atoms in the intermediate in the reaction process, so that the adsorption capacity of the catalyst on the reaction intermediate is improved, and the catalytic reaction efficiency is improved.

Description

Preparation method and application of oxygen-defect-containing rod-shaped core-shell structure catalyst
Technical Field
The invention belongs to the field of preparation of novel heterogeneous catalysts, and particularly relates to a method for preparing 2,5-furandicarboxylic acid (FDCA) by constructing an oxygen-containing defect rod-shaped core-shell structure catalyst and applying the oxygen-containing defect rod-shaped core-shell structure catalyst to selective oxidation of 5-Hydroxymethylfurfural (HMF) serving as a high-efficiency catalytic biomass platform molecule.
Background
The use of renewable biomass energy is driven by environmental problems caused by the increasing depletion and overuse of fossil energy. HMF is a biomass platform compound derived from lignocellulosic biomass that can be converted to a range of high value-added chemicals, for example, HMF can be oxidized to produce 2, 5-Diformylfuran (DFF), 5-Hydroxymethyl-2-furancarboxylic acid (HMFCA), 5-Formylfuran-2-carboxylic acid (5-formamylfuran-2-carboxylic acid, FFCA) and FDCA. Among these oxygenates, FDCA is listed by the U.S. department of energy as one of the 12 most valued additional chemicals in biomass. Due to similar physical and chemical properties, FDCA can be used as a substitute for the petroleum derivative terephthalic acid (PTA). In addition, compared with polyethylene terephthalate (PET) obtained by PTA, the bio-based polyethylene 2, 5-furandicarboxylate (PEF) synthesized by FDCA has better gas barrier property, thermal stability and mechanical property, and can be used for sealing outer package of food, plastic bottle and the like. Therefore, FDCA has wide application prospect and huge market potential.
At present, in the reaction of preparing FDCA by selective oxidation of HMF, a supported noble metal heterogeneous catalyst (Au, Pt, Pd, Ru and alloy) is widely applied because the supported noble metal heterogeneous catalyst is easy to separate from a reaction system, has good stability and reusability and higher catalytic reaction activity. The supported Au catalyst can show better stability, selectivity and catalytic performance than other noble metal catalysts under mild reaction conditions. In addition, during the reaction of preparing FDCA by oxidizing HMF, O is used 2 As an oxidizing agent, the formation of active oxygen species and the adsorption capacity of the catalyst for the reactant species have a crucial influence on the reaction. The research finds that the oxygen vacancy defect on the surface of the carrier is in contact with the carrier or the metal-carrier interface to form O 2 The adsorption capacity is related, and oxygen vacancy is beneficial to reducing O 2 Chemical adsorption energy of (2), O chemically adsorbed on the surface of the support 2 Can receive delocalized electrons from surface oxygen vacancy and convert the delocalized electrons into active oxygen, and the larger the number of oxygen vacancy defects, the more O 2 The higher the adsorption capacity. Moreover, the oxygen vacancy defect can obviously enhance the interaction between the carrier and the Au nano-particles, the charge state of the loaded metal nano-particles is changed, the charge transmission efficiency between the metal and the carrier is improved, and the activity of the catalytic reaction is greatly improved. In addition, the Lewis acid sites on the surface of the carrier can cause the formation of oxygen vacancies, and particularly, the Lewis acid sites are beneficial to improving the adsorption capacity of the catalyst on the reaction intermediate product HMFCA. Lewis acid sites can be used as catalytic active centers, lone pair electrons provided by O atoms of hydroxyl groups in HMFCA can be captured by the Lewis acid sites on the surface of the carrier, and O-H bonds are broken to form intermediates. Meanwhile, H atoms in hydroxyl groups are taken as Lewis base sites to be adsorbed on lattice oxygen of the carrier, then the intermediate is immediately converted into aldehyde groups through the breakage of C-H bonds, and the aldehyde groups are further oxidized into carboxyl groups, so that the FDCA product is obtained.
Therefore, the selection of the catalyst support is of critical importance. The metal oxide is widely used as a catalyst carrier due to the special structural characteristics and surface properties, and generally has various crystal forms, different crystal forms and atomic arrangement of the metal oxideThe column, coordination environment and surface defects are different, and the surface acid-alkali property, the number of oxygen vacancies and the like are different. For ZrO 2 It has unique properties (containing oxygen vacancy defects and acid sites), good mechanical properties, high thermal stability and different crystal forms (common crystal forms include monoclinic phase, tetragonal phase and cubic phase). In addition, ZrO of different crystal forms 2 The number of oxygen vacancies and the acid strength are different. However, the common coprecipitation method and hydrothermal method are used for preparing ZrO 2 The crystal form is not easy to be regulated and controlled in the process, and the prepared ZrO 2 The particle size is large, agglomeration phenomenon is easy to occur, so that the size of the loaded metal nano particles is large, the exposed number of active sites is reduced, and the catalytic activity is reduced.
Disclosure of Invention
The invention aims to construct a supported Au catalyst with oxygen vacancies and Lewis acid sites. The method comprises the steps of coating amorphous zirconium oxide on the surface of HNTs by a sol-gel method by using the HNTs which is a nano material with a hollow tubular structure, good water dispersibility, environmental friendliness, low price and rich yield as a template to realize rod-shaped ZrO 2 The preparation of the @ HNTs core-shell particles improves the dispersion degree of the catalyst in the solution and increases the contact area of the reaction. In addition, in order to further avoid agglomeration of the zirconium oxide obtained by hydrolysis, the invention provides for quantitative ZrO to be formed by means of the method 2 The precursor is hydrolyzed twice to prepare a sample 2L-ZrO loaded with two layers of zirconia 2 @ HNTs. Thereafter, ZrO was controlled by changing the calcination temperature 2 Of the crystal form of (a) to the support ZrO 2 The structure of @ HNTs has more oxygen vacancies and Lewis acid sites, and Au nano particles are loaded on a carrier, so that the rodlike core-shell catalyst Au/ZrO with more oxygen vacancies and Lewis acid sites is prepared 2 @ HNTs catalyst. The catalyst is used in the reaction of selective oxidation of HMF to FDCA, wherein O 2 As an oxidizing agent, green solvent H 2 O is used as a reaction system.
