CN114797848B - 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

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CN114797848B
CN114797848B CN202210571921.8A CN202210571921A CN114797848B CN 114797848 B CN114797848 B CN 114797848B CN 202210571921 A CN202210571921 A CN 202210571921A CN 114797848 B CN114797848 B CN 114797848B
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solution
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oxygen
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CN114797848A (en
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曹雨
顾美凌
宋忠贤
应钰
翟洪金
张云雷
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Jurong Ningwu New Material Co ltd
Jiangsu University
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Jiangsu University
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    • 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
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Abstract

The invention belongs to the field of preparation of novel heterogeneous catalysts, and discloses a preparation method of an oxygen-defect-containing rod-shaped core-shell structure catalyst and a method for preparing 2,5-furandicarboxylic acid FDCA by applying the oxygen-defect-containing rod-shaped core-shell structure catalyst to efficient catalysis of biomass platform molecule 5-hydroxymethylfurfural HMF selective oxidation. The Au/ZrO obtained 2 The catalyst of @ HNTs has both oxygen vacancies and Lewis acid sites, and the existence of the oxygen vacancies is beneficial to reducing the oxidant O in the reaction process 2 Is adsorbed on the surface of the catalyst 2 Delocalized electrons can be received from oxygen vacancies to be converted into active oxygen, thereby enhancing catalytic reactivity. In addition, the existence of Lewis acid sites can capture lone pair electrons of hydroxyl group oxygen atoms in the reaction process intermediates, so that the adsorption capacity of the catalyst on the reaction intermediates 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-defect-containing rod-shaped core-shell structure catalyst and applying the oxygen-defect-containing rod-shaped core-shell structure catalyst to efficiently catalyzing 5-Hydroxymethylfurfural (HMF) as a biomass platform molecule.
Background
The use of renewable biomass energy is driven by environmental problems arising from the increasing depletion and overuse of fossil energy. HMF is a biomass platform compound derived from lignocellulosic biomass that is converted to a range of highly valuable chemicals, for example HMF is oxidized to produce 2, 5-Diformylfuran (DFF), 5-Hydroxymethyl-2-furancarboxylic acid (5-Hydroxymethyl-2-furancarboxylic acid, HMFCA), 5-Formylfuran-2-carboxylic acid (FFCA) and FDCA. Among these oxidation products, FDCA is classified by the U.S. department of energy as one of the 12 chemicals with the highest added value in biomass. FDCA can be used as a substitute for petroleum derivative terephthalic acid (PTA) due to similar physical and chemical properties. In addition, compared with polyethylene terephthalate (PET) obtained by PTA, the bio-based polyester 2,5-furandicarboxylic acid ethylene ester (PEF) synthesized by FDCA has better gas barrier property, thermal stability and mechanical property, and can be used for sealing and packaging foods, plastic bottles and the like. Therefore, FDCA has wide application prospect and huge market potential.
Currently, in the reaction of preparing FDCA by catalyzing HMF selective oxidation, a supported noble metal heterogeneous catalyst (Au, pt, pd, ru and alloy) is widely used due to easy separation from a reaction system, good stability, reusability and higher catalytic reactivity. Wherein, 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 HMF oxidation, O is used as 2 As an oxidizing agent, the formation of reactive oxygen species and the adsorption capacity of the catalyst for the reactive species are therefore critical for the reactionInfluence. It was found that the oxygen vacancy defect at the support surface was aligned with the O at the support or metal-support interface 2 Adsorption capacity is related, oxygen vacancies are beneficial for reducing O 2 Chemisorbed O on the surface of the support 2 Can receive delocalized electrons from surface oxygen vacancies to be converted into active oxygen, the more the number of oxygen vacancy defects, 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 support surface may lead to the formation of oxygen vacancies, and it is notable that the Lewis acid sites also contribute to the improved adsorption capacity of the catalyst to the reaction intermediate HMFCA. The Lewis acid site can be used as a catalytic active center, and a lone pair electron provided by an O atom of a hydroxyl group in HMFCA can be captured by the Lewis acid site on the surface of the carrier, so that an intermediate is formed by breaking an O-H bond. Simultaneously, H atoms in hydroxyl groups are used as Lewis base sites to be adsorbed on lattice oxygen of a carrier, then the intermediate is immediately converted into aldehyde groups through the cleavage of C-H bonds, and the aldehyde groups are further oxidized into carboxyl groups, so that a product FDCA is obtained.
Therefore, the choice of catalyst support is critical. Metal oxides are widely used as catalyst carriers due to their special structural features and surface properties, and generally have various crystal forms, different atomic arrangements, coordination environments and surface defects of metal oxides, and different surface acid-base properties, number of oxygen vacancies and the like. For ZrO 2 In terms of its unique properties (containing oxygen vacancy defects and acid sites), good mechanical properties, higher thermal stability and different crystalline forms (common crystalline forms include monoclinic, tetragonal and cubic phases). In addition, zrO of different crystal forms 2 The number of oxygen vacancies and the acid strength are different. However, the commonly used coprecipitation method and hydrothermal method are used for preparing ZrO 2 In the process, the regulation and control of the crystal form are not easy to carry out, and the prepared ZrO 2 The particle size is larger, and the agglomeration phenomenon is easy to occur, so that the size of the loaded metal nano particles is largerThe number of active site exposures is reduced, leading to a reduction in catalytic activity.
