CN114453000A - Nitrogen-doped mesoporous hollow carbon sphere loaded metal-based nano catalyst and preparation method thereof - Google Patents

Nitrogen-doped mesoporous hollow carbon sphere loaded metal-based nano catalyst and preparation method thereof Download PDF

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CN114453000A
CN114453000A CN202210192858.7A CN202210192858A CN114453000A CN 114453000 A CN114453000 A CN 114453000A CN 202210192858 A CN202210192858 A CN 202210192858A CN 114453000 A CN114453000 A CN 114453000A
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nitrogen
hollow carbon
doped mesoporous
carbon sphere
mesoporous hollow
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吴君
严鑫悦
王成兵
靳明
谢宇航
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Shaanxi University of Science and Technology
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    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
    • C07C41/26—Preparation of ethers by reactions not forming ether-oxygen bonds by introduction of hydroxy or O-metal groups

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Abstract

The invention discloses a nitrogen-doped mesoporous hollow carbon sphere loaded metal-based nano catalyst and a preparation method thereof. The catalyst is prepared by different methods, and the expression is M @ NHCS, wherein NHCS is a nitrogen-doped mesoporous hollow carbon sphere, and M is any one of metal nickel, copper, cobalt, iron, ruthenium, platinum, palladium, iridium, rhodium and gold. The invention uses hollow carbon spheres as a stable carrier, and can be loaded with metal to realize functionalization. The metal is loaded on the surface of the carbon sphere, so that the metal particles are not easy to agglomerate, and more active sites can be provided. In addition, the hollow carbon sphere also has an adjustable pore structure and an easily-modified surface, the macroscopic size and the shell thickness can be adjusted by a synthesis method, and the characteristics enable the hollow carbon sphere material to have huge performance potential.

Description

Nitrogen-doped mesoporous hollow carbon sphere loaded metal-based nano catalyst and preparation method thereof
Technical Field
The invention belongs to the technical field of nano materials, and particularly relates to a nitrogen-doped mesoporous hollow carbon sphere loaded metal-based nano catalyst and a preparation method thereof.
Background
With the increasing exhaustion of fossil resources, people are urgently required to find alternative energy sources of fossil energy, and the sustainable biomass resource conversion into fuels and chemicals is an effective way for solving the problem. Lignin is the only renewable resource for the production of aromatic compounds, its structure consisting of highly functionalized aromatic rings bound together by inter-unit bonds consisting of carbon-oxygen and carbon-carbon bonds, but its high oxygen and unsaturation degree makes unrefined biofuels low in energy density, low in thermal and chemical stability, limiting their direct combustion in modern diesel engines. The hydrodeoxygenation process breaks the carbon-oxygen bond and significantly reduces the oxygen content of the crude oil biofuel, and is therefore the best option for upgrading biofuels. Vanillin (4-hydroxy-3-methoxybenzaldehyde), which is a phenolic aldehyde, contains both hydroxy and methoxy groups (p-and m-groups, respectively), is an important component of bio-oil, and the hydrodeoxygenation product 2-methoxy-4-methylphenol thereof plays an important role in perfumes, medicines and other organic synthesis intermediates, and is also a potential biofuel, so that the development of a green and efficient catalyst for the selective hydrodeoxygenation of vanillin to prepare a 2-methoxy-4-methylphenol system has important significance for environmental protection and the search of alternative energy of limited crude oil.
The carbon material has the characteristics of large specific surface area, large pore volume, good electrical conductivity, good thermal stability, chemical stability and mechanical stability, low cost, suitability for large-scale production and the like, and is widely used as a carrier material of the catalyst. Among the numerous carbon-based catalytic materials, the activated carbon supported metal-type catalyst is the most studied and widely used catalyst in the chemical industry. But the activated carbon still has excessive closed pore structures, so that the reaction mass transfer in the catalytic process is limited; the defects of uneven dispersion of metal particles on the surface of carrier carbon, easy agglomeration and leaching in the use process and the like caused by the shortage of active site anchoring sites. In recent years, research shows that more and more novel carbon-based catalytic materials are developed, such as Au/carbon nano tube, Ru nano agglomerate, Ru/carbon nano tube and Pd/single-wall carbon nano tube-SiO2And Pd/MSMF (MSMF: super-hydrophilic mesoporous sulfonation)Triamino amine-formaldehyde resin), and the like. However, in the construction of these high activity catalysts, cumbersome synthetic strategies or complex supports are often unavoidable, and agglomeration of nanoparticles is often accompanied by growth and loss during the synthesis of metal nanoparticle supported catalysts, which results in severe degradation of the activity of the catalyst and even eventual deactivation. In the current hot heterogeneous catalytic reaction, the performance of the supported metal nano-catalyst is particularly outstanding. The hollow carbon sphere is a hollow core-shell structure composed of carbon, and generally refers to a micron-sized and nanometer-sized hollow structure carbon sphere. The hollow structure has the characteristics of large specific surface area, small density, stable structure and the like, so that the metal nanoparticles have excellent catalytic activity in the field of catalysis, but the catalytic performance of the metal nanoparticles is weakened due to higher surface energy.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a nitrogen-doped mesoporous hollow carbon sphere-loaded metal-based nano catalyst and a preparation method thereof, so as to solve the problems of high surface energy and poor catalytic performance when metal nano particles are used as the catalyst in the prior art.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
a nitrogen-doped mesoporous hollow carbon sphere loaded metal-based nano catalyst comprises a carrier and an active component, wherein the active component is attached to the carrier; the carrier is nitrogen-doped mesoporous hollow carbon, and the active component is any one of metal nickel, copper, cobalt, iron, ruthenium, platinum, palladium, iridium, rhodium and gold;
the mass content of the active component in the catalyst is 0.5-10 wt% in terms of mass fraction.
A preparation method of a nitrogen-doped mesoporous hollow carbon sphere loaded metal-based nano catalyst comprises the following steps:
step 1, adding tetraethyl orthosilicate into a reaction medium of water and ethanol, and stirring by adopting a sol-gel method to prepare nano silicon dioxide pellets;
step 2, placing the nano-silica spheres in a trihydroxymethyl aminomethane buffer solution, performing ultrasonic treatment, then adding dopamine hydrochloride and a metal source, performing polymerization reaction, and washing and drying a reaction product to obtain a precursor;
step 3, roasting the precursor in a furnace;
step 4, placing the roasted product in sodium hydroxide and stirring to obtain a nitrogen-doped mesoporous hollow carbon sphere supported metal-based nano catalyst;
the nitrogen-doped mesoporous hollow carbon sphere loaded metal-based nano catalyst comprises a carrier and an active component, wherein the active component is attached to the carrier; the carrier is nitrogen-doped mesoporous hollow carbon, and the active component is any one of metal nickel, copper, cobalt, iron, ruthenium, platinum, palladium, iridium, rhodium and gold.
The invention is further improved in that:
preferably, in the step 2, the ultrasonic treatment time is 1h, the polymerization reaction time is 12-24 h, and the polymerization reaction temperature is 25 ℃.
Preferably, in the step 2, the concentration of the nano silicon dioxide in the tris is 2-100 mg/mL.
Preferably, in the step 2, the mixing mass ratio of the dopamine hydrochloride to the tris buffer solution is (0.5-1): 1; the addition amount of the metal source is selected to be 0.5-10 wt% of the mass content of the active component in the catalyst.
Preferably, in the step 3, the roasting temperature is 600-900 ℃, and the roasting time is 1-5 hours.