The technical scheme adopted by the invention is as follows:
oxygen-containing defect rod-like core-shell structure Au/ZrO 2 @ HNTs catalysisThe preparation method of the agent comprises the following steps:
a1, adding HNTs into an acid solution, heating and refluxing under the stirring state, washing the obtained reaction solution by deionized water until the reaction solution is neutral after the reaction is finished, and then centrifugally collecting and drying in vacuum. Then, placing the sample in a tubular furnace to calcine in air atmosphere to obtain a product which is pretreated HNTs;
a2, taking the pretreated HNTs obtained in the step A1, dispersing the HNTs in ethanol, adding a surfactant and deionized water, and ultrasonically dispersing and uniformly mixing the sample. Then slowly dropwise adding the hydrolyzed zirconium salt solution into the mixed system under stirring. After the hydrolysis reaction is finished, the product is centrifugally collected and then is placed in an oven for drying to obtain a sample (1L-ZrO) loaded with amorphous zirconia 2 @HNTs)；
A3 taking 1L-ZrO obtained in the step A2 2 Substituting the HNTs pretreated in the step A2 with the @ HNTs, and repeating the hydrolysis reaction in the step A2 to obtain a zirconium oxide product 2L-ZrO loaded on two layers of the outer surface of the HNTs 2 @ HNTs. Then 2L-ZrO is put in air atmosphere 2 The @ HNTs is placed in a tubular furnace to be calcined at different temperatures to obtain two layers of zirconia products X-2L-ZrO of different crystal forms loaded on the surface of the HNTs 2 @HNTs；
A4, mixing the tetrachloroauric acid solution (HAuCl) 4 ·3H 2 O) adding the mixture into a stabilizer, adding a reducing agent after uniform dispersion, and then dropwise adding an acidic solution to adjust the pH value to be neutral. Then the X-2L-ZrO prepared in the step A3 2 @ HNTs were added to the solution and reacted in a water bath. After the reaction is finished, washing with deionized water, centrifugally collecting, and drying in vacuum to obtain the oxygen-containing defect rodlike core-shell structure catalyst X-Au/2L-ZrO 2 @HNTs。
In step A1, the ratio of HNTs to acid solution is (10-40g) to (63-250mL), wherein the acid solution is 3M nitric acid, sulfuric acid or hydrochloric acid solution.
In the step A1, the heating reflux temperature is 75-80 ℃, and the heating reflux time is 8-12 h; the temperature of vacuum drying is 50-60 ℃, the drying time is 12-24h, the calcining temperature of the tubular furnace is 200-300 ℃, the heating speed is 5 ℃/min, and the calcining time is 1-2 h.
In step A2, the ratio of the pretreated HNTs, ethanol, surfactant, deionized water and hydrolyzed zirconium salt solution is (23-92mg): 20-80mL): 10-40 mg: (0.1-0.4mL): 5-20mL,
in the step A2, the hydrolysis reaction temperature is 25 ℃, and the hydrolysis reaction time is 20-24 h; the drying temperature in the oven is 60-70 deg.C, and the drying time is 12-24 h.
In the step A3, the 1L-ZrO 2 The proportion of @ HNTs, ethanol, surfactant, deionized water and the hydrolyzed zirconium salt solution is (23-92mg): (20-80mL): 10-40mg): 0.1-0.4mL): 5-20 mL;
in the step A3, the hydrolysis reaction temperature is 25 ℃, and the hydrolysis reaction time is 20-24 h; the drying temperature in the oven is 60-70 ℃, and the drying time is 12-24 h; the calcination temperature of the tubular furnace is 350-850 ℃, the heating rate is 5 ℃/min, and the calcination time is 2 h.
In the steps A2 and A3, the hydrolysable zirconium salt solution is 50-80 wt% of zirconium n-butoxide (ZBOT) or zirconium n-propoxide solution; the surfactant is one or more of carboxymethyl cellulose (CMC), hydroxyethyl cellulose (HEC), hydroxypropyl cellulose (HPC) or hydroxypropyl methyl cellulose (HPMC).
In step A4, HAuCl 4 ·3H 2 O solution, stabilizer, reducing agent and X-2L-ZrO 2 The ratio of @ HNTs is (0.8-4.0mL): (75-375mL): (1.0-5.0mL): (0.2-1.0g), the HAuCl is described 4 ·3H 2 The mass percentage concentration of the O solution is 1 wt%, and the stabilizing agent is polyvinyl alcohol (PVA) solution, sodium Polyacrylate (PNAA) solution, polyvinylpyrrolidone (PVP) solution or monomer sodium acrylate (NAA) solution with the mass percentage concentration of 1 wt%; the reducing agent is sodium borohydride (NaBH) with the molar concentration of 0.1M 4 ) Solution, sodium citrate (C) 6 H 5 Na 3 O 7 ) Solutions or potassium borohydride (KBH) 4 ) The acid solution is 1M hydrochloric acid (HCl) and 1M HNO with molar concentration 3 Or 2M acetic acid (CH) 3 COOH) solution;
in the step A4, the water bath reaction temperature is 25 ℃, and the reaction time is 2-4 h; the vacuum drying temperature is 50-60 deg.C, and the drying time is 12-24 h.
The oxygen defect-containing rodlike core-shell structure catalyst prepared by the invention is X-Au/2L-ZrO 2 The application of @ HNTs in preparing FDCA by catalyzing HMF oxidation comprises the following steps: using water as a reaction solvent, adding HMF, alkali and a rod-shaped core-shell structure catalyst X-Au/2L-ZrO with oxygen defects into a reaction kettle 2 @ HNTs followed by introduction of O 2 And starting the oxidation reaction after the temperature is raised to the set reaction temperature.
Wherein, the X-Au/2L-ZrO 2 The proportion of @ HNTs, HMF, alkali and deionized water is (40-80mg): (40-80mg): 60-300mg): 30-60 mL; the reaction temperature is 80-110 ℃, the reaction time is 1-12h, and the pressure of reaction oxygen is 0.5-2 MPa.
Wherein the alkali is sodium hydroxide (NaOH) or sodium carbonate (Na) 2 CO 3 ) Sodium bicarbonate (NaHCO) 3 ) Potassium bicarbonate (KHCO) 3 ) Potassium carbonate (K) 2 CO 3 ) Potassium hydroxide (KOH).