Disclosure of Invention
The invention aims to construct a supported Au catalyst with both oxygen vacancies and Lewis acid sites. The nano material HNTs with a hollow tubular structure, good water dispersibility, environmental friendliness, low price and rich yield is used as a template, and the amorphous zirconia is coated on the surface of the HNTs by a sol-gel method to realize rod-shaped ZrO 2 And (3) preparing the@HNTs core-shell particles, so that the dispersity of the catalyst in the solution is improved, and the contact area of the reaction is increased. In addition, in order to further avoid agglomeration of the zirconia obtained by hydrolysis, the present invention relates to a method for quantifying ZrO 2 The precursor is hydrolyzed twice to prepare a sample 2L-ZrO loaded with two layers of zirconia 2 @HNTs. Thereafter, zrO is regulated by changing the calcination temperature 2 Crystalline form of (C) and (D) a support ZrO 2 The @ HNTs structure has more oxygen vacancies and Lewis acid sites, and Au nano particles are loaded on the carrier, so that the rod-shaped core-shell structure catalyst Au/ZrO with more oxygen vacancies and Lewis acid sites is prepared 2 Catalyst @ HNTs. The catalyst is used in the selective oxidation of HMF to FDCA, wherein O 2 As an oxidizing agent, green solvent H 2 O was used as the reaction system.
The technical scheme adopted by the invention is as follows:
Au/ZrO with oxygen-defect rod-shaped core-shell structure 2 The preparation method of the @ HNTs catalyst comprises the following steps:
a1, adding HNTs into an acid solution, heating and refluxing under a stirring state, washing the obtained reaction solution until the reaction solution is neutral by deionized water after the reaction is finished, and then collecting the reaction solution by centrifugation and drying the reaction solution in vacuum. Then placing the sample in a tube furnace to calcine in an air atmosphere to obtain a pretreated HNTs product;
a2, taking the pretreated HNTs obtained in the step A1, dispersing the HNTs in ethanol, then adding a surfactant and deionized water, and uniformly mixing the sample through ultrasonic dispersion. Then slowly dripping the zirconium salt solution into the mixed system under the condition of stirring. After the hydrolysis reaction, the product was collected by centrifugation and then dried in an oven to obtain a sample (1L-ZrO 2) loaded with amorphous zirconia 2 @HNTs)；
A3, taking the 1L-ZrO obtained in the step A2 2 The pretreated HNTs in the step A2 are replaced by the @ HNTs, and the hydrolysis reaction in the step A2 is repeated to obtain a zirconia product 2L-ZrO loaded on two layers of the outer surface of the HNTs 2 @HNTs. Then under the air atmosphere, 2L-ZrO 2 Calcining HNTs in a tube furnace at different temperatures to obtain two-layer zirconia products X-2L-ZrO with different crystal forms supported on the surface of HNTs 2 @HNTs；
A4, stirring the aqueous solution of tetrachloroauric acid (HAuCl) 4 ·3H 2 And O) adding the stabilizer, uniformly dispersing, adding the reducing agent, and then dropwise adding the acidic solution to adjust the pH value to be neutral. Then X-2L-ZrO obtained in the step A3 2 The @ HNTs were added to the solution and reacted in a water bath. After the reaction is finished, washing with deionized water, centrifugally collecting, and vacuum drying to obtain the oxygen-containing defect rod-shaped core-shell structure catalyst X-Au/2L-ZrO 2 @HNTs。
In the step A1, the proportion of HNTs to the acid solution is (10-40 g) (63-250 mL), wherein the acid solution is nitric acid, sulfuric acid or hydrochloric acid solution with the molar concentration of 3M.
In the step A1, the temperature of heating reflux is 75-80 ℃, and the time of heating reflux is 8-12h; the vacuum drying temperature is 50-60 ℃, the drying time is 12-24h, the tube furnace calcining temperature is 200-300 ℃, the heating speed is 5 ℃/min, and the calcining time is 1-2h.
In the step A2, the proportion of the pretreated HNTs, the ethanol, the surfactant, the deionized water and the hydrolyzed zirconium salt solution is (23-92 mg), 20-80mL, 10-40mg, 0.1-0.4mL, 5-20mL,
in the step A2, the hydrolysis reaction temperature is 25 ℃, and the hydrolysis reaction time is 20-24 hours; the drying temperature in the oven is 60-70 ℃ and the drying time is 12-24h.
In step A3, the 1L-ZrO 2 The ratio of @ HNTs, ethanol, surfactant, deionized water and hydrolyzed zirconium salt solution was (23-92mg):(20-80mL):(10-40mg):(0.1-0.4mL):(5-20mL)；
In the step A3, the hydrolysis reaction temperature is 25 ℃, and the hydrolysis reaction time is 20-24 hours; the drying temperature in the oven is 60-70 ℃ and the drying time is 12-24h; the calcination temperature of the tube furnace is 350-850 ℃, the temperature rising speed is 5 ℃/min, and the calcination time is 2h.