A preparation method of a nitrogen-doped mesoporous hollow carbon sphere loaded metal-based nano catalyst comprises the following steps:
step 1, adding tetraethyl orthosilicate into a reaction medium of water and ethanol, and stirring by adopting a sol-gel method to prepare nano silicon dioxide pellets;
step 2, placing the nano silicon dioxide pellets in a trihydroxymethyl aminomethane buffer solution, carrying out ultrasonic treatment, adding dopamine hydrochloride for polymerization reaction, and centrifugally washing and drying a reaction product to obtain a precursor;
step 3, roasting the precursor;
step 4, stirring the roasted sample in a sodium hydroxide solution to obtain a nitrogen-doped mesoporous hollow carbon sphere carrier;
step 5, preparing the nitrogen-doped mesoporous hollow carbon sphere supported metal-based nano catalyst by using a nitrogen-doped mesoporous hollow carbon sphere carrier through an impregnation method or a deposition precipitation method;
the process of the impregnation method is as follows: ultrasonically dispersing a nitrogen-doped mesoporous hollow carbon sphere carrier in water, adding a metal source, after completely ultrasonic treating, adding sodium borohydride for reduction reaction, and centrifugally drying a reaction product to obtain a nitrogen-doped mesoporous hollow carbon sphere loaded metal-based nano catalyst;
the process of the deposition precipitation method comprises the following steps: ultrasonically dispersing a nitrogen-doped mesoporous hollow carbon sphere carrier in water, adjusting the pH value to 9.5-10.5, adding a metal source after the whole solution system is stable, ultrasonically dispersing, adding sodium borohydride into the metal source for reduction reaction, and centrifugally drying a reaction product to obtain a nitrogen-doped mesoporous hollow carbon sphere supported metal-based nano catalyst;
the nitrogen-doped mesoporous hollow carbon sphere supported metal-based nano catalyst comprises a carrier and an active component group, wherein the active component group is attached to the carrier; the carrier is nitrogen-doped mesoporous hollow carbon, and the active component is any one of metal nickel, copper, cobalt, iron, ruthenium, platinum, palladium, iridium, rhodium and gold.
Preferably, in the preparation process of the impregnation method and the deposition precipitation method, 0.001 g-0.3 g of metal source is added into each 2-50 mg/mL of hollow sphere carrier.
Preferably, in the immersion method and the precipitation method, the molar ratio of the sodium borohydride to the metal source is (10-50): 1.
preferably, the metal source is nickel nitrate, palladium chloride, palladium nitrate, cobalt nitrate hexahydrate, potassium tetrachloropalladate, chloroplatinic acid, ruthenium trichloride, copper sulfate, tetrachloro-alloying acid, ferrous nitrate, rhodium trichloride, chloroauric acid or iridium trichloride hydrate.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a nitrogen-doped mesoporous hollow carbon sphere loaded metal-based nano catalyst for selective hydrodeoxygenation of vanillin into 2-methoxy-4-methylphenol. The catalyst is prepared by different methods, and the expression is M @ NHCS, wherein NHCS is a nitrogen-doped mesoporous hollow carbon sphere, and M is any one of metal nickel, copper, cobalt, iron, ruthenium, platinum, palladium, iridium, rhodium and gold. The invention uses hollow carbon spheres as a stable carrier, and can be loaded with metal to realize functionalization. The metal is loaded on the surface of the carbon sphere, so that the metal particles are not easy to agglomerate, and more active sites can be provided. In addition, the hollow carbon sphere also has an adjustable pore structure and an easily-modified surface, the macroscopic size and the shell thickness can be adjusted by a synthesis method, and the characteristics enable the hollow carbon sphere material to have huge performance potential. The introduction of the heteroatom into the carbon material can effectively adjust and improve the properties of the carbon material, including electrical properties, surface and internal chemical properties and the like. Meanwhile, the catalytic performance of the catalyst can be improved by the synergistic effect between the doping atoms and the metal particles. Among the numerous heteroatoms (e.g., boron (B), nitrogen (N), fluorine (F), phosphorus (P), etc.), nitrogen atoms are adjacent to carbon atoms with similar atomic radii and more readily substitute for carbon atoms in the carbon material atomic lattice, thereby forming a nitrogen-doped carbon material. Meanwhile, a large number of mesoporous structures (the aperture is between 2 and 50 nm) in the carbon material are more beneficial to mass transfer in the reaction process than microporous structures (the aperture is below 2 nm); when the metal particles are supported, the dispersion of the metal particles is also facilitated. The high catalytic activity of the catalyst can be ensured by using metal. The invention adopts the metal-based catalyst, has high catalytic performance, high yield, simple green and environment-friendly preparation process, easy separation of the catalyst, good circulation stability and good industrial application prospect.
The invention discloses a preparation method of a nitrogen-doped mesoporous hollow carbon sphere loaded metal-based nano catalyst, which is a direct synthesis method, wherein metal nano particles in the catalyst prepared by the direct synthesis method are positioned on the inner wall of a hollow carbon sphere, and the catalyst with the structure has the characteristics that: has the characteristics of high specific surface area, good monodispersity, adjustable porosity, controllable particle size distribution and the like. The invention also discloses a preparation method of the nitrogen-doped mesoporous hollow carbon sphere loaded metal-based nano catalyst, which comprises an impregnation method and a deposition precipitation method; the metal nano particles in the catalyst obtained by the dipping method are mainly positioned on the outer surface of the hollow carbon ball and in the shell layer pore canal, and the metal nano particles in the catalyst obtained by the deposition precipitation method are positioned on the inner wall of the hollow carbon ball and in the shell layer pore canal. The nitrogen-doped mesoporous hollow carbon sphere loaded metal nano-catalyst obtained by the two methods can be used as a nano-reactor and has a unique confinement effect, and a shell pore passage and a hollow cavity can realize enrichment of reactants and intermediates to promote conversion of the reactants and the intermediates, and can inhibit agglomeration and loss of metal nano-particles, so that the stability of the catalyst is improved. Furthermore, different preparation methods have influence on the structure of the nitrogen-doped hollow carbon sphere supported metal nano catalyst, and the different positions of the metal nano particles in the catalyst in the hollow carbon sphere carrier directly determine the different structures of the catalyst, so that the interaction between the active metal and the carbon sphere carrier is influenced, and the difference of the activity, the selectivity and the stability of the catalyst in a catalytic reaction can be further caused.
Furthermore, dopamine hydrochloride is used as a carbon source and a nitrogen source, so that the dopamine hydrochloride can be mixed with SiO at normal temperature2The carbon shell can be formed only by simple sintering, so that the industrial production is facilitated, more importantly, heteroatom N can be doped into hollow carbon spheres by N in dopamine hydrochloride, and the electron transport capability of the carbon material is enhanced through a synergistic effect.
Furthermore, the nitrogen-doped mesoporous hollow carbon spheres are selected as a load structure, and the structure has a large specific surface area, so that more active sites can be provided for reaction, and simultaneously, the agglomeration of active components of metal ions can be effectively inhibited, so that the metal particles are in a highly dispersed state, the catalytic activity of the catalyst is improved, and the catalyst is more stable.
Furthermore, the catalyst M @ NHCS nitrogen-doped mesoporous hollow carbon sphere loaded metal-based nano catalyst is a heterogeneous catalyst, the preparation process is simple, the catalyst is pollution-free to the environment, green and efficient, high in yield and good in circulation stability, and the catalyst is suitable for industrial production.
Drawings
FIG. 1 is a scanning electron micrograph of a hard template silica sphere;
FIG. 2 is a transmission electron microscope photograph of a nitrogen-doped mesoporous hollow carbon sphere carrier;
FIG. 3 is a transmission electron microscope photograph of Pd @ NHCS-1000 ℃ nitrogen-doped mesoporous hollow carbon sphere loaded metal-based nano-catalyst.
Detailed Description
The invention is described in further detail below with reference to the following figures and specific examples:
the invention adopts a nitrogen-doped mesoporous hollow carbon sphere loaded metal-based nano catalyst, which comprises the following specific steps:
step 1, a preparation method of a nitrogen-doped mesoporous hollow carbon sphere carrier comprises the following specific steps:
step 1.1 preparation of a silicon dioxide hard template: tetraethyl orthosilicate is added into a reaction medium of water and ethanol, and the nano silicon dioxide spheres are synthesized by stirring at 30 ℃ by adopting a sol-gel method.
Step 1.2, adding the nano-silica spheres prepared in the step 1.1 into a trihydroxymethyl aminomethane buffer solution, and performing ultrasonic treatment for 1h, wherein the concentration of the nano-silica spheres in the trihydroxymethyl aminomethane buffer solution is 2-100 mg/mL; and then adding dopamine hydrochloride for polymerization reaction, wherein the polymerization reaction time is 24 hours at 25 ℃, and the mass ratio of the dopamine hydrochloride to the nano silicon dioxide pellets is (0.25-5): 1, obtaining a precursor through centrifugal washing and drying.
Step 1.3, placing the precursor in the step 1.2 in a tubular furnace, roasting in a nitrogen atmosphere, and keeping the temperature for 1-5 hours, wherein the roasting temperature is 600-1000 ℃.