The invention has the beneficial effects that:
(1) selecting nano material HNTs with low price, rich yield, stable performance and environmental protection as a carrier template.
(2) The superfine amorphous zirconia is prepared by a sol-gel method, and ZrO can be enabled by changing the calcination temperature 2 The crystal form has controllability, and the calcination can generate oxygen defects in the material structure, so that the catalyst has more oxygen vacancies and Lewis acid sites, and the O pair of the catalyst is improved 2 The activation capacity of the catalyst and the adsorption capacity of the intermediate product, thereby leading the HMF to be efficiently and selectively oxidized to prepare the FDCA. In addition, because the particles of the zirconia layer are very small, the particle size of the loaded Au nano-particles is small, so that the catalyst can expose more reaction active sites, and has good catalytic activity.
(3) Quantitative ZrO by means of sol-gel process 2 The precursor is hydrolyzed twice to prepare a sample loaded with two layers of zirconia, so that the phenomenon that the sample is completely hydrolyzed once is avoidedPartial ZrO 2 Is not loaded on HNTs, but is agglomerated and dispersed in the reaction system, so that ZrO 2 ZrO with @ HNTs dispersed in reaction system 2 The wrapping causes the phenomenon of reducing the dispersion degree. The zirconium oxide can be uniformly loaded on the outer surface of the rod-shaped structure through twice hydrolysis, so that the dispersity and the stability are improved, the subsequent loading of Au nano particles is facilitated, and the catalytic activity is improved.
(4) The rod-shaped core-shell structure catalyst prepared by the invention is easy to separate from a reaction system, has good reusability, is simple in preparation process and easy to operate, and is suitable for industrial production.
Drawings
FIG. 1 shows the pretreated HNTs (a, d),1L-ZrO in example 1 2 @ HNTs (b, e) and 2L-ZrO 2 (c, f) scanning Electron microscopy and Transmission Electron microscopy of @ HNTs.
FIG. 2 is (a) a transmission electron microscope and high resolution lattice plot and a size distribution plot (b) of supported Au nanoparticles for the oxygen-containing defect rod-like core-shell structures 650 deg.C-Au/2L-ZrO 2@ HNTs catalyst prepared in example 1.
FIG. 3 shows the pretreated HNTs,650 deg.C-2L-ZrO in example 1 2 X-ray diffraction patterns of @ HNTs and 650 ℃ -Au/2L-ZrO2@ HNTs.
FIG. 4 shows 650 ℃ Au/2L-ZrO in example 1 2 Electron paramagnetic resonance spectrum of @ HNTs.
FIG. 5 shows the pretreated HNTs supports of example 1 and 650 ℃ Au/2L-ZrO 2 NH of @ HNTs 3 Temperature programmed desorption is shown in the attached figure.
FIG. 6 is a 650 ℃ Au/2L-ZrO of oxygen deficient rod-like core-shell structure catalyst prepared in example 1 2 Infrared spectrum of pyridine of @ HNTs.
FIG. 7 shows 650 ℃ to 2L-ZrO in example 1 2 @ HNTs and prepared oxygen-defect-containing rod-shaped core-shell structure catalyst 650 ℃ -Au/2L-ZrO 2 XPS full spectrum (a) of @ HNTs, Au/HNTs and 650 ℃ -Au/2L-ZrO 2 High resolution spectrogram (b) of Au 4f region of @ HNTs and 650 ℃ -2L-ZrO 2 @ HNTs and 650 ℃ Au/2L-ZrO 2 High resolution spectrum (c) of O1s region of @ HNTs and high resolution spectrum of Zr 3d regionFIG. d shows a schematic view.
Detailed Description
The invention will be further described with reference to the drawings and the specific examples, but the scope of the invention is not limited thereto.
Example 1:
1. oxygen defect-containing rod-shaped core-shell structure 650 ℃ -Au/2L-ZrO 2 Preparation of @ HNTs catalyst.
(1) Weighing 40g of HNTs, placing the HNTs in a three-neck flask, and measuring 250mL of HNO by using a measuring cylinder 3 The solution was placed in a three-necked flask. Then it was placed in an oil bath and equipped with a reflux condenser and stirred at 75 ℃ for 12 h. After the reaction was completed, the resulting reaction mixture was washed to neutrality with deionized water and then collected by centrifugation. The sample was dried in a vacuum oven at 60 ℃ for 12 h. The resulting solid was then ground to a powder and placed in a tube furnace under air atmosphere and calcined at 200 ℃ for 2 h.
(2) 0.23g of pretreated HNTs and 0.01g of HPC are weighed, dispersed in 20mL of ethanol, and then 0.1mL of deionized water is added dropwise, and the samples are uniformly mixed through ultrasonic dispersion. The flask was then placed in a 25 ℃ water bath and stirred for 30 min. 0.6mL of ZBOT solution was measured in 4.5mL of ethanol solution (5.1 mL of hydrolyzed zirconium salt solution), and after mixing well, it was slowly added dropwise to the reaction solution to react for 20 hours. After the reaction is finished, washing the obtained solution with ethanol, collecting precipitate by centrifugation, and drying in an oven at 60 ℃ for 12h to obtain a sample 1L-ZrO loaded with amorphous zirconia 2 @HNTs。
(3) 0.23g of the 1L-ZrO obtained in the preceding step are weighed 2 @ HNTs and 0.01g HPC, redispersed in 20mL ethanol and stirred for 30 min. Then, 0.6mL of ZBOT was measured, dispersed in 4.5mL of ethanol (5.1 mL of the hydrolyzed zirconium salt solution), and added dropwise to the reaction system after mixing uniformly. After the reaction system reacts at 25 ℃ for 20h, the obtained product is washed 3-4 times by ethanol, centrifugally collected and dried in an oven at 60 ℃ for 12 h. Then placing the dried sample powder in a tubular furnace, calcining for 2h at 650 ℃ in air atmosphere at the heating rate of 5 ℃/min to obtain mixed crystal form (monoclinic phase ZrO) loaded on the surface of HNTs and having mixed crystal form 2 And tetragonal phase ZrO 2 ) Of 650 ℃ -2L-ZrO 2 @HNTs。
(4) 75mL of a1 wt% aqueous PVA solution was weighed out, and 0.8mL of 1 wt% HAuCl was added 4 ·3H 2 Adding O solution, stirring in 25 deg.C water bath for 5min, and adding 1mL of 0.1M NaBH 4 And (3) solution. After stirring the mixture uniformly, 0.4mL of HCl was added to the reaction system to adjust the pH of the reaction system to 7. Then 0.2g of 650 ℃ -2L-ZrO was weighed 2 And adding the @ HNTs into the reaction system, and stirring for 2 h. After the reaction is finished, washing the obtained product with deionized water for 4-5 times, centrifugally collecting and drying the product in vacuum at 60 ℃ for 24 hours to obtain the rod-shaped core-shell catalyst 650-Au/2L-ZrO for preparing FDCA by catalyzing HMF oxidation 2 @HNTs。