In the steps A2 and A3, the hydrolyzable zirconium salt solution is 50-80wt% 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 methylcellulose (HPMC).
In step A4, HAuCl 4 ·3H 2 O solution, stabilizer, reducing agent and X-2L-ZrO 2 The ratio of @ HNTs is (0.8-4.0 mL): (75-375 mL): (1.0-5.0 mL): (0.2-1.0 g), the HAuCl 4 ·3H 2 The mass percentage concentration of the O solution is 1wt%, and 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 1wt%; 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 acidic solution is 1M hydrochloric acid (HCl) and 1M HNO 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 2-4h; the vacuum drying temperature is 50-60 ℃ and the drying time is 12-24h.
The oxygen-defect-containing rod-shaped core-shell structure catalyst prepared by the invention is X-Au/2L-ZrO 2 Application of @ HNTs in catalyzing oxidation of HMF to prepare FDCA comprises the following steps: taking water as a reaction solvent, adding HMF, alkali and an oxygen-containing defect rod-shaped core-shell structure catalyst X-Au/2L-ZrO into a reaction kettle 2 @HNTs, then let in O 2 And after the temperature is increased to the set reaction temperature, the oxidation reaction is started.
Wherein, the X-Au/2L-ZrO 2 Ratio of @ HNTs, HMF, alkali to deionized waterExamples are (40-80 mg) (60-300 mg) (30-60 mL); the reaction temperature is 80-110 ℃, the reaction time is 1-12h, and the reaction oxygen pressure is 0.5-2MPa.
Wherein the alkali is sodium hydroxide (NaOH), 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) The nano material HNTs with low price, rich yield, stable performance and environmental friendliness is selected as a carrier template.
(2) Ultrafine amorphous zirconia prepared by sol-gel method, zrO can be obtained by changing calcination temperature 2 The crystal form has adjustable property, 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 catalyst is improved in O 2 And the adsorption capacity of intermediate products, thereby enabling efficient selective oxidation of HMF to produce FDCA. In addition, the particle size of the supported Au nano-particles is smaller due to the fact that the particles of the zirconia layer are small, so that the catalyst can expose more reactive sites, and good catalytic activity is achieved.
(3) Quantitative ZrO by means of sol-gel method 2 The precursor is hydrolyzed twice to prepare a sample loaded with two layers of zirconia, so that partial ZrO caused by one-time complete hydrolysis is avoided 2 Not supported on HNTs, but agglomerated and dispersed in the reaction system so that ZrO 2 ZrO where @ HNTs are dispersed in the reaction System 2 Coating, causing the phenomenon of reduced dispersity. 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, is easy to operate, and is suitable for industrial production.
Drawings
FIG. 1 shows HNTs (a, d), 1L-ZrO after pretreatment 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 graph of (a) transmission electron microscopy and high resolution lattice diagram and (b) size distribution of supported Au nanoparticles of the oxygen defect containing rod-shaped core-shell structure 650-Au/2L-zro2@hnts catalyst prepared in example 1.
FIG. 3 shows HNTs,650 ℃ C. -2L-ZrO after pretreatment in example 1 2 X-ray diffraction patterns of @ HNTs and 650-Au/2L-ZrO2@HNTs.
FIG. 4 is a diagram of 650℃Au/2L-ZrO in example 1 2 Electron paramagnetic resonance spectrogram of @ HNTs.
FIG. 5 shows the pretreated HNTs support of example 1 and 650 ℃ C. -Au/2L-ZrO 2 NH of @ HNTs 3 Temperature programmed desorption drawing.
FIG. 6 is a schematic diagram of a catalyst 650℃Au/2L-ZrO in a rod-like core-shell structure containing oxygen defects as prepared in example 1 2 Pyridine infrared spectrum of @ HNTs.
FIG. 7 is a drawing of 650-2L-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, 650-2L-ZrO 2 @HNTs and 650-Au/2L-ZrO 2 High resolution spectra (c) of O1s region of @ HNTs and (d) of Zr 3d region.
Detailed Description
The invention will be further described with reference to the accompanying drawings and specific examples, to which the scope of the invention is not limited.
Example 1:
1. 650-Au/2L-ZrO with oxygen defect rod-shaped core-shell structure 2 Preparation of the @ HNTs catalyst.
(1) 40g HNTs are weighed and placed in a three-necked flask, and 250mL HNO is weighed by using a cylinder 3 The solution was placed in a three-necked flask. Then, it was placed in an oil bath and was fitted with a reflux condenser and stirred at 75℃for 12 hours. After the reaction is finishedThe resulting reaction mixture was washed to neutrality with deionized water and then collected by centrifugation. The resulting sample was dried in a vacuum oven at 60℃for 12h. The resulting solid was then ground to a powder, placed in a tube furnace under an air atmosphere, and calcined at 200 ℃ for 2h.