And step 1.4, placing the sample roasted in the step 1.3 in a sodium hydroxide solution, and etching to remove the silicon dioxide template to obtain the nitrogen-doped mesoporous hollow carbon sphere carrier.
Step 2, preparing a catalyst, specifically:
2.1 direct Synthesis:
adding the nano-silica spheres obtained in the step 1.1 into a trihydroxymethyl aminomethane buffer solution, and performing ultrasonic treatment, wherein the concentration of the nano-silica spheres in the trihydroxymethyl aminomethane buffer solution is 2-100 mg/mL, then adding dopamine hydrochloride and 0.001-0.3 g of metal source for polymerization reaction, the polymerization reaction temperature is 25 ℃, the polymerization reaction time is 12-24 h, and the metal source is nickel nitrate, palladium chloride, palladium nitrate, cobalt nitrate hexahydrate, potassium tetrachloropalladate, chloroplatinic acid, ruthenium trichloride, copper sulfate, tetrachloroauric acid, ferrous nitrate, rhodium trichloride, chloroauric acid or iridium trichloride hydrate. The adding amount of the metal source is selected to be that the mass content of the active component in the catalyst is 0.5-10 wt%, and the reaction product is centrifugally washed and dried to obtain a precursor, and then the precursor is placed in a tubular furnace to be roasted at 600-900 ℃ in a nitrogen atmosphere and is subjected to heat preservation for 1-5 hours. And (3) placing the roasted sample in a sodium hydroxide solution with a certain concentration to etch and remove the silicon dioxide template, so as to obtain the nitrogen-doped mesoporous hollow carbon sphere loaded metal-based nano catalyst M @ NHCS.
2.2 impregnation method
Adding deionized water into the nitrogen-doped mesoporous hollow carbon sphere carrier obtained in the step 1.4, and dispersing under ultrasonic waves, wherein the content of the nitrogen-doped mesoporous hollow carbon sphere carrier in water is 2-50 mg/mL; adding 0.001 g-0.3 g of metal source, wherein the mass content of the active component in the catalyst is 0.5-10 wt% of the metal source, and the metal source is nickel nitrate, palladium chloride, palladium nitrate, cobalt nitrate hexahydrate, potassium tetrachloropalladate, chloroplatinic acid, ruthenium trichloride, copper sulfate, tetrachloro-alloy acid, ferrous nitrate, rhodium trichloride, chloroauric acid or iridium trichloride hydrate. Dispersing for a period of time under ultrasonic waves, and after the ultrasonic waves are completely performed, adding a reducing agent sodium borohydride/metal source according to a molar ratio of (10-50) under a low-temperature condition of 0-10 ℃ (sodium borohydride can be slowly decomposed into hydrogen under the low-temperature condition, so that complete reduction is ensured): 1, reducing, centrifuging and drying to obtain the nitrogen-doped mesoporous hollow carbon sphere loaded metal-based nano catalyst M @ NHCS.
2.3 deposition precipitation method
Adding deionized water into the nitrogen-doped mesoporous hollow carbon sphere carrier obtained in the step 1.4, and dispersing under ultrasonic waves, wherein the content of the nitrogen-doped mesoporous hollow carbon sphere carrier in water is 2-50 mg/mL; adjusting the pH value of the solution to 9.5-10.5, adding 0.001-0.3 g of metal source after the pH value of the solution system is kept stable at 9.5-10.5 and does not change, wherein the mass content of active components in the catalyst is selected from 0.5-10 wt%, and the metal source is dispersed for a period of time under ultrasonic waves and is nickel nitrate, palladium chloride, palladium nitrate, cobalt nitrate hexahydrate, potassium tetrachloropalladate, chloroplatinic acid, ruthenium trichloride, copper sulfate, tetrachloroauric acid, ferrous nitrate, rhodium trichloride, chloroauric acid or iridium trichloride hydrate. Adding a reducing agent sodium borohydride/metal source in a molar ratio of (10-50) under a low-temperature condition of 0-10 ℃ (sodium borohydride can be slowly decomposed into hydrogen under the low-temperature condition, so that complete reduction is ensured): 1, reducing, centrifuging and drying to obtain the nitrogen-doped mesoporous hollow carbon sphere loaded metal-based nano catalyst M @ NHCS.
The nitrogen-doped mesoporous hollow carbon sphere loaded metal-based nano catalyst M @ NHCS prepared by the preparation method comprises a carrier and an active component, wherein the content of the active component of the catalyst in the catalyst is 0.5-10 wt% in percentage by mass (the nitrogen-rich carrier and the metal active component interact with each other, and the metal is doped on the surface of the carrier hollow carbon sphere and in the carbon sphere), the carrier is nitrogen-doped mesoporous hollow carbon, and M is any one of metal nickel, copper, cobalt, iron, ruthenium, platinum, palladium, iridium, rhodium and gold.
The mass ratio of the dopamine hydrochloride to the hard template silicon dioxide is (0.25-5): 1. further, in the nitrogen-doped mesoporous hollow carbon sphere supported metal-based nano catalyst M @ NHCS, the metal M is any one of nickel, copper, cobalt, iron, ruthenium, platinum, palladium, iridium, rhodium and gold.
Example 1
Direct synthesis method Pd @ NHCS-600 ℃ (wherein Pd:2.5 wt%, silica: dopamine hydrochloride ═ 1:1) preparation of catalyst: weighing 500mg of nano-silica spheres, adding 50mL of trihydroxymethyl aminomethane buffer solution, carrying out ultrasonic treatment for 1h, adding 500mg of dopamine hydrochloride, polymerizing and stirring for 30min, adding 77.8mg of potassium tetrachloropalladate, continuously stirring for 24h, carrying out centrifugal washing, and drying to obtain a precursor. The precursor is placed in a tube furnace to be roasted at the temperature of 600 ℃ in a nitrogen atmosphere at the temperature of 10 ℃/min and is kept for 1 h. And (2) placing the roasted sample in 5mol/L sodium hydroxide solution, stirring for 6h at 60 ℃, and etching the silicon dioxide template to obtain the nitrogen-doped mesoporous hollow carbon sphere loaded metal-based nano catalyst Pd @ NHCS-600 ℃.
FIG. 1 is a scanning electron micrograph of a hard template silica sphere; from SEM picture, it can be seen that the silica nano-spheres have uniform particle size distribution, good dispersibility, no agglomeration and regular and complete shape.
FIG. 2 is a transmission electron microscope photograph of a nitrogen-doped mesoporous hollow carbon sphere carrier; it can be seen from the figure that the hollow carbon spheres have uniform particle size distribution, the diameter of the hollow carbon spheres is between 320nm and 430nm, and no template residue exists.
Example 2
Direct synthesis Pd @ NHCS-900 deg.C (where Pd:1.5 wt%, silica: dopamine hydrochloride ═ 2:1) catalyst preparation: weighing 500mg of nano-silica spheres, adding 50mL of trihydroxymethyl aminomethane buffer solution, carrying out ultrasonic treatment for 1h, adding 250mg of dopamine hydrochloride, polymerizing and stirring for 30min, adding 35mg of potassium tetrachloropalladate, continuing stirring for 24h, and carrying out centrifugal washing and drying to obtain a precursor. The precursor is placed in a tube furnace to be roasted at the temperature of 900 ℃ in a nitrogen atmosphere at the temperature of 10 ℃/min and is kept for 1 h. And (3) placing the roasted sample in 5mol/L sodium hydroxide solution, stirring for 6h at 60 ℃, and etching the silicon dioxide template to obtain the nitrogen-doped mesoporous hollow carbon sphere loaded metal-based nano catalyst Pd @ NHCS-900 ℃.
Example 3
Direct synthesis Pd @ NHCS-1000 deg.C (where Pd:10 wt%, dopamine hydrochloride: 2:1) catalyst preparation: weighing 500mg of nano-silica spheres, adding 50mL of trihydroxymethyl aminomethane buffer solution, carrying out ultrasonic treatment for 1h, adding 250mg of dopamine hydrochloride, polymerizing and stirring for 30min, adding 232.4mg of potassium tetrachloropalladate, continuously stirring for 24h, carrying out centrifugal washing, and drying to obtain a precursor. The precursor is placed in a tube furnace to be roasted at the temperature of 1000 ℃ in the nitrogen atmosphere at the temperature of 10 ℃/min and is kept for 1 h. And (2) placing the roasted sample in 5mol/L sodium hydroxide solution, stirring for 6h at 60 ℃, and etching the silicon dioxide template to obtain the nitrogen-doped mesoporous hollow carbon sphere loaded metal-based nano catalyst Pd @ NHCS-1000 ℃.