It can be observed from the scanning electron micrograph (a) and the transmission electron micrograph (d) of FIG. 1 that HNTs have a hollow rod-like structure, and from the scanning electron micrographs (b) and (c), 1L-ZrO can be observed 2 @ HNTs and 2L-ZrO 2 The @ HNTs still has a rod-shaped structure, in addition, the transmission electron microscope images (e) and (f) can observe that zirconia is successfully loaded on the surface of the HNTs, the diameter of the rod loaded with one layer of zirconia is 88nm, the diameter of the rod loaded with two layers of zirconia is 93nm, and the transmission electron microscope images further prove that the prepared sample has the rod-shaped core-shell structure.
From the transmission electron micrograph (a) of FIG. 2, it can be observed that Au nanoparticles are successfully loaded to 650 ℃ -2L-ZrO 2 @ HNTs surface, and ZrO obtained by calcination at 650 ℃ was observed after measuring the crystal lattice according to the photographed high resolution 2 Is a mixed crystal form (monoclinic m-ZrO) 2 Phase and tetragonal phase t-ZrO 2 ). From the particle size distribution diagram (b), it can be observed that the particle size of the supported Au is small, the average size is about 2.25nm, and the smaller the particle size of Au, the more active sites the catalyst provides for the reaction, and the better the catalytic performance.
From FIG. 3, it can be seen from the X-ray diffraction pattern that the prepared rod-like core-shell structure catalyst is 650 ℃ -Au/2L-ZrO 2 @ HNTs showed ZrO of different crystal forms 2 Characteristic peak. Peaks at 28.2 ° and 31.5 ° correspond to monoclinic phase ZrO, respectively 2 (m-ZrO 2 ) The (-111) and (111) crystal planes of (A), and 30.2 °, 35.3 °, 50.4 °, and 5 °9.7 ℃ each corresponding to a tetragonal phase of ZrO 2 (t-ZrO 2 ) The (111), (200), (220) and (311) planes of (a), which indicates that the zirconia obtained by calcination at 650 ℃ is of mixed crystal form (monoclinic phase and tetragonal phase). The characteristic peaks of Au should appear at 38.3 °, 44.4 ° and 64.5 °, but are not observed in the spectra, which is presumed to be because Au nanoparticles are uniformly distributed on the support and have a small size, lower than the limit of X-ray diffraction detection, in combination with the results observed in transmission electron microscopy.
From FIG. 4, 650 ℃ to Au/2L-ZrO 2 The electron paramagnetic resonance spectrogram of @ HNTs can observe a peak with a g value of 2.003, and the peak corresponds to the characteristic peak of oxygen defects, and the result shows that the prepared catalyst is 650-Au/2L-ZrO 2 @ HNTs have oxygen vacancies.
From FIG. 5, HNTs and 650 ℃ Au/2L-ZrO 2 NH of @ HNTs 3 The temperature programmed desorption figure can observe that the surfaces of HNTs hardly have any acid sites, but the prepared catalyst is 650-Au/2L-ZrO 2 The surface of @ HNTs has strong acid sites, and the total amount of strong acid in the catalyst is 5.1057mmol g after curve integration and quantitative analysis -1 。
The prepared rodlike core-shell structure catalyst 650 ℃ -Au/2L-ZrO can be observed from the pyridine infrared spectrogram in FIG. 6 2 @ HNTs exhibit Bronsted acid (1542 cm) simultaneously -1 ) And a Lewis acid (1447 cm) -1 ) Characteristic band of active site, 1490cm -1 The characteristic bands of (A) are assigned to the Bronsted acid and Lewis acid sites. The curve integral is quantitatively analyzed to obtain 0.0556mmol g of Lewis acid sites on the surface of the prepared catalyst -1 . The Lewis acid sites are beneficial to the adsorption of the catalyst on reaction intermediate products, so that the catalytic reaction activity is improved.
From 650 ℃ to 2L-ZrO in FIG. 7 2 @ HNTs and prepared rod-shaped core-shell structure catalyst 650-Au/2L-ZrO 2 The XPS full spectrum (a) of @ HNTs can show the occurrence of Zr 3d and Au 4f signal peaks, which proves that the zirconia and Au nanoparticles are successfully loaded on the HNTs. From the scheme (b) Au/HNTs and 650 ℃ -Au/2L-ZrO 2 Of @ HNTsThe high resolution spectrum of the Au 4f region can be observed, and compared with the binding energy of Au 4f of Au/HNTs, the catalyst is 650 ℃ -Au/2L-ZrO 2 The Au 4f binding energy of @ HNTs moves in a lower direction. This indicates ZrO 2 The charge on the carrier (mixed crystal form) is transferred to the Au nano-particles, so that the Au nano-particles are in a negative charge state, and the charge transfer exists between the carrier and the metal. From the graph (c), 650 ℃ Au/2L-ZrO was observed 2 The binding energy of Zr 3d in @ HNTs was shifted toward the rising direction, indicating that the charge of Zr ions was transferred to the Au nanoparticles. FIG. d is a high resolution spectrum of the O1s region for the catalyst 650 deg.C-Au/2L-ZrO 2 For @ HNTs, the peak at 531.60eV is attributed to surface-adsorbed oxygen (O) ads ) And the surface adsorbed oxygen is closely related to oxygen vacancy, so the result shows that the prepared ZrO with mixed crystal form 2 The catalyst surface of (2) contains oxygen vacancies. In addition, it can be observed that the binding energy of O1s after loading Au on the sample is shifted to a lower direction, which further indicates the interaction between the carrier and the metal.
2. And (3) testing the catalytic activity:
0.05g of HMF, 0.06g of NaOH and 0.05g of 650 ℃ -Au/2L-ZrO were weighed out 2 @ HNTs, dispersing in 40mL of deionized water, and then charging O into the reaction kettle 2 The pressure is 2MPa, the reaction system reacts for 3 hours at 100 ℃, and the rotating speed is 600 rpm. Detecting the liquid product obtained by the reaction by using a High Performance Liquid Chromatograph (HPLC) with an ultraviolet detector and a hydrogen column, diluting the obtained liquid product by 80 times by using deionized water, and filtering the liquid by using a 0.2 mu m polytetrafluoroethylene filter membrane. The detection conditions are as follows: the column temperature was 65 ℃; the mobile phase was 0.01M H 2 SO 4 (ii) a The flow rate is 0.4 mL/min; the amount of sample was 20. mu.L. The FDCA sample calibration curve is 352.03x-81.042(y represents the concentration corresponding to FDCA, and is in mg/L, and x represents the peak area), and the concentration of FDCA can be calculated from the calibration curve and converted into the molar concentration. The product yield was calculated as Y (molar yield) ═ n 1 /n 0 ×100，n 1 Represents the molar amount of FDCA obtained, n 0 Representing the molar amount of HMF as the reaction substrate. The calculation result shows that the product FDCA can achieve higher yieldThe yield of FDCA after 3h of reaction was 99.36%.