(2) 0.23g of pretreated HNTs and 0.01g of HPC are weighed, dispersed in 20mL of ethanol, added with 0.1mL of deionized water in a dropwise manner, and the samples are uniformly mixed through ultrasonic dispersion. The flask was then placed in a 25 ℃ water bath and stirred for 30min. 0.6mL of ZBOT solution is measured in 4.5mL of ethanol solution (5.1 mL of hydrolyzed zirconium salt solution), and after being uniformly mixed, the solution is slowly added dropwise into the reaction solution for reaction for 20h. After the reaction is finished, the obtained solution is washed by ethanol, the sediment is collected by centrifugation, and is dried for 12 hours in a 60 ℃ oven, thus obtaining a sample 1L-ZrO loaded with amorphous zirconia 2 @HNTs。
(3) Weighing 0.23g of 1L-ZrO obtained in the last step 2 The @ HNTs and 0.01g HPC were redispersed in 20mL ethanol and stirred for 30min. Then, 0.6mL of ZBOT was measured, dispersed in 4.5mL of ethanol (5.1 mL of hydrolyzed zirconium salt solution), and after uniform mixing, added dropwise to the reaction system. After the reaction system reacts for 20 hours at 25 ℃, the obtained product is washed 3-4 times by ethanol, centrifugally collected and dried for 12 hours in a 60 ℃ oven. Then placing the dried sample powder in a tube furnace, calcining at 650 ℃ for 2 hours in air atmosphere at a heating rate of 5 ℃/min to obtain the mixed crystal form (monoclinic phase ZrO loaded on the surface of HNTs 2 And tetragonal ZrO 2 ) 650-2L-ZrO in a two-layer zirconia product of (C) 2 @HNTs。
(4) 75mL of a 1wt% PVA aqueous solution was measured, and 0.8mL of 1wt% HAuCl was added 4 ·3H 2 Adding O solution, stirring in water bath at 25deg.C for 5min, and dripping 1mL of 0.1M NaBH 4 A solution. After stirring uniformly, 0.4mL of HCl was added to the reaction system to bring the pH of the reaction system to 7. Then 0.2g of 650-2L-ZrO was weighed out 2 Adding @ HNTs into the reaction system, and stirring for 2h. After the reaction is finished, washing the obtained product with deionized water for 4-5 times, centrifugally collecting, and vacuum drying at 60 ℃ for 24 hours to obtain the rod-shaped core-shell for catalyzing HMF oxidation to prepare FDCAStructural catalyst 650-Au/2L-ZrO 2 @HNTs。
From the scanning electron microscope (a) and the transmission electron microscope (d) of FIG. 1, a hollow rod-like structure of HNTs can be observed, and from the scanning electron microscope (b) and (c), 1L-ZrO can be observed 2 @HNTs and 2L-ZrO 2 Still show bar-shaped structure by @ HNTs, in addition, can observe that zirconia is successfully loaded on HNTs surface by transmission electron microscope pictures (e) and (f), the diameter of the bar after loading one layer of zirconia is 88nm, the diameter after loading two layers of zirconia is 93nm, and transmission electron microscope pictures further prove that the prepared sample is bar-shaped core-shell structure.
From the transmission electron microscope image (a) of FIG. 2, it can be observed that Au nanoparticles were successfully loaded to 650-2L-ZrO 2 The surface of @ HNTs and the ZrO obtained by calcination at 650℃as observed after measurement of the crystal lattice according to the high resolution image taken 2 Is a mixed crystal form (monoclinic m-ZrO 2 Phase and tetragonal phase t-ZrO 2 ). From the particle size distribution chart (b), it can be observed that the particle size of the supported Au is smaller, the average size thereof is about 2.25nm, and the smaller the particle size of Au is, the more active sites the catalyst provides for the reaction, and the better the catalytic performance.
From FIG. 3, the X-ray diffraction pattern can be seen that the prepared rod-shaped core-shell structure catalyst is 650-Au/2L-ZrO 2 The @ HNTs show ZrO of different crystal forms 2 Characteristic peaks. Peaks at 28.2℃and 31.5℃correspond to monoclinic ZrO-phase, respectively 2 (m-ZrO 2 ) (-111) and (111) planes, and 30.2 °, 35.3 °, 50.4 °, and 59.7 ° respectively correspond to tetragonal phase ZrO 2 (t-ZrO 2 ) The (111), (200), (220) and (311) planes of (b), which indicate that zirconium oxide obtained by calcination at 650 ℃ is a mixed crystal form (monoclinic phase and tetragonal phase). Characteristic peaks of Au should appear at 38.3 °, 44.4 ° and 64.5 °, but no characteristic peaks of Au are observed in the spectrogram, combined with the results observed by transmission electron microscopy, presumably because Au nanoparticles are uniformly distributed on the support and are small in size, below the limit of X-ray diffraction detection.
From FIG. 4, 650 ℃ C. -Au/2L-ZrO 2 Electron paramagnetic resonance spectrogram of @ HNTs can observe that a peak having g value of 2.003 appears, which corresponds to an oxygen defectThe characteristic peaks of (2) indicate that the catalyst prepared is 650-Au/2L-ZrO 2 The @ HNTs have oxygen vacancies.