Example 4
Direct synthesis Pd @ NHCS-700 deg.C (where Pd:0.5 wt%, silica: dopamine hydrochloride ═ 2:1) catalyst preparation: weighing 500mg of nano-silica spheres, adding 50mL of trihydroxymethyl aminomethane buffer solution, carrying out ultrasonic treatment for 1h, adding 250mg of dopamine hydrochloride, polymerizing and stirring for 30min, adding 15mg of potassium tetrachloropalladate, continuing stirring for 12h, and carrying out centrifugal washing and drying to obtain a precursor. The precursor is placed in a tube furnace to be roasted at the temperature of 700 ℃ in a nitrogen atmosphere at the temperature of 10 ℃/min and is kept for 3 hours. And (2) placing the roasted sample in 5mol/L sodium hydroxide solution, stirring for 6h at 60 ℃, and etching the silicon dioxide template to obtain the nitrogen-doped mesoporous hollow carbon sphere loaded metal-based nano catalyst Pd @ NHCS-700 ℃.
Example 5
Direct synthesis method Pd @ NHCS-800 ℃ (wherein Pd:5 wt%, silica: dopamine hydrochloride ═ 1:1) preparation of catalyst: weighing 500mg of nano-silica spheres, adding 50mL of trihydroxymethyl aminomethane buffer solution, carrying out ultrasonic treatment for 1h, adding 500mg of dopamine hydrochloride, polymerizing and stirring for 30min, adding 160mg of potassium tetrachloropalladate, continuing stirring for 20h, and carrying out centrifugal washing and drying to obtain a precursor. Placing the precursor in a tube furnace, roasting at 800 ℃ in a nitrogen atmosphere at 10 ℃/min, and keeping the temperature for 5 h. And (2) placing the roasted sample in 5mol/L sodium hydroxide solution, stirring for 6h at 60 ℃, and etching the silicon dioxide template to obtain the nitrogen-doped mesoporous hollow carbon sphere loaded metal-based nano catalyst Pd @ NHCS-800 ℃.
Example 6
Impregnation Pd @ NHCS-800 ℃ (wherein Pd:5 wt%, silica: dopamine hydrochloride ═ 1:1) preparation of catalyst: weighing 250mg of nano silicon dioxide pellets, adding 50mL of trihydroxymethyl aminomethane buffer solution, carrying out ultrasonic treatment for 1h, adding 500mg of dopamine hydrochloride, polymerizing, stirring and stirring for 24h, and carrying out centrifugal washing and drying to obtain a precursor. Placing the precursor in a tube furnace, roasting at 800 ℃ in a nitrogen atmosphere at 10 ℃/min, and keeping the temperature for 1 h. And (3) placing the roasted sample in 5mol/L sodium hydroxide solution, stirring for 6h at 60 ℃, and etching the silicon dioxide template to obtain the N-doped mesoporous hollow carbon sphere NHCS. Weighing 50mg of the obtained nitrogen-doped mesoporous hollow carbon sphere carrier, adding 20ml of deionized water, dispersing for 1 hour under ultrasonic waves, adding 8.2mg of potassium tetrachloropalladate, dispersing for 1 hour under ultrasonic waves, adding 0.25g of reducing agent sodium borohydride at 5 ℃ after complete ultrasonic waves are carried out, fully reducing for 6 hours, and carrying out centrifugal drying to obtain the nitrogen-doped mesoporous hollow carbon sphere loaded metal-based nano catalyst Pd @ NHCS-800 ℃.
Example 7
Impregnation Pd @ NHCS-1000 ℃ (where Pd:0.5 wt%, silica: dopamine hydrochloride ═ 1:1) preparation of catalyst: weighing 500mg of nano silicon dioxide pellets, adding 50mL of trihydroxymethyl aminomethane buffer solution, carrying out ultrasonic treatment for 1h, adding 500mg of dopamine hydrochloride, polymerizing and stirring for 24h, and carrying out centrifugal washing and drying to obtain a precursor. The precursor is placed in a tube furnace to be roasted at the temperature of 1000 ℃ in the nitrogen atmosphere at the temperature of 10 ℃/min and is kept for 1 h. And (3) placing the roasted sample in 5mol/L sodium hydroxide solution, stirring for 6h at 60 ℃, and etching the silicon dioxide template to obtain the N-doped mesoporous hollow carbon sphere NHCS. Weighing 50mg of the obtained nitrogen-doped mesoporous hollow carbon sphere carrier, adding 20ml of deionized water, dispersing for 1 hour under ultrasonic waves, adding 0.8mg of potassium tetrachloropalladate, dispersing for 1 hour under ultrasonic waves, adding 0.25g of reducing agent sodium borohydride at 0 ℃ after complete ultrasonic waves, fully reducing for 6 hours, and centrifugally drying to obtain the nitrogen-doped mesoporous hollow carbon sphere loaded metal-based nano catalyst Pd @ NHCS-1000 ℃.
FIG. 3 is a transmission electron microscope photograph of Pd @ NHCS-1000 ℃ nitrogen-doped mesoporous hollow carbon sphere loaded metal-based nano-catalyst. TEM photographs of the material showed that the supported Pd nanoparticles were uniformly dispersed on the hollow carbon sphere support, and no agglomerated Pd nanoparticles were observed.
Example 8
Impregnation Pd @ NHCS-900 ℃ (where Pd:3 wt%, silica: dopamine hydrochloride ═ 2:1) preparation of catalyst: weighing 500mg of nano silicon dioxide pellets, adding 50mL of trihydroxymethyl aminomethane buffer solution, carrying out ultrasonic treatment for 1h, adding 250mg of dopamine hydrochloride, polymerizing, stirring and stirring for 24h, and carrying out centrifugal washing and drying to obtain a precursor. The precursor is placed in a tube furnace to be roasted at the temperature of 900 ℃ in a nitrogen atmosphere at the temperature of 10 ℃/min and is kept for 1 h. And (3) placing the roasted sample in 5mol/L sodium hydroxide solution, stirring for 6h at 60 ℃, and etching the silicon dioxide template to obtain the N-doped mesoporous hollow carbon sphere NHCS. Weighing 50mg of the obtained nitrogen-doped mesoporous hollow carbon sphere carrier, adding 20ml of deionized water, dispersing for 1 hour under ultrasonic waves, adding 4.92mg of potassium tetrachloropalladate, dispersing for 1 hour under ultrasonic waves, adding 0.25g of reducing agent sodium borohydride for full reduction for 6 hours at 10 ℃ after complete ultrasonic waves are obtained, and performing centrifugal drying to obtain the nitrogen-doped mesoporous hollow carbon sphere loaded metal-based nano catalyst Pd @ NHCS-900 ℃.
Example 9
Impregnation Pd @ NHCS-600 ℃ (where Pd:10 wt%, silica: dopamine hydrochloride ═ 1:1) preparation of catalyst: weighing 100mg of nano silicon dioxide pellets, adding 50mL of trihydroxymethyl aminomethane buffer solution, carrying out ultrasonic treatment for 1h, adding 100mg of dopamine hydrochloride, polymerizing and stirring for 24h, and carrying out centrifugal washing and drying to obtain a precursor. The precursor is put into a tube furnace to be roasted at the temperature of 600 ℃ in a nitrogen atmosphere at the temperature of 10 ℃/min and is kept for 5 hours. And (3) placing the roasted sample in 5mol/L sodium hydroxide solution, stirring for 6h at 60 ℃, and etching the silicon dioxide template to obtain the N-doped mesoporous hollow carbon sphere NHCS. Weighing 1000mg of the obtained nitrogen-doped mesoporous hollow carbon sphere carrier, adding 20ml of deionized water, dispersing for 1 hour under ultrasonic waves, adding 16.4mg of potassium tetrachloropalladate, dispersing for 1 hour under ultrasonic waves, adding 0.25g of reducing agent sodium borohydride at 0 ℃ after complete ultrasonic waves, fully reducing for 6 hours, and centrifugally drying to obtain the nitrogen-doped mesoporous hollow carbon sphere loaded metal-based nano catalyst Pd @ NHCS-600 ℃.