3. Test for regeneration Performance
In the invention, the prepared rod-shaped core-shell structure catalyst is 650 ℃ -Au/2L-ZrO 2 The @ HNTs can be obtained by centrifugation, separation and drying. Putting the recovered catalyst into the catalytic experiment again to test the catalytic effect; four regeneration experiments were performed in this way. The detection method and experimental conditions of the obtained liquid product are the same as those of the catalytic experiment. The results show that: the loss of catalyst activity during the regeneration process is low, and the yield of FDCA is 95.04%, 89.02%, 88.40% and 87.68% in sequence during one to four times of experiments.
Example 2:
1. oxygen defect-containing rod-shaped core-shell structure 450 ℃ -Au/2L-ZrO 2 Preparation of @ HNTs catalyst.
(1) 10g of HNTs were weighed into a three-necked flask, and 63mL of H was measured in a measuring cylinder 2 SO 4 The solution was placed in a three-necked flask. Then it was placed in an oil bath and equipped with a reflux condenser and stirred at 75 ℃ for 8 h. After the reaction was completed, the resulting reaction mixture was washed to neutrality with deionized water and then collected by centrifugation. The sample was dried in a vacuum oven at 60 ℃ for 24 h. The resulting solid was then ground to a powder and calcined in a tube furnace at 300 ℃ for 1h under an air atmosphere.
(2) 0.92g of pretreated HNTs and 0.04g of HEC are weighed, dispersed in 80mL of ethanol, and then 0.4mL of deionized water is added dropwise, and the samples are uniformly mixed through ultrasonic dispersion. The flask was then placed in a 25 ℃ water bath and stirred for 30 min. 2.4mL of ZBOT solution was measured in 18mL of ethanol solution (20.4 mL of hydrolyzed zirconium salt solution), mixed well, and slowly added dropwise to the flask for reaction for 24 h. After the reaction is finished, washing the obtained solution with ethanol, centrifuging, collecting precipitate, and drying in an oven at 60 ℃ for 12h to obtain a sample 1L-ZrO loaded with amorphous zirconia 2 @HNTs。
(3) 0.46g of 1L-ZrO was weighed 2 @ HNTs, 0.02g HEC, added to 40mL ethanol and stirred for 30min to mix well. 10.2mL of hydrolyzed zirconium salt solution (1.2 m) was preparedL ZBOT, 9.0mL ethanol) was added slowly dropwise to the reaction mixture. After the reaction system reacts at 25 ℃ for 24h, the obtained product is washed by ethanol, centrifugally collected and dried in an oven at 60 ℃ for 12 h. Then placing the dried sample powder in a tubular furnace, calcining for 2h at 450 ℃ in air atmosphere at the heating rate of 5 ℃/min to obtain a tetragonal two-layer zirconia product 450 ℃ -2L-ZrO loaded on the outer surface of HNTs 2 @HNTs。
(4) 150mL of 1 wt% PVP aqueous solution was measured and 1.6mL of 1 wt% HAuCl was added 4 ·3H 2 Adding O solution, stirring in 25 deg.C water bath for 5min, and adding 1mL of 0.1M KBH 4 And (3) solution. After stirring uniformly, 0.4mL of 1M HNO was added to the reaction system 3 The reaction system was brought to pH 7. Then 0.4g of 450 ℃ -2L-ZrO was weighed 2 And adding the @ HNTs into the reaction system, and stirring for 3 hours. After the reaction is finished, washing the obtained product with deionized water for 4-5 times, centrifugally collecting and drying the product in vacuum at 70 ℃ for 12 hours to obtain the rod-shaped core-shell catalyst 450-Au/2L-ZrO for catalyzing the HMF oxidation to prepare FDCA 2 @HNTs。
2. And (3) testing the catalytic performance:
0.06g of HMF and 0.16g of NaHCO are weighed out 3 And 0.06g of 450 ℃ Au/2L-ZrO 2 @ HNTs, dispersing in 50mL of deionized water, and then charging O into the reaction kettle 2 The pressure is 2MPa, the reaction system reacts for 8 hours at 100 ℃, and the rotating speed is 600 rpm. The liquid product obtained from the reaction was detected by High Performance Liquid Chromatography (HPLC) using an ultraviolet detector and a hydrogen column, in the same manner as in step 2 of example 1. The calculation result shows that the product FDCA can achieve higher yield, and the yield of the FDCA of the reaction 8h is 97.07%.
3. And (3) testing the regeneration performance:
the regeneration performance was tested in the same manner as in example 1. The results show that the activity of the catalyst is not greatly lost in the regeneration reaction, and the yield of the FDCA is 95.96%, 92.02%, 89.89% and 88.98% in sequence during one to four times of regeneration experiments.
Example 3:
1. oxygen defect-containing rod-shaped core-shell structure 350 ℃ -Au/2L-ZrO 2 Catalyst of @ HNTsAnd (4) preparing.
(1) Weighing 20g of HNTs, placing the HNTs in a three-neck flask, and measuring 126mL of HNO by using a measuring cylinder 3 The solution was placed in a three-necked flask. Then it was placed in an oil bath and equipped with a reflux condenser and stirred at 80 ℃ for 8 h. After the reaction was completed, the resulting reaction mixture was washed to neutrality with deionized water and then collected by centrifugation. The sample was dried in a vacuum oven at 50 ℃ for 24 h. The resulting solid was then ground to a powder and placed in a tube furnace under air atmosphere and calcined at 200 ℃ for 2 h.
(2) 0.69g of pretreated HNTs and 0.03g of HPC are weighed, dispersed in 60mL of ethanol, and then 0.3mL of deionized water is added dropwise, and the samples are uniformly mixed through ultrasonic dispersion. The flask was then placed in a 25 ℃ water bath and stirred for 30 min. 1.8mL of ZBOT solution was weighed into 13.5mL of ethanol solution (15.3 mL of hydrolyzed zirconium salt solution), mixed well, and slowly added dropwise to the flask for 20 h. After the reaction is finished, washing the obtained solution with ethanol, centrifuging, collecting precipitate, drying the precipitate in an oven at 70 ℃ for 12h to obtain a sample 1L-ZrO loaded with amorphous zirconia 2 @HNTs。