From FIG. 5, HNTs and 650 ℃ C. -Au/2L-ZrO 2 NH of @ HNTs 3 The temperature programming desorption drawing can observe that the surface of HNTs hardly presents any acid site, however, the prepared catalyst is 650-Au/2L-ZrO 2 The surface of the @ HNTs is provided with a strong acid site, and the total amount of the strong acid of the catalyst obtained after quantitative analysis of curve integral is 5.1057mmol g -1 。
The prepared rod-shaped core-shell structure catalyst 650-Au/2L-ZrO can be observed by the pyridine infrared spectrogram of FIG. 6 2 HNTs exhibit Bronsted acids (1542 cm) -1 ) And Lewis acid (1447 cm) -1 ) Characteristic band of active site, 1490cm -1 The characteristic bands at which are assigned to the Bronsted and Lewis acid sites. The curve integral is quantitatively analyzed to obtain 0.0556mmol of Lewis acid sites on the surface of the prepared catalyst -1 . Wherein the lewis acid sites facilitate the adsorption of the catalyst to the reaction intermediate, thereby enhancing the catalytic activity.
From 650-2L-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 shows the appearance of Zr 3d and Au 4f signal peaks, which demonstrates that zirconia and Au nanoparticles have been successfully loaded onto HNTs. From the graph (b) Au/HNTs and 650-Au/2L-ZrO 2 As can be seen from the high resolution spectra of the Au 4f region of the @ HNTs, the catalyst is 650-Au/2L-ZrO compared to the binding energy of Au 4f of the Au/HNTs 2 Au 4f binding energy of @ HNTs moves toward a lower direction. This indicates ZrO 2 The charges on the (mixed crystal form) carrier are transferred to the Au nano-particles, so that the Au nano-particles are in a negative charge state, and the charges are transferred between the carrier and the metal. From FIG. (c), it can be observed that 650℃Au/2L-ZrO 2 The binding energy of Zr 3d in @ HNTs is shifted in the direction of the rise, indicating that the charge, which is Zr ion, is transferred to the Au nanoparticle. FIG. d is a high resolution spectrum of the O1s region for a catalyst of 650℃Au/2L-ZrO 2 For @ HNTs, located at 531.60The peak of eV is attributed to surface adsorbed oxygen (O ads ) The surface adsorption of oxygen is closely related to oxygen vacancies, so that the result shows that the prepared ZrO with mixed crystal forms 2 The catalyst surface of (2) contains oxygen vacancies. In addition, it was observed that the binding energy of O1s after Au loading of the sample shifted to a lower direction, further indicating the interaction between the support and the metal.
2. Catalytic activity test:
0.05g HMF,0.06g NaOH and 0.05g of 650-Au/2L-ZrO were weighed out 2 Dispersing @ HNTs in 40mL deionized water, and then filling O into a reaction kettle 2 The pressure is 2MPa, the reaction system reacts for 3 hours at 100 ℃, and the rotating speed is 600rpm. The liquid product obtained by the reaction was detected by configuring an ultraviolet detector and a hydrogen column with a High Performance Liquid Chromatograph (HPLC), and the obtained liquid product was diluted 80 times with deionized water, and then the liquid was filtered with a 0.2 μm polytetrafluoroethylene filter membrane. The detection conditions are as follows: the column temperature is 65 ℃; mobile phase 0.01M H 2 SO 4 The method comprises the steps of carrying out a first treatment on the surface of the The flow rate is 0.4mL/min; the sample loading was 20. Mu.L. The standard curve of the FDCA sample is y= 352.03x-81.042 (y represents the concentration corresponding to FDCA, the unit is mg/L, and x represents the peak area), and the concentration of FDCA can be calculated according to the standard curve and converted into the molar concentration. The product yield calculation formula is Y (molar yield) =n 1 /n 0 ×100，n 1 Represents the molar amount of the FDCA obtained, n 0 Representing the molar amount of the substrate HMF. The calculation result shows that the product FDCA can reach higher yield, and the FDCA yield in the reaction for 3 hours is 99.36 percent.
3. Regeneration Performance test
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, and testing 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 regeneration was low, and the yields of FDCA were 95.04%, 89.02%, 88.40%, 87.68% in sequence during one to four experiments of regeneration.
Example 2:
1. oxygen-defect-containing rod-shaped core-shell structure with 450-Au/2L-ZrO 2 Preparation of the @ HNTs catalyst.
(1) 10g HNTs are weighed and placed in a three-necked flask, and 63mL of H is weighed by using a cylinder 2 SO 4 The solution was placed in a three-necked flask. Then, it was placed in an oil bath and was fitted with a reflux condenser and stirred at 75℃for 8 hours. After the reaction was completed, the resultant reaction mixture was washed to neutrality with deionized water and then collected by centrifugation. The resulting sample was dried in a vacuum oven at 60℃for 24h. The resulting solid was then ground to a powder, placed in a tube furnace under an air atmosphere, and calcined at 300 ℃ for 1h.
(2) 0.92g of pretreated HNTs and 0.04g of HEC are weighed, dispersed in 80mL of ethanol, added with 0.4mL of deionized water in a dropwise manner, and subjected to ultrasonic dispersion to uniformly mix the samples. The flask was then placed in a 25 ℃ water bath and stirred for 30min. 2.4mL of the ZBOT solution was taken in 18mL of ethanol solution (20.4 mL of hydrolyzed zirconium salt solution), and after mixing well, the solution was slowly added dropwise to the flask for reaction for 24h. After the reaction is finished, the obtained solution is washed by ethanol, the sediment is collected by centrifugation, and is dried for 12 hours in a 60 ℃ oven to obtain a sample 1L-ZrO loaded with amorphous zirconia 2 @HNTs。
(3) 0.46g of 1L-ZrO was weighed out 2 @HNTs, 0.02g HEC, was added to 40mL ethanol and stirred for 30min to allow thorough mixing. 10.2mL of a zirconium salt solution of hydrolysis (1.2 mL of ZBOT, 9.0mL of ethanol) was prepared and added slowly dropwise to the reaction mixture. After the reaction system had reacted at 25℃for 24 hours, the resulting product was washed with ethanol, collected by centrifugation and oven-dried at 60℃for 12 hours. Then placing the dried sample powder in a tube furnace, calcining for 2 hours at 450 ℃ in air atmosphere, and heating at a speed of 5 ℃/min to obtain a tetragonal phase two-layer zirconia product 450-2L-ZrO loaded on the outer surface of HNTs 2 @HNTs。
(4) 150mL of a 1wt% PVP aqueous solution was measured, and 1.6mL of 1wt% HAuCl was added 4 ·3H 2 Adding O solution, stirring in water bath at 25deg.C for 5min, and dripping 1mL of 0.1M KBH 4 A solution. After the stirring is carried out uniformly, the mixture is stirred,to the reaction system was added 0.4mL of 1M HNO 3 The pH of the reaction system was set to 7. Then 0.4g of 450-2L-ZrO was weighed out 2 Adding @ 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 vacuum drying at 70 ℃ for 12 hours to obtain the rod-shaped core-shell catalyst 450-Au/2L-ZrO for catalyzing HMF oxidation to prepare FDCA 2 @HNTs。
2. Catalytic performance test:
weighing 0.06g HMF,0.16g NaHCO 3 0.06g of 450-Au/2L-ZrO 2 Dispersing @ HNTs in 50mL deionized water, and then filling O into a reaction kettle 2 The pressure is 2MPa, the reaction system reacts for 8 hours at 100 ℃, and the rotating speed is 600rpm. The liquid product obtained by the reaction was detected by using a High Performance Liquid Chromatograph (HPLC) equipped with an ultraviolet detector and a hydrogen column, and the detection method was the same as in step 2 of example 1. The calculation result shows that the product FDCA can reach higher yield, and the yield of FDCA in the reaction for 8 hours is 97.07 percent.
3. Regeneration performance test:
the regeneration performance test method was the same as in example 1. The results showed that the catalyst activity was not significantly lost during the regeneration reaction, and the yields of FDCA were 95.96%, 92.02%, 89.89%, 88.98% in the order of one to four regeneration runs.
Example 3:
1. 350-Au/2L-ZrO with oxygen-defect rod-shaped core-shell structure 2 Preparation of the @ HNTs catalyst.
(1) 20g HNTs are weighed and placed in a three-necked flask, and 126mL HNO is weighed by using a cylinder 3 The solution was placed in a three-necked flask. Then, it was placed in an oil bath and was fitted with a reflux condenser and stirred at 80℃for 8 hours. After the reaction was completed, the resultant reaction mixture was washed to neutrality with deionized water and then collected by centrifugation. The resulting sample was dried in a vacuum oven at 50℃for 24h. The resulting solid was then ground to a powder, placed in a tube furnace under an air atmosphere, and calcined at 200 ℃ for 2h.
(2) Weighing 0.69g of pretreated HNTs and 0.03g of HPC, dispersing the HNTs in 60mL of ethanol, and then dripping 0.3mLThe deionized water of (2) is subjected to ultrasonic dispersion to uniformly mix the samples. The flask was then placed in a 25 ℃ water bath and stirred for 30min. 1.8mL of the ZBOT solution was taken in 13.5mL of ethanol solution (15.3 mL of hydrolyzed zirconium salt solution), and after mixing well, the solution was slowly added dropwise to the flask for reaction for 20h. After the reaction is finished, washing the obtained solution with ethanol, centrifugally collecting the precipitate, and drying the precipitate in an oven at 70 ℃ for 12 hours to obtain a sample 1L-ZrO loaded with amorphous zirconia 2 @HNTs。
(3) 0.92g of 1L-ZrO are added to 80mL of ethanol 2 @HNTs and 0.04g HPC, followed by ultrasonic dispersion and stirring in a 25℃water bath for 30min. Then, 2.4mL of ZBOT (hydrolyzed zirconium salt solution 20.4. 20.4 mL) was added to 18mL of ethanol, and after mixing well, it was slowly added dropwise to the reaction solution. After 20h of reaction, the resulting reaction solution was washed with ethanol and the precipitate was collected by centrifugation, after which the resulting sample was dried in an oven at 70 ℃ for 12h. Then placing the dried sample powder in a tube furnace for calcining for 2 hours at 350 ℃ in an air atmosphere, wherein the heating rate is 5 ℃/min, and obtaining a monoclinic phase two-layer zirconia product 350-2L-ZrO loaded on the outer surface of HNTs 2 @HNTs。
(4) 4.0mL of 1wt% HAuCl 4 ·3H 2 Aqueous O solution was added to 37ml of 1wt% PVP solution. After stirring in a water bath at 25℃for 5min, 5mL of 0.1M NaBH was added dropwise to the reaction solution 4 A solution. After stirring well, 2mL of HCl was added dropwise to adjust the ph=7 of the solution. Then 1.0g of 350-2L-ZrO was weighed 2 Adding @ HNTs into the reaction system, and stirring for 4 hours. After the reaction is finished, washing the reaction solution with deionized water, centrifugally collecting the precipitate, and vacuum drying at 60 ℃ for 12 hours to prepare the catalyst 350-Au/2L-ZrO 2 @HNTs。
2. Catalytic performance test:
weighing 0.08g HMF,0.26g Na 2 CO 3 0.08g of 350-Au/2L-ZrO 2 Dispersing @ HNTs in 60mL deionized water, and then filling O into a reaction kettle 2 The pressure is 2MPa, the reaction system reacts for 12 hours at 110 ℃, and the rotating speed is 600rpm. 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 reach higherThe yield of FDCA in reaction 8h was 93.20%.
3. Regeneration performance test:
the regeneration performance test method was the same as in example 1. The results showed that the catalyst activity was not significantly lost during the regeneration reaction, and the yields of FDCA were 92.02%, 90.92%, 89.48%, 88.86% in the order of one to four regeneration runs. Example 4:
1. oxygen-defect-containing rod-shaped core-shell structure 850-Au/2L-ZrO 2 Preparation of the @ HNTs catalyst.
(1) 30g of HNTs are weighed and placed in a three-necked flask, and 189mL of HNO is weighed by using a cylinder 3 The solution was placed in a three-necked flask. Then, it was placed in an oil bath and was fitted with a reflux condenser and stirred at 80℃for 12 hours. After the reaction was completed, the resultant reaction mixture was washed to neutrality with deionized water and then collected by centrifugation. The resulting sample was dried in a vacuum oven at 60℃for 24h. The resulting solid was then ground to a powder, placed in a tube furnace under an air atmosphere, and calcined at 200 ℃ for 2h.
(2) 0.46g of pretreated HNTs and 0.02g of HPMC are weighed, dispersed in 40mL of ethanol, added with 0.2mL of deionized water in a dropwise manner, and subjected to ultrasonic dispersion to uniformly mix the samples. The flask was then placed in a 25 ℃ water bath and stirred for 30min. 1.2mL of the ZBOT solution was taken in 9.0mL of ethanol solution (10.2 mL of hydrolyzed zirconium salt solution), and after mixing well, the solution was slowly added dropwise to the flask for reaction for 24h. After the reaction is finished, the obtained solution is washed by ethanol, the sediment is collected by centrifugation, and is dried for 12 hours in a 70 ℃ oven to obtain a sample 1L-ZrO loaded with amorphous zirconia 2 @HNTs。
(3) 0.46g of 1L-ZrO are added to 40mL of ethanol 2 @HNTs and 0.02g HPMC, followed by ultrasonic dispersion and stirring in a 25℃water bath for 30min. Then, 1.2mL of ZBOT (10.2 mL of hydrolyzed zirconium salt solution) was added to 9mL of ethanol, and after uniform mixing, it was slowly added dropwise to the reaction solution. After 20h of reaction, the resulting reaction solution was washed with ethanol and the precipitate was collected by centrifugation, after which the resulting sample was dried in an oven at 70 ℃ for 12h. The dried sample powder was then placed in a tube furnace under an air atmosphere at 85Calcining at 0 ℃ for 2 hours at a heating rate of 5 ℃/min to obtain a mixed phase two-layer zirconia product of 850-2L-ZrO loaded on the outer surface of HNTs 2 @HNTs。
(4) 3.2mL of 1wt% HAuCl 4 ·3H 2 Aqueous O solution 300ml of 1wt% PNaA solution was added. After stirring in a water bath at 25℃for 5min, 4mL of 0.1M NaBH was added dropwise to the reaction solution 4 A solution. After stirring evenly, add 1.6mL CH dropwise 3 COOH adjusts the pH of the solution=7. 1.0g of 850-2L-ZrO was then weighed 2 Adding @ HNTs into the reaction system, and stirring for 4 hours. After the reaction is finished, washing the reaction solution with deionized water, centrifugally collecting the precipitate, and vacuum drying at 60 ℃ for 12 hours to prepare the catalyst 850-Au/2L-ZrO 2 @HNTs。
2. Catalytic performance test:
weighing 0.07g HMF,0.24g Na 2 CO 3 0.07g of 850-Au/2L-ZrO 2 Dispersing @ HNTs in 50mL deionized water, and then filling O into a reaction kettle 2 The pressure is 1.5MPa, the reaction system reacts for 8 hours at 90 ℃ and the rotating speed is 600rpm. 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 reach higher yield, and the yield of FDCA in 4h of reaction is 95.60%.
3. Regeneration performance test:
the regeneration performance test method was the same as in example 1. The results showed that the catalyst activity was not significantly lost during the regeneration reaction, and the yields of FDCA were 94.48%, 90.42%, 86.48%, 85.86% in this order during one to four regeneration runs.

Claims (10)

1. The preparation method of the oxygen-defect-containing rod-shaped 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, washing the obtained reaction solution until the reaction is neutral by deionized water after the reaction is finished, collecting the reaction solution by centrifugation, drying the reaction solution in vacuum, and calcining a sample in a tube furnace under an air atmosphere to obtain a pretreated HNTs product;
a2, taking the pretreated HNTs obtained in the step A1, dispersing the HNTs in ethanol, then adding a surfactant and deionized water, uniformly dispersing and mixing the sample by ultrasonic, slowly dripping a zirconium salt solution into the mixed system under the condition of stirring, centrifugally collecting the product after the hydrolysis reaction is finished, and then drying in an oven to obtain the sample 1L-ZrO loaded with amorphous zirconia 2 @HNTs；
A3, taking the 1L-ZrO obtained in the step A2 2 The pretreated HNTs in the step A2 are replaced by the @ HNTs, and the hydrolysis reaction in the step A2 is repeated to obtain a zirconia product 2L-ZrO loaded on two layers of the outer surface of the HNTs 2 @HNTs；
Then under the air atmosphere, 2L-ZrO 2 Calcining HNTs in a tube furnace at different temperatures to obtain two-layer zirconia products X-2L-ZrO with different crystal forms loaded on the surface of HNTs 2 @HNTs；
A4, stirring the aqueous solution HAuCl of the tetrachloroauric acid 4 ·3H 2 Adding O into a stabilizer, uniformly dispersing, adding a reducing agent, and then dropwise adding an acidic solution to adjust the pH value to be neutral; then X-2L-ZrO obtained in the step A3 2 Adding @ HNTs into the solution, performing reaction in water bath, washing with deionized water after the reaction is finished, centrifugally collecting, and vacuum drying to obtain the oxygen-containing defect rod-shaped core-shell catalyst X-Au/2L-ZrO 2 @HNTs。
2. The process according to claim 1, wherein in step A1, the ratio of HNTs to the acid solution is (10-40 g) (63-250 mL), wherein the acid solution is a nitric acid, sulfuric acid or hydrochloric acid solution having a molar concentration of 3M;
the temperature of heating reflux is 75-80 ℃, and the time of heating reflux is 8-12h; the vacuum drying temperature is 50-60 ℃, the drying time is 12-24h, the tube furnace calcining temperature is 200-300 ℃, the heating speed is 5 ℃/min, and the calcining time is 1-2h.
3. The preparation method according to claim 1, wherein in the step A2, the ratio of the pretreated HNTs, ethanol, surfactant, deionized water and hydrolyzed zirconium salt solution is (23-92 mg): (20-80 mL): (10-40 mg): (0.1-0.4 mL): (5-20 mL); the hydrolysis reaction temperature is 25 ℃, and the hydrolysis reaction time is 20-24 hours; the drying temperature in the oven is 60-70 ℃ and the drying time is 12-24h.
4. The process according to claim 1, wherein in step A3, the 1L-ZrO 2 The proportion of HNTs, ethanol, surfactant, deionized water and hydrolyzed zirconium salt solution is (23-92 mg): (20-80 mL): (10-40 mg): (0.1-0.4 mL): (5-20 mL); the hydrolysis reaction temperature is 25 ℃, and the hydrolysis reaction time is 20-24 hours; the drying temperature in the oven is 60-70 ℃ and the drying time is 12-24h; the calcination temperature of the tube furnace is 350-850 ℃, the temperature rising speed is 5 ℃/min, and the calcination time is 2h.
5. The preparation method according to claim 3 or 4, wherein in the steps A2 and A3, the hydrolyzable zirconium salt solution is 50-80wt% of 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 process according to claim 1, wherein in step A4, HAuCl is added 4 ·3H 2 O solution, stabilizer, reducing agent and X-2L-ZrO 2 The proportion of @ HNTs is (0.8-4.0 mL): (75-375 mL): (1.0-5.0 mL): (0.2-1.0 g);
wherein the HAuCl 4 ·3H 2 The mass percentage concentration of the O solution is 1wt%;
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 1wt%;
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 1M hydrochloric acid and 1M HNO with molar concentration 3 Or a 2M acetic acid solution.
7. The preparation method according to claim 1, wherein in the step A4, the water bath reaction temperature is 25 ℃ and the reaction time is 2-4 hours; the vacuum drying temperature is 50-60 ℃ and the drying time is 12-24h.
8. An oxygen-defect-containing rod-like core-shell catalyst prepared by the method of any one of claims 1 to 4 and 6 to 7, and denoted as X-Au/2L-ZrO 2 @HNTs。
9. Use of the oxygen-deficient rod-shaped core-shell structured catalyst of claim 8 for catalyzing the oxidation of HMF to produce FDCA.
10. The use according to claim 9, characterized by the steps of: taking water as a reaction solvent, adding HMF, alkali and an oxygen-containing defect rod-shaped core-shell structure catalyst X-Au/2L-ZrO into a reaction kettle 2 @HNTs, then let in O 2 And after the temperature is increased to the set reaction temperature, the oxidation reaction is started.
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