Example 10
Impregnation Pd @ NHCS-1000 ℃ (where Pd:8 wt%, silica: dopamine hydrochloride ═ 2:1) preparation of catalyst: weighing 5000mg of nano silicon dioxide pellets, adding 50mL of trihydroxymethyl aminomethane buffer solution, carrying out ultrasonic treatment for 1h, adding 250mg of dopamine hydrochloride, polymerizing, stirring and stirring for 24h, and carrying out centrifugal washing and drying to obtain a precursor. The precursor is placed in a tube furnace to be roasted at the temperature of 1000 ℃ in the nitrogen atmosphere at the temperature of 10 ℃/min and is kept for 2 hours. And (3) placing the roasted sample in 5mol/L sodium hydroxide solution, stirring for 6h at 60 ℃, and etching the silicon dioxide template to obtain the N-doped mesoporous hollow carbon sphere NHCS. Weighing 50mg of the obtained nitrogen-doped mesoporous hollow carbon sphere carrier, adding 20ml of deionized water, dispersing for 1 hour under ultrasonic waves, adding 13.1mg of potassium tetrachloropalladate, dispersing for 1 hour under ultrasonic waves, adding 0.25g of reducing agent sodium borohydride at 10 ℃ after complete ultrasonic waves, fully reducing for 6 hours, and centrifugally drying to obtain the nitrogen-doped mesoporous hollow carbon sphere loaded metal-based nano catalyst Pd @ NHCS-1000 ℃.
Example 11
Precipitation method Pd @ NHCS-700 ℃ (where Pd:1.5 wt%, silica: dopamine hydrochloride ═ 0.5: 1) preparation of catalyst: weighing 250mg of nano silicon dioxide pellets, adding 50mL of trihydroxymethyl aminomethane buffer solution, carrying out ultrasonic treatment for 1h, adding 500mg of dopamine hydrochloride, polymerizing, stirring and stirring for 24h, and carrying out centrifugal washing and drying to obtain a precursor. The precursor is placed in a tube furnace to be roasted at the temperature of 700 ℃ in a nitrogen atmosphere at the temperature of 10 ℃/min and is kept for 1 h. And (3) placing the roasted sample in 5mol/L sodium hydroxide solution, stirring for 6h at 60 ℃, and etching the silicon dioxide template to obtain the N-doped mesoporous hollow carbon sphere NHCS. Weighing 50mg of the obtained nitrogen-doped mesoporous hollow carbon sphere carrier, adding 20ml of deionized water, dispersing for 1 hour under ultrasonic waves, adjusting the pH of the solution to 10 by using 1mol/L of sodium hydroxide, adding 2.5mg of potassium tetrachloropalladate, dispersing for 1 hour under ultrasonic waves, adding 0.25g of sodium borohydride as a reducing agent for reduction for 6 hours at 10 ℃ after complete ultrasonic waves are carried out, and centrifugally drying to obtain the nitrogen-doped mesoporous hollow carbon sphere loaded metal-based nano catalyst Pd @ NHCS-700 ℃.
Example 12
Precipitation method Pd @ NHCS-600 ℃ (wherein Pd:5 wt%, silica: dopamine hydrochloride ═ 0.5: 1) preparation of catalyst: weighing 250mg of nano silicon dioxide pellets, adding 50mL of trihydroxymethyl aminomethane buffer solution, carrying out ultrasonic treatment for 1h, adding 500mg of dopamine hydrochloride, polymerizing, stirring and stirring for 24h, and carrying out centrifugal washing and drying to obtain a precursor. The precursor is placed in a tube furnace to be roasted at the temperature of 600 ℃ in a nitrogen atmosphere at the temperature of 10 ℃/min and is kept for 1 h. And (3) placing the roasted sample in 5mol/L sodium hydroxide solution, stirring for 6h at 60 ℃, and etching the silicon dioxide template to obtain the N-doped mesoporous hollow carbon sphere NHCS. Weighing 50mg of the obtained nitrogen-doped mesoporous hollow carbon sphere carrier, adding 20ml of deionized water, dispersing for 1 hour under ultrasonic waves, adjusting the pH of the solution to 10 by using 1mol/L of sodium hydroxide, adding 8.2mg of potassium tetrachloropalladate, dispersing for 1 hour under ultrasonic waves, adding 0.25g of sodium borohydride as a reducing agent to reduce for 6 hours under the condition of low temperature after complete ultrasonic waves are carried out, and centrifugally drying to obtain the nitrogen-doped mesoporous hollow carbon sphere loaded metal-based nano catalyst Pd @ NHCS-600 ℃.
Example 13
Precipitation method Pd @ NHCS-1000 ℃ (where Pd:1.5 wt%, silica: dopamine hydrochloride ═ 0.5: 1) preparation of catalyst: weighing 250mg of nano silicon dioxide pellets, adding 50mL of trihydroxymethyl aminomethane buffer solution, carrying out ultrasonic treatment for 1h, adding 500mg of dopamine hydrochloride, polymerizing, stirring and stirring for 24h, and carrying out centrifugal washing and drying to obtain a precursor. The precursor is placed in a tube furnace to be roasted at the temperature of 1000 ℃ in the nitrogen atmosphere at the temperature of 10 ℃/min and is kept for 1 h. And (3) placing the roasted sample in 5mol/L sodium hydroxide solution, stirring for 6h at 60 ℃, and etching the silicon dioxide template to obtain the N-doped mesoporous hollow carbon sphere NHCS. Weighing 50mg of the obtained nitrogen-doped mesoporous hollow carbon sphere carrier, adding 20ml of deionized water, dispersing for 1 hour under ultrasonic waves, adjusting the pH of the solution to 10 by using 1mol/L of sodium hydroxide, adding 2.5mg of potassium tetrachloropalladate, dispersing for 1 hour under ultrasonic waves, adding 0.25g of sodium borohydride as a reducing agent to reduce for 6 hours under the condition of low temperature after complete ultrasonic waves are carried out, and centrifugally drying to obtain the nitrogen-doped mesoporous hollow carbon sphere loaded metal-based nano catalyst Pd @ NHCS-1000 ℃.
Example 14
Precipitation method Pd @ NHCS-600 ℃ (where Pd:10 wt%, silica: dopamine hydrochloride ═ 0.5: 1) preparation of catalyst: weighing 100mg of nano silicon dioxide pellets, adding 50mL of trihydroxymethyl aminomethane buffer solution, carrying out ultrasonic treatment for 1h, adding 250mg of dopamine hydrochloride, polymerizing, stirring and stirring for 24h, and carrying out centrifugal washing and drying to obtain a precursor. The precursor is put into a tube furnace to be roasted at the temperature of 600 ℃ in a nitrogen atmosphere at the temperature of 10 ℃/min and is kept for 5 hours. And (3) placing the roasted sample in 5mol/L sodium hydroxide solution, stirring for 6h at 60 ℃, and etching the silicon dioxide template to obtain the N-doped mesoporous hollow carbon sphere NHCS. Weighing 1000mg of the obtained nitrogen-doped mesoporous hollow carbon sphere carrier, adding 20ml of deionized water, dispersing for 1 hour under ultrasonic waves, adjusting the pH of the solution to 10 by using 1mol/L of sodium hydroxide, adding 16.4mg of potassium tetrachloropalladate, dispersing for 1 hour under ultrasonic waves, adding 0.25g of sodium borohydride as a reducing agent for reduction for 6 hours at 10 ℃ after complete ultrasonic waves are carried out, and centrifugally drying to obtain the nitrogen-doped mesoporous hollow carbon sphere loaded metal-based nano catalyst Pd @ NHCS-700 ℃.
Example 15
Precipitation method Pd @ NHCS-1000 ℃ (where Pd:8 wt%, silica: dopamine hydrochloride ═ 0.5: 1) preparation of catalyst: weighing 5000mg of nano silicon dioxide pellets, adding 50mL of trihydroxymethyl aminomethane buffer solution, carrying out ultrasonic treatment for 1h, adding 250mg of dopamine hydrochloride, polymerizing, stirring and stirring for 24h, and carrying out centrifugal washing and drying to obtain a precursor. The precursor is placed in a tube furnace to be roasted at the temperature of 1000 ℃ in the nitrogen atmosphere at the temperature of 10 ℃/min and is kept for 2 hours. And (3) placing the roasted sample in 5mol/L sodium hydroxide solution, stirring for 6h at 60 ℃, and etching the silicon dioxide template to obtain the N-doped mesoporous hollow carbon sphere NHCS. Weighing 40mg of the obtained nitrogen-doped mesoporous hollow carbon sphere carrier, adding 20ml of deionized water, dispersing for 1 hour under ultrasonic waves, adjusting the pH of the solution to 10 by using 1mol/L of sodium hydroxide, adding 13.1mg of potassium tetrachloropalladate, dispersing for 1 hour under ultrasonic waves, adding 0.25g of sodium borohydride as a reducing agent to reduce for 6 hours under the condition of low temperature after complete ultrasonic waves are carried out, and centrifugally drying to obtain the nitrogen-doped mesoporous hollow carbon sphere loaded metal-based nano catalyst Pd @ NHCS-1000 ℃.
Example 16
Adding 0.01g of direct synthesis Pd @ NHCS-1000 ℃ (wherein Pd:1.5 wt%, silicon dioxide: dopamine hydrochloride: 1) catalyst, 0.076g of vanillin and 5mL of deionized water into a 30mL reaction kettle lining, introducing high-purity hydrogen to replace gas for 5 times, introducing hydrogen to 2MPa, heating to 100 ℃, keeping for 6 hours, after the reaction is finished, rapidly cooling to room temperature, then carrying out centrifugal separation on reaction liquid, taking supernatant liquid for liquid chromatography detection, and the result shows that the yield of 2-methoxy-4 methylphenol is 89%.
Example 17
Adding 0.01g of precipitated Pd @ NHCS-1000 ℃ (wherein Pd is 5 wt%, silicon dioxide is dopamine hydrochloride is 1:1) catalyst, 0.076g of vanillin and 5mL of deionized water into a 30mL reaction kettle lining, introducing high-purity hydrogen to replace gas for 5 times, introducing hydrogen to 0.1MPa, heating to 60 ℃, keeping for 2 hours, after the reaction is finished, rapidly cooling to room temperature, then carrying out centrifugal separation on reaction liquid, taking supernatant liquid, and carrying out liquid chromatography detection, wherein the result shows that the yield of 2-methoxy-4 methylphenol is 99%.
Example 18
Adding 0.01g of direct synthesis Pd @ NHCS-1000 ℃ (wherein Pd is 5 wt%, silicon dioxide is dopamine hydrochloride is 1:1) catalyst, 0.076g of vanillin and 5mL of deionized water into a 30mL reaction kettle lining, introducing high-purity hydrogen to replace gas for 5 times, introducing hydrogen to 3MPa, heating to 140 ℃, keeping for 6 hours, after the reaction is finished, rapidly cooling to room temperature, then carrying out centrifugal separation on reaction liquid, taking supernatant liquid to carry out liquid chromatography detection, and the result shows that the yield of 2-methoxy-4 methylphenol is 99%.
Example 19
Adding 0.01g of impregnation method Pd @ NHCS-900 ℃ (wherein Pd:3.5 wt%, silicon dioxide: dopamine hydrochloride ═ 2:1) catalyst, 0.076g of vanillin and 5mL of isopropanol into a 50mL glass test tube, introducing high-purity hydrogen to replace gas for 5 times, introducing hydrogen to 0.1MPa, heating to 80 ℃, keeping for 4 hours, after the reaction is finished, rapidly cooling to room temperature, then carrying out centrifugal separation on reaction liquid, taking supernatant liquid, and carrying out liquid chromatography detection, wherein the result shows that the yield of 2-methoxy-4 methylphenol is 39%.
Example 20
Direct synthesis Ni @ NHCS-600 ℃ (with Pd:2.5 wt%, silica: dopamine hydrochloride ═ 1:1) catalyst preparation: weighing 500mg of nano-silica spheres, adding 50mL of trihydroxymethyl aminomethane buffer solution, carrying out ultrasonic treatment for 1h, adding 500mg of dopamine hydrochloride, polymerizing and stirring for 30min, adding nickel nitrate, continuously stirring for 24h, carrying out centrifugal washing, and drying to obtain a precursor. The precursor is placed in a tube furnace to be roasted at the temperature of 600 ℃ in a nitrogen atmosphere at the temperature of 10 ℃/min and is kept for 1 h. And (2) placing the roasted sample in 5mol/L sodium hydroxide solution, stirring for 6h at 60 ℃, and etching the silicon dioxide template to obtain the nitrogen-doped mesoporous hollow carbon sphere loaded metal-based nano catalyst Ni @ NHCS-600 ℃.
Example 21
Direct synthesis Pd @ NHCS-900 deg.C (where Pd:1.5 wt%, silica: dopamine hydrochloride ═ 2:1) catalyst preparation: weighing 500mg of nano-silica spheres, adding 50mL of trihydroxymethyl aminomethane buffer solution, carrying out ultrasonic treatment for 1h, adding 250mg of dopamine hydrochloride, polymerizing and stirring for 30min, adding palladium chloride, continuing stirring for 24h, carrying out centrifugal washing, and drying to obtain a precursor. The precursor is placed in a tube furnace to be roasted at the temperature of 900 ℃ in a nitrogen atmosphere at the temperature of 10 ℃/min and is kept for 1 h. And (3) placing the roasted sample in 5mol/L sodium hydroxide solution, stirring for 6h at 60 ℃, and etching the silicon dioxide template to obtain the nitrogen-doped mesoporous hollow carbon sphere loaded metal-based nano catalyst Pd @ NHCS-900 ℃.
Example 22
Direct synthesis Pd @ NHCS-1000 deg.C (where Pd:10 wt%, dopamine hydrochloride: 2:1) catalyst preparation: weighing 500mg of nano silicon dioxide pellets, adding 50mL of trihydroxymethyl aminomethane buffer solution, carrying out ultrasonic treatment for 1h, adding 250mg of dopamine hydrochloride, polymerizing and stirring for 30min, adding palladium nitrate, continuing stirring for 24h, carrying out centrifugal washing, and drying to obtain a precursor. The precursor is placed in a tube furnace to be roasted at the temperature of 1000 ℃ in the nitrogen atmosphere at the temperature of 10 ℃/min and is kept for 1 h. And (2) placing the roasted sample in 5mol/L sodium hydroxide solution, stirring for 6h at 60 ℃, and etching the silicon dioxide template to obtain the nitrogen-doped mesoporous hollow carbon sphere loaded metal-based nano catalyst Pd @ NHCS-1000 ℃.
Example 23
Direct synthesis Co @ NHCS-700 deg.C (where Co:0.5 wt%, silica: dopamine hydrochloride ═ 2:1) catalyst preparation: weighing 500mg of nano-silica spheres, adding 50mL of trihydroxymethyl aminomethane buffer solution, carrying out ultrasonic treatment for 1h, adding 250mg of dopamine hydrochloride, polymerizing and stirring for 30min, adding cobalt nitrate hexahydrate, continuing stirring for 12h, and carrying out centrifugal washing and drying to obtain a precursor. The precursor is placed in a tube furnace to be roasted at the temperature of 700 ℃ in a nitrogen atmosphere at the temperature of 10 ℃/min and is kept for 3 hours. And (2) placing the roasted sample in 5mol/L sodium hydroxide solution, stirring for 6h at 60 ℃, and etching the silicon dioxide template to obtain the nitrogen-doped mesoporous hollow carbon sphere loaded metal-based nano catalyst Co @ NHCS-700 ℃.
Example 24
Direct synthesis method Pt @ NHCS-800 ℃ (wherein Pt:5 wt%, silica: dopamine hydrochloride ═ 1:1) preparation of catalyst: weighing 500mg of nano-silica spheres, adding 50mL of trihydroxymethyl aminomethane buffer solution, carrying out ultrasonic treatment for 1h, adding 500mg of dopamine hydrochloride, polymerizing and stirring for 30min, adding chloroplatinic acid, continuing stirring for 20h, carrying out centrifugal washing, and drying to obtain a precursor. Placing the precursor in a tube furnace, roasting at 800 ℃ in a nitrogen atmosphere at 10 ℃/min, and keeping the temperature for 5 h. And (2) placing the roasted sample in 5mol/L sodium hydroxide solution, stirring for 6h at 60 ℃, and etching the silicon dioxide template to obtain the nitrogen-doped mesoporous hollow carbon sphere loaded metal-based nano catalyst Pt @ NHCS-800 ℃.
Example 25
Impregnation preparation of Ru @ NHCS-800 ℃ (where Ru:5 wt%, silica: dopamine hydrochloride ═ 1:1) catalyst: weighing 250mg of nano silicon dioxide pellets, adding 50mL of trihydroxymethyl aminomethane buffer solution, carrying out ultrasonic treatment for 1h, adding 500mg of dopamine hydrochloride, polymerizing, stirring and stirring for 24h, and carrying out centrifugal washing and drying to obtain a precursor. Placing the precursor in a tube furnace, roasting at 800 ℃ in a nitrogen atmosphere at 10 ℃/min, and keeping the temperature for 1 h. And (3) placing the roasted sample in 5mol/L sodium hydroxide solution, stirring for 6h at 60 ℃, and etching the silicon dioxide template to obtain the N-doped mesoporous hollow carbon sphere NHCS. Weighing 50mg of the obtained nitrogen-doped mesoporous hollow carbon sphere carrier, adding 20ml of deionized water, dispersing for 1 hour under ultrasonic waves, adding ruthenium trichloride, dispersing for 1 hour under ultrasonic waves, adding 0.25g of reducing agent sodium borohydride at 5 ℃ after ultrasonic waves are completely dispersed, fully reducing for 6 hours, and centrifugally drying to obtain the nitrogen-doped mesoporous hollow carbon sphere loaded metal-based nano catalyst Ru @ NHCS-800 ℃.
Example 26
Impregnation method preparation of Cu @ NHCS-1000 ℃ (where Cu:0.5 wt%, silica: dopamine hydrochloride ═ 1:1) catalyst: weighing 500mg of nano silicon dioxide pellets, adding 50mL of trihydroxymethyl aminomethane buffer solution, carrying out ultrasonic treatment for 1h, adding 500mg of dopamine hydrochloride, polymerizing and stirring for 24h, and carrying out centrifugal washing and drying to obtain a precursor. The precursor is placed in a tube furnace to be roasted at the temperature of 10 DEG/min to 1000 ℃ under the nitrogen atmosphere and is kept warm for 1 h. And (3) placing the roasted sample in 5mol/L sodium hydroxide solution, stirring for 6h at 60 ℃, and etching the silicon dioxide template to obtain the N-doped mesoporous hollow carbon sphere NHCS. Weighing 50mg of the obtained nitrogen-doped mesoporous hollow carbon sphere carrier, adding 20ml of deionized water, dispersing for 1 hour under ultrasonic waves, adding copper sulfate, dispersing for 1 hour under ultrasonic waves, adding 0.25g of reducing agent sodium borohydride at 0 ℃ after ultrasonic waves are completely removed, fully reducing for 6 hours, and centrifugally drying to obtain the nitrogen-doped mesoporous hollow carbon sphere loaded metal-based nano catalyst Cu @ NHCS-1000 ℃.
Example 27
Impregnation method preparation of Au @ NHCS-900 ℃ (where Au:3 wt%, silica: dopamine hydrochloride ═ 2:1) catalyst: weighing 500mg of nano silicon dioxide pellets, adding 50mL of trihydroxymethyl aminomethane buffer solution, carrying out ultrasonic treatment for 1h, adding 250mg of dopamine hydrochloride, polymerizing, stirring and stirring for 24h, and carrying out centrifugal washing and drying to obtain a precursor. The precursor is placed in a tube furnace to be roasted at the temperature of 900 ℃ in a nitrogen atmosphere at the temperature of 10 ℃/min and is kept for 1 h. And (3) placing the roasted sample in 5mol/L sodium hydroxide solution, stirring for 6h at 60 ℃, and etching the silicon dioxide template to obtain the N-doped mesoporous hollow carbon sphere NHCS. Weighing 50mg of the obtained nitrogen-doped mesoporous hollow carbon sphere carrier, adding 20ml of deionized water, dispersing for 1 hour under ultrasonic waves, adding tetrachloroalloy acid, dispersing for 1 hour under ultrasonic waves, adding 0.25g of reducing agent sodium borohydride for full reduction for 6 hours at 10 ℃ after ultrasonic waves are completely removed, and performing centrifugal drying to obtain the nitrogen-doped mesoporous hollow carbon sphere loaded metal-based nano catalyst Au @ NHCS-900 ℃.
Example 28
Impregnation method preparation of Fe @ NHCS-600 ℃ (where Fe:10 wt%, silica: dopamine hydrochloride ═ 1:1) catalyst: weighing 100mg of nano silicon dioxide pellets, adding 50mL of trihydroxymethyl aminomethane buffer solution, carrying out ultrasonic treatment for 1h, adding 100mg of dopamine hydrochloride, polymerizing and stirring for 24h, and carrying out centrifugal washing and drying to obtain a precursor. The precursor is put into a tube furnace to be roasted at the temperature of 600 ℃ in a nitrogen atmosphere at the temperature of 10 ℃/min and is kept for 5 hours. And (3) placing the roasted sample in 5mol/L sodium hydroxide solution, stirring for 6h at 60 ℃, and etching the silicon dioxide template to obtain the N-doped mesoporous hollow carbon sphere NHCS. Weighing 1000mg of the obtained nitrogen-doped mesoporous hollow carbon sphere carrier, adding 20ml of deionized water, dispersing for 1 hour under ultrasonic waves, adding ferrous nitrate, dispersing for 1 hour under ultrasonic waves, adding 0.25g of reducing agent sodium borohydride at 0 ℃ after ultrasonic waves are completely dispersed, fully reducing for 6 hours, and centrifugally drying to obtain the nitrogen-doped mesoporous hollow carbon sphere loaded metal-based nano catalyst Fe @ NHCS-600 ℃.
Example 29
Impregnation method preparation of Rh @ NHCS-1000 ℃ (where Rh:8 wt%, silica: dopamine hydrochloride ═ 2:1) catalyst: weighing 5000mg of nano silicon dioxide pellets, adding 50mL of trihydroxymethyl aminomethane buffer solution, carrying out ultrasonic treatment for 1h, adding 250mg of dopamine hydrochloride, polymerizing, stirring and stirring for 24h, carrying out centrifugal washing, and drying to obtain a precursor. The precursor is placed in a tube furnace to be roasted at the temperature of 1000 ℃ in the nitrogen atmosphere at the temperature of 10 ℃/min and is kept for 2 hours. And (3) placing the roasted sample in 5mol/L sodium hydroxide solution, stirring for 6h at 60 ℃, and etching the silicon dioxide template to obtain the N-doped mesoporous hollow carbon sphere NHCS. Weighing 50mg of the obtained nitrogen-doped mesoporous hollow carbon sphere carrier, adding 20ml of deionized water, dispersing for 1 hour under ultrasonic waves, adding 13.1mg of rhodium trichloride, dispersing for 1 hour under ultrasonic waves, adding 0.25g of reducing agent sodium borohydride for full reduction for 6 hours at 10 ℃ after ultrasonic waves are completely removed, and performing centrifugal drying to obtain the nitrogen-doped mesoporous hollow carbon sphere loaded metal-based nano catalyst Rh @ NHCS-1000 ℃.
Example 30
Precipitation method Au @ NHCS-700 ℃ (where Au:1.5 wt%, silica: dopamine hydrochloride ═ 0.5: 1) preparation of catalyst: weighing 250mg of nano silicon dioxide pellets, adding 50mL of trihydroxymethyl aminomethane buffer solution, carrying out ultrasonic treatment for 1h, adding 500mg of dopamine hydrochloride, polymerizing, stirring and stirring for 24h, and carrying out centrifugal washing and drying to obtain a precursor. The precursor is placed in a tube furnace to be roasted at the temperature of 700 ℃ in a nitrogen atmosphere at the temperature of 10 ℃/min and is kept for 1 h. And (3) placing the roasted sample in 5mol/L sodium hydroxide solution, stirring for 6h at 60 ℃, and etching the silicon dioxide template to obtain the N-doped mesoporous hollow carbon sphere NHCS. Weighing 50mg of the obtained nitrogen-doped mesoporous hollow carbon sphere carrier, adding 20ml of deionized water, dispersing for 1 hour under ultrasonic waves, adjusting the pH of the solution to 10 by using 1mol/L of sodium hydroxide, adding chloroauric acid, dispersing for 1 hour under ultrasonic waves, adding 0.25g of sodium borohydride reducing agent for reduction for 6 hours at 10 ℃ after ultrasonic waves are completely removed, and centrifugally drying to obtain the nitrogen-doped mesoporous hollow carbon sphere loaded metal-based nano catalyst Au NHCS-700 ℃.
Example 31
Precipitation method Ir @ NHCS-600 ℃ (where Ir:5 wt%, silica: dopamine hydrochloride ═ 0.5: 1) preparation of catalyst: weighing 250mg of nano silicon dioxide pellets, adding 50mL of trihydroxymethyl aminomethane buffer solution, carrying out ultrasonic treatment for 1h, adding 500mg of dopamine hydrochloride, polymerizing, stirring and stirring for 24h, and carrying out centrifugal washing and drying to obtain a precursor. The precursor is placed in a tube furnace to be roasted at the temperature of 600 ℃ in a nitrogen atmosphere at the temperature of 10 ℃/min and is kept for 1 h. And (3) placing the roasted sample in 5mol/L sodium hydroxide solution, stirring for 6h at 60 ℃, and etching the silicon dioxide template to obtain the N-doped mesoporous hollow carbon sphere NHCS. And weighing 50mg of the obtained nitrogen-doped mesoporous hollow carbon sphere carrier, adding 20ml of deionized water, dispersing for 1 hour under ultrasonic waves, adjusting the pH of the solution to 10 with 1mol/L of sodium hydroxide, adding iridium trichloride hydrate, dispersing for 1 hour under ultrasonic waves, adding 0.25g of sodium borohydride into the solution under a low-temperature condition after completely ultrasonic waves are carried out, reducing for 6 hours, and carrying out centrifugal drying to obtain the nitrogen-doped mesoporous hollow carbon sphere loaded metal-based nano catalyst Ir @ NHCS-600 ℃.
In conclusion, the invention mainly researches a green and efficient preparation method of the nitrogen-doped mesoporous hollow carbon sphere loaded metal-based nano catalyst for selective hydrodeoxygenation of vanillin into 2-methoxy-4-methylphenol. The invention adopts the metal-based catalyst, has high catalytic performance, high yield, simple green and environment-friendly preparation process, easy separation of the catalyst, good circulation stability and good industrial application prospect.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (10)

1. The nitrogen-doped mesoporous hollow carbon sphere supported metal-based nano catalyst is characterized by comprising a carrier and an active component, wherein the active component is attached to the carrier; the carrier is nitrogen-doped mesoporous hollow carbon, and the active component is any one of metal nickel, copper, cobalt, iron, ruthenium, platinum, palladium, iridium, rhodium and gold;
the mass content of the active component in the catalyst is 0.5-10 wt% in terms of mass fraction.
2. A preparation method of a nitrogen-doped mesoporous hollow carbon sphere loaded metal-based nano catalyst is characterized by comprising the following steps:
step 1, adding tetraethyl orthosilicate into a reaction medium of water and ethanol, and stirring by adopting a sol-gel method to prepare nano silicon dioxide pellets;
step 2, placing the nano-silica spheres in a trihydroxymethyl aminomethane buffer solution, performing ultrasonic treatment, then adding dopamine hydrochloride and a metal source, performing polymerization reaction, and washing and drying a reaction product to obtain a precursor;
step 3, roasting the precursor in a furnace;
step 4, placing the roasted product in sodium hydroxide and stirring to obtain a nitrogen-doped mesoporous hollow carbon sphere supported metal-based nano catalyst;
the nitrogen-doped mesoporous hollow carbon sphere loaded metal-based nano catalyst comprises a carrier and an active component, wherein the active component is attached to the carrier; the carrier is nitrogen-doped mesoporous hollow carbon, and the active component is any one of metal nickel, copper, cobalt, iron, ruthenium, platinum, palladium, iridium, rhodium and gold.
3. The method for preparing the nitrogen-doped mesoporous hollow carbon sphere supported metal-based nano catalyst according to claim 2, wherein in the step 2, the ultrasonic treatment time is 1 hour, the polymerization reaction time is 12-24 hours, and the polymerization reaction temperature is 25 ℃.
4. The preparation method of the nitrogen-doped mesoporous hollow carbon sphere supported metal-based nano catalyst according to claim 2, wherein in the step 2, the concentration of the nano silica in the tris is 2-100 mg/mL.
5. The preparation method of the nitrogen-doped mesoporous hollow carbon sphere supported metal-based nano catalyst according to claim 2, wherein in the step 2, the mixing mass ratio of dopamine hydrochloride to tris (hydroxymethyl) aminomethane buffer solution is (0.5-1): 1; the addition amount of the metal source is selected to be 0.5-10 wt% of the mass content of the active component in the catalyst.
6. The preparation method of the nitrogen-doped mesoporous hollow carbon sphere supported metal-based nano catalyst according to claim 2, wherein in the step 3, the roasting temperature is 600-900 ℃ and the roasting time is 1-5 hours.
7. A preparation method of a nitrogen-doped mesoporous hollow carbon sphere loaded metal-based nano catalyst is characterized by comprising the following steps:
step 1, adding tetraethyl orthosilicate into a reaction medium of water and ethanol, and stirring by adopting a sol-gel method to prepare nano silicon dioxide pellets;
step 2, placing the nano silicon dioxide pellets in a trihydroxymethyl aminomethane buffer solution, carrying out ultrasonic treatment, adding dopamine hydrochloride for polymerization reaction, and centrifugally washing and drying a reaction product to obtain a precursor;
step 3, roasting the precursor;
step 4, stirring the roasted sample in a sodium hydroxide solution to obtain a nitrogen-doped mesoporous hollow carbon sphere carrier;
step 5, preparing the nitrogen-doped mesoporous hollow carbon sphere supported metal-based nano catalyst by using a nitrogen-doped mesoporous hollow carbon sphere carrier through an impregnation method or a deposition precipitation method;
the process of the impregnation method is as follows: ultrasonically dispersing a nitrogen-doped mesoporous hollow carbon sphere carrier in water, adding a metal source, after completely ultrasonic treating, adding sodium borohydride for reduction reaction, and centrifugally drying a reaction product to obtain a nitrogen-doped mesoporous hollow carbon sphere loaded metal-based nano catalyst;
the process of the deposition precipitation method comprises the following steps: ultrasonically dispersing a nitrogen-doped mesoporous hollow carbon sphere carrier in water, adjusting the pH value to 9.5-10.5, adding a metal source after the whole solution system is stable, ultrasonically dispersing, adding sodium borohydride into the metal source for reduction reaction, and centrifugally drying a reaction product to obtain a nitrogen-doped mesoporous hollow carbon sphere supported metal-based nano catalyst;
the nitrogen-doped mesoporous hollow carbon sphere loaded metal-based nano catalyst comprises a carrier and an active component group, wherein the active component group is attached to the carrier; the carrier is nitrogen-doped mesoporous hollow carbon, and the active component is any one of metal nickel, copper, cobalt, iron, ruthenium, platinum, palladium, iridium, rhodium and gold.
8. The preparation method of the nitrogen-doped mesoporous hollow carbon sphere-supported metal-based nano catalyst according to claim 7, wherein in the preparation processes of the impregnation method and the deposition precipitation method, 0.001g to 0.3g of metal source is added to each 2 mg/mL to 50mg/mL of hollow sphere carrier.
9. The preparation method of the nitrogen-doped mesoporous hollow carbon sphere supported metal-based nano catalyst according to claim 7, wherein in the impregnation method and the precipitation deposition method, the molar ratio of the sodium borohydride to the metal source is (10-50): 1.
10. the method for preparing the nitrogen-doped mesoporous hollow carbon sphere supported metal-based nanocatalyst of claim 2 or 7, wherein the metal source is nickel nitrate, palladium chloride, palladium nitrate, cobalt nitrate hexahydrate, potassium tetrachloropalladate, chloroplatinic acid, ruthenium trichloride, copper sulfate, tetrachloroalloy acid, ferrous nitrate, rhodium trichloride, chloroauric acid or iridium trichloride hydrate.
CN202210192858.7A 2022-02-28 2022-02-28 Nitrogen-doped mesoporous hollow carbon sphere loaded metal-based nano catalyst and preparation method thereof Pending CN114453000A (en)

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