(3) 0.92g of 1L-ZrO was added to 80mL of ethanol 2 @ HNTs and 0.04g HPC, followed by ultrasonic dispersion and stirring in a 25 ℃ water bath for 30 min. Then, 2.4mL of ZBOT (20.4 mL of a zirconium salt hydrate solution) was added to 18mL of ethanol, and after mixing uniformly, it was slowly added dropwise to the reaction solution. After the reaction for 20 hours, the resulting reaction solution was washed with ethanol and the precipitate was collected by centrifugation, after which the resulting sample was placed in an oven at 70 ℃ for 12 hours. Then, under the air atmosphere, the dried sample powder is placed in a tubular furnace to be calcined for 2h at 350 ℃, the temperature rising speed is 5 ℃/min, and a monoclinic phase two-layer zirconium oxide product 350-2L-ZrO loaded on the outer surface of HNTs is obtained 2 @HNTs。
(4)4.0mL of 1 wt% HAuCl 4 ·3H 2 The O aqueous solution was added to 375ml of 1 wt% PVP solution. Stirring in a 25 ℃ water bath for 5min, and then dropwise adding 5mL of 0.1M NaBH into the reaction solution 4 And (3) solution. After stirring, 2mL of HCl was added dropwise to adjust the pH of the solution to 7. Then 1.0g of 350 ℃ -2L-ZrO was weighed 2 Adding the @ HNTs into a reaction systemAnd stirring for 4 hours. After the reaction is finished, washing the reaction solution by deionized water, centrifugally collecting precipitates, and drying the precipitates in vacuum at the temperature of 60 ℃ for 12 hours to prepare the catalyst 350-Au/2L-ZrO 2 @HNTs。
2. And (3) testing the catalytic performance:
0.08g HMF and 0.26g Na were weighed out 2 CO 3 And 0.08g of 350 ℃ to Au/2L-ZrO 2 @ HNTs, dispersing in 60mL of deionized water, and then charging O into the reaction kettle 2 The pressure is 2MPa, the reaction system reacts for 12 hours at the temperature of 110 ℃, and the rotating speed is 600 rpm. The liquid product obtained by the reaction was detected in the same manner as in step 2 of example 1. The calculation result shows that the product FDCA can achieve higher yield, and the yield of the FDCA of the reaction 8h is 93.20%.
3. And (3) testing the regeneration performance:
the regeneration performance was tested in the same manner as in example 1. The results show that the activity of the catalyst is not greatly lost in the regeneration reaction, and the yield of the FDCA is 92.02%, 90.92%, 89.48% and 88.86% in sequence during one to four times of the regeneration experiment. Example 4:
1. oxygen defect-containing rod-shaped core-shell structure 850 ℃ -Au/2L-ZrO 2 Preparation of @ HNTs catalyst.
(1) Weighing 30g of HNTs, placing the HNTs in a three-neck flask, and measuring 189mL of HNO by using a measuring cylinder 3 The solution was placed in a three-necked flask. Then it was placed in an oil bath and equipped with a reflux condenser and stirred at 80 ℃ for 12 h. After the reaction was completed, the resulting reaction mixture was washed to neutrality with deionized water and then collected by centrifugation. The sample was dried in a vacuum oven at 60 ℃ for 24 h. The resulting solid was then ground to a powder and placed in a tube furnace under air atmosphere and calcined at 200 ℃ for 2 h.
(2) 0.46g of pretreated HNTs and 0.02g of HPMC are weighed, dispersed in 40mL of ethanol, and then 0.2mL of deionized water is added dropwise, and the samples are uniformly mixed through ultrasonic dispersion. The flask was then placed in a 25 ℃ water bath and stirred for 30 min. 1.2mL of ZBOT solution was measured and added to 9.0mL of ethanol solution (10.2 mL of hydrolyzed zirconium salt solution), and after mixing well, the mixture was slowly added dropwise to the flask and reacted for 24 hours. After the reaction is finished, the obtained solution isWashing with ethanol, centrifuging, collecting precipitate, and oven drying at 70 deg.C for 12 hr to obtain sample 1L-ZrO loaded with amorphous zirconia 2 @HNTs。
(3) 0.46g of 1L-ZrO was added to 40mL of ethanol 2 @ HNTs and 0.02g HPMC, followed by ultrasonic dispersion and stirring in a 25 ℃ water bath for 30 min. Then, 1.2mL of ZBOT (hydrolyzed zirconium salt solution, 10.2mL) was added to 9mL of ethanol, and after mixing uniformly, it was slowly added dropwise to the reaction solution. After the reaction for 20 hours, the resulting reaction solution was washed with ethanol and the precipitate was collected by centrifugation, after which the resulting sample was placed in an oven at 70 ℃ for 12 hours. Then, under the air atmosphere, the dried sample powder is placed in a tubular furnace to be calcined for 2h at 850 ℃, the temperature rising speed is 5 ℃/min, and a two-layer zirconium oxide product 850-2L-ZrO loaded on the mixed phase of the outer surface of HNTs is obtained 2 @HNTs。
(4)3.2mL of 1 wt% HAuCl 4 ·3H 2 The O aqueous solution was added to 300ml of a1 wt% PNAA solution. Stirring in a 25 ℃ water bath for 5min, and then dropwise adding 4mL of 0.1M NaBH into the reaction solution 4 And (3) solution. After stirring well, 1.6mL of CH was added dropwise 3 COOH adjusted the pH of the solution to 7. Thereafter, 1.0g of 850 ℃ to 2L-ZrO was weighed 2 @ HNTs was added to the reaction system and stirred for 4 h. After the reaction is finished, washing the reaction solution by deionized water, centrifugally collecting precipitates, and drying the precipitates in vacuum at the temperature of 60 ℃ for 12 hours to prepare the catalyst 850-Au/2L-ZrO 2 @HNTs。
2. And (3) testing the catalytic performance:
weighing 0.07g HMF and 0.24g Na 2 CO 3 And 0.07g of 850 ℃ to Au/2L-ZrO 2 @ HNTs, dispersing in 50mL of deionized water, and then charging O into the reaction kettle 2 The pressure is 1.5MPa, the reaction system reacts for 8 hours at the temperature of 90 ℃, and the rotating speed is 600 rpm. The liquid product obtained by the reaction was detected in the same manner as in step 2 of example 1. The calculation result shows that the product FDCA can achieve higher yield, and the yield of the FDCA in 4h of reaction is 95.60%.
3. And (3) testing the regeneration performance:
the regeneration performance was tested in the same manner as in example 1. The results show that the activity of the catalyst is not greatly lost in the regeneration reaction, and the yields of FDCA are 94.48%, 90.42%, 86.48% and 85.86% in sequence during one to four experiments of regeneration.

Claims (10)

1. The preparation method of the oxygen-containing defect rodlike core-shell structure catalyst is characterized by comprising the following steps of:
a1, adding HNTs into an acid solution, heating and refluxing under a stirring state, after the reaction is finished, washing the obtained reaction solution by deionized water until the reaction solution is neutral, then centrifugally collecting and drying in vacuum, and then calcining a sample in a tubular furnace in an air atmosphere to obtain a product which is the pretreated HNTs;
a2, taking the pretreated HNTs obtained in the step A1, dispersing the HNTs in ethanol, adding a surfactant and deionized water, ultrasonically dispersing and uniformly mixing the HNTs, slowly dropwise adding a hydrolyzed zirconium salt solution into a mixing system under the stirring condition, centrifugally collecting the product after the hydrolysis reaction is finished, and drying the product in a drying oven to obtain a sample 1L-ZrO-loaded with amorphous zirconium oxide 2 @HNTs；
A3 taking 1L-ZrO obtained in the step A2 2 Substituting the HNTs pretreated in the step A2 with the @ HNTs, and repeating the hydrolysis reaction in the step A2 to obtain a zirconium oxide product 2L-ZrO loaded on two layers of the outer surface of the HNTs 2 @HNTs；
Then 2L-ZrO is put in air atmosphere 2 The @ HNTs is placed in a tubular furnace to be calcined at different temperatures to obtain two layers of zirconia products X-2L-ZrO of different crystal forms loaded on the surface of the HNTs 2 @HNTs；
A4, mixing HAuCl in tetrachloroauric acid aqueous solution under stirring 4 ·3H 2 Adding O into a stabilizer, adding a reducing agent after uniform dispersion, and then dropwise adding an acidic solution to adjust the pH value to be neutral; then the X-2L-ZrO prepared in the step A3 2 Adding the @ HNTs into the solution, reacting in a water bath, washing with deionized water after the reaction is finished, centrifugally collecting, and drying in vacuum to obtain the oxygen-containing defect rodlike core-shell structure catalyst X-Au/2L-ZrO 2 @HNTs。
2. The method of claim 1 wherein in step A1, the ratio of HNTs to acid solution is (10-40g) to (63-250mL), wherein the acid solution is 3M solution of nitric acid, sulfuric acid or hydrochloric acid;
the heating reflux temperature is 75-80 ℃, and the heating reflux time is 8-12 h; the temperature of vacuum drying is 50-60 ℃, the drying time is 12-24h, the calcining temperature of the tubular furnace is 200-300 ℃, the heating speed is 5 ℃/min, and the calcining time is 1-2 h.
3. The method of claim 1 wherein in step a2, the ratio of the pretreated HNTs, ethanol, surfactant, deionized water, and hydrolyzed zirconium salt solution is (23-92mg): (20-80mL): (10-40mg): (0.1-0.4mL): (5-20 mL); the hydrolysis reaction temperature is 25 ℃, and the hydrolysis reaction time is 20-24 h; the drying temperature in the oven is 60-70 deg.C, and the drying time is 12-24 h.
4. The method according to claim 1, wherein the 1L-ZrO is subjected to the step A3 2 The proportion of @ HNTs, ethanol, surfactant, deionized water and the hydrolyzed zirconium salt solution is (23-92mg): (20-80mL): 10-40mg): 0.1-0.4mL): 5-20 mL; the hydrolysis reaction temperature is 25 ℃, and the hydrolysis reaction time is 20-24 h; the drying temperature in the oven is 60-70 ℃, and the drying time is 12-24 h; the calcination temperature of the tubular furnace is 350-850 ℃, the heating speed is 5 ℃/min, and the calcination time is 2 h.
5. The method of claim 3 or 4, wherein in steps A2 and A3, the hydrolyzable zirconium salt solution is 50-80 wt% zirconium n-butoxide or zirconium n-propoxide solution; the surfactant is one or more of carboxymethyl cellulose CMC, hydroxyethyl cellulose HEC, hydroxypropyl cellulose HPC or hydroxypropyl methyl cellulose HPMC.
6. The method of claim 1, wherein in step a4, HAuCl is added 4 ·3H 2 O solution, stabilizer, andthe original agent and X-2L-ZrO 2 The proportion of @ HNTs is (0.8-4.0mL): (75-375mL): (1.0-5.0mL): (0.2-1.0 g);
wherein, the HAuCl 4 ·3H 2 The mass percentage concentration of the O solution is 1 wt%;
the stabilizer is polyvinyl alcohol PVA solution, sodium polyacrylate PNAA solution, polyvinylpyrrolidone PVP solution or monomer sodium acrylate NAA solution with the mass percentage concentration of 1 wt%;
the reducing agent is sodium borohydride solution, sodium citrate solution or potassium borohydride solution with the molar concentration of 0.1M;
the acid solution is hydrochloric acid with the molar concentration of 1M and 1M HNO 3 Or 2M acetic acid solution.
7. The method of claim 1, wherein in step a4, the water bath reaction temperature is 25 ℃ and the reaction time is 2-4 h; the vacuum drying temperature is 50-60 deg.C, and the drying time is 12-24 h.
8. An oxygen-containing defect rod-shaped core-shell structure catalyst, which is characterized by being prepared by the preparation method of any one of claims 1-4 and 6-7 and marked as X-Au/2L-ZrO 2 @HNTs。
9. Use of the oxygen-containing defective rod-shaped core-shell structured catalyst of claim 8 for catalyzing the oxidation of HMF to FDCA.
10. The use according to claim 9, characterized by the steps of: using water as a reaction solvent, adding HMF, alkali and a rod-shaped core-shell structure catalyst X-Au/2L-ZrO with oxygen defects into a reaction kettle 2 @ HNTs followed by introduction of O 2 And starting the oxidation reaction after the temperature is raised to the set reaction temperature.
CN202210571921.8A 2022-05-25 2022-05-25 Preparation method and application of oxygen-defect-containing rod-shaped core-shell structure catalyst Active CN114797848B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210571921.8A CN114797848B (en) 2022-05-25 2022-05-25 Preparation method and application of oxygen-defect-containing rod-shaped core-shell structure catalyst

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210571921.8A CN114797848B (en) 2022-05-25 2022-05-25 Preparation method and application of oxygen-defect-containing rod-shaped core-shell structure catalyst

Publications (2)

Publication Number Publication Date
CN114797848A true CN114797848A (en) 2022-07-29
CN114797848B CN114797848B (en) 2023-07-28

Family

ID=82516532

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210571921.8A Active CN114797848B (en) 2022-05-25 2022-05-25 Preparation method and application of oxygen-defect-containing rod-shaped core-shell structure catalyst

Country Status (1)

Country Link
CN (1) CN114797848B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115582121A (en) * 2022-10-26 2023-01-10 江苏大学 Preparation method and application of porous carbon-coated gold-palladium alloy rod-shaped nano reactor catalyst

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103657684A (en) * 2013-11-22 2014-03-26 江苏大学 Preparation method for halloysite nanotube-sulfonic acid group-Cr (III) ion acid composite catalyst
CN106166499A (en) * 2016-07-25 2016-11-30 江苏大学 A kind of method that in green solvent system, catalysis fibre element converts preparation 5 Hydroxymethylfurfural
CN106311345A (en) * 2016-07-25 2017-01-11 江苏大学 Acid-base bifunctional solid catalyst and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103657684A (en) * 2013-11-22 2014-03-26 江苏大学 Preparation method for halloysite nanotube-sulfonic acid group-Cr (III) ion acid composite catalyst
CN106166499A (en) * 2016-07-25 2016-11-30 江苏大学 A kind of method that in green solvent system, catalysis fibre element converts preparation 5 Hydroxymethylfurfural
CN106311345A (en) * 2016-07-25 2017-01-11 江苏大学 Acid-base bifunctional solid catalyst and preparation method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
刘雪晨;邢娟娟;王海鹏;周沅逸;张玲;王文中;: "HMF催化合成生物基聚酯单体FDCA", 化学进展, no. 09 *
李月;李一鸣;张雪艳;王晓红;: "多金属氧酸盐纳米纤维催化O_2氧化5-HMF", 科学通报, no. 10 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115582121A (en) * 2022-10-26 2023-01-10 江苏大学 Preparation method and application of porous carbon-coated gold-palladium alloy rod-shaped nano reactor catalyst
CN115582121B (en) * 2022-10-26 2023-09-26 江苏大学 Preparation method and application of porous carbon coated gold-palladium alloy rod-shaped nano reactor catalyst

Also Published As

Publication number Publication date
CN114797848B (en) 2023-07-28

Similar Documents

Publication Publication Date Title
Zhang et al. A simple large-scale synthesis of mesoporous In2O3 for gas sensing applications
CN101703935A (en) Load type metal catalyst and preparation method thereof
CN107364897A (en) A kind of preparation method of ferrous acid zinc nano material
CN111514893A (en) Catalyst with sub-nanometer composite structure and preparation method thereof
CN107792887A (en) A kind of high-specific surface area ZnMn2O4Preparation method
CN114405505B (en) Platinum modified indium-based oxide catalyst and preparation method and application thereof
CN102161498B (en) Preparation method of uniformly dispersed nano lanthanum oxide
CN113209976A (en) Catalyst for methanol steam reforming hydrogen production, preparation method and application thereof, and methanol steam reforming hydrogen production reaction
CN114797848B (en) Preparation method and application of oxygen-defect-containing rod-shaped core-shell structure catalyst
CN112191246A (en) Supported palladium monatomic catalyst and application thereof in selective hydrogenation of cinnamaldehyde
CN112007637B (en) Bimetallic alloy-halloysite composite catalyst and preparation method and application thereof
CN108636412B (en) Preparation method of multi-core-shell hollow catalyst nickel-nickel silicate for methane and carbon dioxide reforming
CN114917907A (en) Supported non-noble metal catalyst with high catalytic hydrogenation activity, preparation method and application thereof
Huang et al. β-Cyclodextrin promoted the formation of copper phyllosilicate on Cu-SiO2 microspheres catalysts to enhance the low-temperature hydrogenation of dimethyl oxalate
Fang et al. Efficient hydrogenation of furfural to fufuryl alcohol over hierarchical MOF immobilized metal catalysts
CN106693965A (en) Sol-gel preparation method and application of Pd/MgTiO3 catalyst
CN108996557A (en) A kind of hollow ball structure nickel oxide/copper oxide composite nano materials and preparation method thereof
CN101224903A (en) Method for preparing cerium dioxide nano cubic block
CN112086648A (en) Method for synthesizing AuPd @ C material for oxygen reduction reaction electrocatalysis
CN103949271B (en) A kind of cobalt manganese hydrotalcite supported nanometer gold catalyst and preparation method thereof
CN101767997B (en) Method for preparing NiTiO3 nano-powder by sol-gel
CN112221509B (en) Preparation method of high-stability methanol synthesis catalyst
CN106232230A (en) Method and the application thereof of metal/metal oxide material is prepared by nano-structured matrix
CN106984314A (en) A kind of preparation method of high-dispersion loading type copper-based nano-catalyst
CN101343043B (en) Amphoteric metal compound nano-material and method of preparing the same

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant