CN115160266A - Method for applying catalyst with platinum nanoparticles loaded on inner wall of carbon nanotube to furfural hydrogenation reaction - Google Patents
Method for applying catalyst with platinum nanoparticles loaded on inner wall of carbon nanotube to furfural hydrogenation reaction Download PDFInfo
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- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 112
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 112
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 104
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 title claims abstract description 78
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—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 substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/42—Singly bound oxygen atoms
- C07D307/44—Furfuryl alcohol
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
- B01J35/399—Distribution of the active metal ingredient homogeneously throughout the support particle
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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Abstract
The invention provides a method for a furfural hydrogenation reaction by using a platinum nanoparticle catalyst loaded on the inner wall of a carbon nanotube. Stirring and grinding through external force to react with the surface of the carbon nano tube with the opening. During the slow evaporation of the solvent, the filled metal precursor is continuously introduced into the cavity of the carbon tube. By milling, slow drying is controlled so that there is enough time for more platinum ions to enter the lumen of the carbon tube. The method has strong experimental controllability, can selectively control the filling of the metal particles in the tube wall of the carbon nano tube, and the percentage of the metal particles in the tube can reach 90 percent or more. Under normal temperature and normal pressure, isopropanol is used as a solvent, 5wt.% of Pt-in-MWNT catalyst is in a reaction solution with furfural mass concentration of 5wt.%, and after 100 hours of reaction, the conversion rate of furfural can still reach 90%, and the selectivity of furfuryl alcohol can still reach 95%.
Description
Technical Field
The invention relates to a preparation method of a catalyst loading metal nano particles on the inner wall of a carbon nano tube. In particular to a method for selectively and uniformly dispersing a metal platinum nanoparticle catalyst on the inner wall of a carbon nanotube, which is mainly used for the catalytic hydrogenation reaction of furfural and derivatives thereof and belongs to the technical field of composite materials and the technical field of hydrogenation reaction.
Background
Carbon nanotubes are a class of nanomaterials consisting of a two-dimensional hexagonal lattice of carbon atoms, which are bent in one direction and combined to form a hollow cylinder. Carbon nanotubes are one of the allotropes of carbon, between fullerene (0-dimensional) and graphene (2-dimensional). Carbon nanotubes are receiving much attention from researchers in various fields due to their unique physical and chemical properties on a nanometer scale. One of the most interesting properties of carbon nanotubes is that their quasi-one-dimensional nanoscale tubular structures can be used as nano-scale containers or reactors, and a series of novel nanocomposites with specific structures and properties can be obtained [ Monthiouxet al, j.mater.res.2006,21,2774].
The unique quasi-one-dimensional nano-scale tubular cavity structure of the carbon nano tube enables the carbon nano tube to become a new catalyst carrier, researches are carried out to fill fullerene molecules, metal/metal oxides, metal carbides, even biomolecules and the like into the tubular cavity of the carbon nano tube, and the filled carbon nano tube composite material is found to show excellent physicochemical properties such as electric conductivity, heat conductivity, electromagnetism and mechanical properties. Thus laying a foundation for researching and developing composite materials with peculiar properties and application. For example, a metal catalyst supported on the inner wall surface of a carbon nanotube also shows good catalytic performance, such as hydrogen-involved reaction, and the catalyst confined in the lumen has higher catalytic activity than the catalyst outside the tube, and the selectivity of the product is different, as reported in Nature Materials 6 (2007) 507.
From the current research situation at home and abroad, the filling of the carbon nano tube mainly comprises: arc discharge, physical, chemical, and the like. These methods require severe conditions, have low filling efficiency, are difficult to control the amount of supported metal, and are more uneconomical methods for filling with noble metals. In addition, the small particles agglomerated by the non-uniform dispersion of the metal cause the blockage of the lumen of the carbon tube, which is not favorable for the transport of the reactants and products of the chemical reaction in the lumen, thereby causing the reduction of the reactivity. For the catalytic reaction, the metal is finally uniformly dispersed on the carrier in the form of uniform nanoparticles, which is advantageous for obtaining the highest activity and selectivity. Therefore, it is still a challenge to selectively and uniformly disperse the metal catalyst particles on the inner wall or only on the outer wall of the carbon nanotube.
Disclosure of Invention
In order to solve the technical problems, a preparation method for controlling the loading of the metal nanoparticle catalyst in the carbon nano tube is provided, in particular to a method for selectively and uniformly dispersing the metal platinum nanoparticle catalyst on the inner wall of the carbon nano tube, which is mainly used for catalytic hydrogenation reaction of furfural and derivatives thereof. Under normal temperature and normal pressure, isopropanol is used as a solvent, 5wt.% of Pt-in-MWNT catalyst is in a reaction solution with furfural mass concentration of 5wt.%, and after 100h of reaction, the conversion rate of furfural can still reach 90%, and the selectivity of furfuryl alcohol can still reach 95%.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: a method for applying a platinum nanoparticle catalyst loaded on the inner wall of a carbon nanotube to furfural hydrogenation comprises the following steps:
(1) Pretreatment of the carbon nanotubes: including purification, opening and cutting.
Immersing the carbon nano tube by using concentrated nitric acid with the mass concentration of 68wt.%, wherein the average inner diameter is 40-60nm, the outer diameter is 80-100nm, and the length is 10-30um, stirring and heating, and carrying out oil bath condensation reflux at 120 ℃ for 4 hours. Adding 200mL of deionized water, cooling, diluting the acid concentration, filtering, and washing with water until the pH value of the filtrate is neutral; purifying, opening, cutting, placing in a 70 ℃ drying oven, keeping the temperature for 12h, taking out the dried carbon nanotubes, grinding in a mortar, and sieving with a 100-mesh standard sieve to obtain a functionalized carbon nanotube carrier;
(2) Preparing a catalyst with platinum nanoparticles loaded inside the carbon nanotubes: according to the mass ratio of 95; then dissolving the weighed precursor salt of the tetraammine platinum nitrate into proper amount of water, and oscillating and ultrasonically treating for 15min; after the carbon nano tube carrier is fully dissolved, uniformly dripping the carbon nano tube carrier on the carbon nano tube carrier to completely soak the carbon nano tube carrier; fully grinding, wherein the saturated vapor pressure of the liquid in the carbon tube is low, the solution state is always maintained in the tube in the slow evaporation process of the solvent, platinum ions continuously enter the tube cavity of the carbon tube under the drive of concentration difference, and slow drying is controlled, so that enough time is provided for more platinum ions to enter the tube cavity of the carbon tube; after the moisture is volatilized, transferring the sample to a vacuum drying oven, keeping the vacuum degree at 0.08MPa, and heating the sample at 60 ℃ for 12 hours to dry the sample; placing the dried sample into a tube furnace, heating the sample from room temperature to 400 ℃ at the speed of 5 ℃/min under the protection of nitrogen, calcining the sample for 4 hours, and then reducing the calcined sample for 2 hours at 250 ℃ in a hydrogen atmosphere; then cooling to room temperature in a nitrogen atmosphere, taking out and placing in a vacuum drying oven to obtain a catalyst loaded with metal platinum nanoparticles in the 5wt.% Pt-in-MWNT carbon nanotube;
(3) The reaction for preparing furfuryl alcohol by catalytic hydrogenation of furfural: dissolving 2mL of furfural serving as a raw material into 55mL of isopropanol serving as a solvent and 0.5mL of ultrapure water, adding 0.57mL of dodecane serving as an internal standard substance to prepare a reaction solution with the mass fraction of 5wt.% of furfural, and injecting the reaction solution by a micro-injection pump. 200mg of 5wt.% Pt-in-MWNT catalyst was weighed and loaded into a quartz tube at a constant temperature. And introducing nitrogen into the reactor to replace the gas for three times, then filling nitrogen with the pressure of 1MPa, and keeping the pressure for a certain time for leak detection. The reaction solution was introduced at a flow rate of 2mL/min to soak the catalyst, and after soaking was complete, the flow rate was changed to 0.05mL/min. Introducing 20mL/min of hydrogen into a gas flow meter, mixing the hydrogen with a reaction liquid, and allowing the mixture to pass through a catalyst bed layer to perform catalytic hydrogenation reaction on the furfural, wherein the reaction temperature is 25 ℃, the pressure is normal pressure, the reaction liquid is taken out from a liquid storage tank every one hour, and the composition and the content of a product are analyzed through gas chromatography, so that the conversion rate of the furfural after 10 hours is 90%, the selectivity of furfuryl alcohol is 95%, and the average yield of the furfuryl alcohol after 100 hours is about 85.5%; the specific reaction route is as follows:
preferably, the carbon nanotubes are multi-walled carbon nanotubes.
Preferably, in the step (1), during the pretreatment of the carbon nanotubes, adding concentrated nitric acid according to the proportion of adding 100ml of nitric acid to each gram of carbon nanotubes;
preferably, the carbon nanotubes in the step (1) are purified to remove impurities, cut, opened, washed, dried, ground, and sieved by a standard sieve of 100 meshes to obtain the functionalized carbon nanotube carrier.
Preferably, the step (2) includes configuring the metal salt solution with a volume such that the carbon nanotubes are completely wetted, sufficiently grinding, and controlling a sufficient time for more metal salt solution to enter the carbon nanotubes by capillary action during the slow evaporation of the solvent.
Preferably, the carbon nanotubes soaked by the metal salt solution in the step (2) are ground until the moisture is volatilized, and then transferred to a vacuum drying oven, the vacuum degree is maintained at 0.08MPa, the temperature is slowly increased, and the sample is dried by heating at 60 ℃ for 12 hours.
Activity test of the catalyst in which the metal platinum nanoparticles are supported inside the carbon nanotubes:
the use of the catalyst prepared by the present invention, in which the platinum nanoparticles are supported on the inside of the carbon nanotubes, for the catalytic activity will be described below through a specific experiment.
The experimental method comprises the following steps: dissolving a raw material furfural in an isopropanol solvent to prepare a reaction solution with the mass fraction of 2.5-10wt.%, and adding a certain amount of internal standard substance dodecane to prepare the reaction solution. Leading the reaction solution and hydrogen to pass through a trickle bed reactor filled with a Pt-in-MWNT catalyst together to enable furfural to carry out catalytic hydrogenation reaction, wherein the hydrogen flow rate is 10-20mL/min, the flow rate of the reaction liquid is 0.05-1mL/min, the reaction temperature is 20-35 ℃, the pressure is normal pressure, the reaction time is 10 hours, taking out the reaction liquid every 1 hour after the reaction, and calculating the conversion rate and the selectivity of the reaction liquid by a gas chromatograph.
Reaction route:
the experimental results are as follows: the catalyst loaded with the metal platinum nanoparticles in the carbon nanotube can realize furfural hydrogenation to prepare furfuryl alcohol under the conditions of normal temperature and normal pressure, so that the energy consumption is greatly reduced, the furfural conversion rate and the furfuryl alcohol selectivity are effectively improved, the furfural conversion rate can be stabilized at 90%, and the furfuryl alcohol selectivity can be stabilized at 95%; meanwhile, the catalyst has stable property and still has better reaction activity after long-time reaction.
In summary, the present invention has the following advantages over the prior art:
the catalyst loaded with the metal platinum nanoparticles in the carbon nanotube prepared by the method can selectively fill metal particles on the inner wall of the open carbon nanotube, and the obtained particles have small particle size, narrow distribution (0.5-5 nm) and uniform dispersion, thereby greatly improving the reaction activity.
The catalyst of the invention has good stability and long catalytic life, can realize the furfural hydrogenation to prepare furfuryl alcohol under the conditions of normal temperature and normal pressure, greatly reduces energy consumption, simplifies industrial operation conditions, and effectively improves the furfural conversion rate and the furfuryl alcohol selectivity. Under normal temperature and normal pressure, isopropanol is used as a solvent, 5wt.% of Pt-in-MWNT catalyst is in a reaction solution with furfural mass concentration of 5wt.%, and after 100 hours of reaction, the conversion rate of furfural can still reach 90%, and the selectivity of furfuryl alcohol can still reach 95%. Comparison of examples 2-6 shows that only 5wt.% of the Pt-in-MWNT catalyst is the highest in furfural conversion and selectivity.
The filling or loading process is carried out at room temperature, has no special equipment requirement, is simple and easy to operate, has small damage effect on the tube wall of the carbon nano tube, and is favorable for further application of the carbon nano tube after the particles are modified.
Drawings
FIG. 1 is an electron microscope image of multi-walled carbon nanotubes without platinum nanoparticle modification after purification treatment
FIG. 2 is an electron microscope image of a 1wt.% Pt-in-MWNT carbon nanotube internally loaded with a platinum nanoparticle catalyst
FIG. 3 is an electron microscope image of a 5wt.% Pt-in-MWNT carbon nanotube internally loaded with a platinum nanoparticle catalyst
FIG. 4 is an electron microscope image of a 10wt.% Pt-in-MWNT carbon nanotube internally supporting a platinum nanoparticle catalyst, FIG. 5 is an evaluation result of 5wt.% Pt-in-MWNT catalyst performance
Detailed Description
The whole process is described in detail below by way of examples, but the scope of the claims of the present invention is not limited by these examples. Meanwhile, the embodiments only give some conditions for achieving the purpose, but do not mean that the conditions must be met for achieving the purpose.
Example 1
Pretreating the carbon nano tube: 3g of pristine multi-walled carbon nanotubes (average inner diameter 60nm, outer diameter 100 nm) were mixed with 300mL of concentrated nitric acid (68 wt.%), heated with stirring, and condensed back in a 120 ℃ oil bath for 4h. Adding 200mL of deionized water, cooling, diluting the acid concentration, filtering, and washing with water until the pH value of the filtrate is neutral; purifying, opening, cutting, placing in a 70 ℃ drying oven, keeping the temperature for 12h, taking out the dried carbon nanotubes, grinding in a mortar, and sieving with a 100-mesh standard sieve to obtain a functionalized carbon nanotube carrier;
example 2
Preparing a solution with the concentration of 25.19mg/mL from 5g of platinum tetraammine nitrate and 100mL of deionized water at room temperature, and carrying out ultrasonic oscillation for 30min; after the solution is uniform, the solution is put into a refrigerator for storage for later use.
Weighing 990mg of functionalized carbon nanotube carrier, uniformly spreading in a mortar, taking 400uL of the prepared platinum tetraammine nitrate solution, adding deionized water to dilute to 7.5mL, and performing ultrasonic treatment for 15min; after the carbon nano tube carrier is fully dissolved, uniformly dripping the carbon nano tube carrier on the carbon nano tube carrier to completely soak the carbon nano tube carrier; stirring and grinding, wherein the saturated vapor pressure of the liquid in the carbon tube is low, the solution state is always maintained in the tube in the slow evaporation process of the solvent, platinum ions continuously enter the tube cavity of the carbon tube under the drive of concentration difference, and slow drying is controlled, so that enough time is provided for more platinum ions to enter the tube cavity of the carbon tube; transferring to a vacuum drying oven until the catalyst is fully impregnated and the moisture is volatilized, keeping the vacuum degree at 0.08MPa, controlling the temperature to rise slowly, and heating at 60 ℃ for 12 hours to dry the sample;
grinding the dried sample, putting the ground sample into a tube furnace, heating the sample from room temperature to 400 ℃ at the speed of 5 ℃/min under the protection of nitrogen, calcining the sample for 4 hours, and then reducing the calcined sample for 2 hours at 250 ℃ in a hydrogen atmosphere; and then cooling to room temperature in a nitrogen atmosphere, taking out and placing in a vacuum drying oven to obtain the metal platinum nanoparticle catalyst loaded in the 1wt.% Pt-in-MWNT carbon nanotube.
Example 3
Preparing a solution with the concentration of 25.19mg/mL from 5g of platinum tetraammine nitrate and 100mL of deionized water at room temperature, and carrying out ultrasonic oscillation for 30min; after the solution is uniform, the solution is put into a refrigerator for storage for later use.
Weighing 970mg of a functionalized carbon nanotube carrier, uniformly spreading in a mortar, taking 1.2mL of platinum precursor solution, adding deionized water to dilute to 7.5mL, and performing ultrasonic treatment for 15min; after the carbon nano tube carrier is fully dissolved, uniformly dripping the carbon nano tube carrier on the carbon nano tube carrier to completely soak the carbon nano tube carrier; stirring and grinding, wherein the saturated vapor pressure of the liquid in the carbon tube is low, the solution state is always maintained in the tube in the slow evaporation process of the solvent, platinum ions continuously enter the tube cavity of the carbon tube under the drive of concentration difference, and slow drying is controlled, so that enough time is provided for more platinum ions to enter the tube cavity of the carbon tube; transferring to a vacuum drying oven until the catalyst is fully impregnated and the moisture is volatilized, keeping the vacuum degree at 0.08MPa, controlling the temperature to rise slowly, and heating at 60 ℃ for 12 hours to dry the sample;
grinding the dried sample, putting the ground sample into a tube furnace, heating the sample from room temperature to 400 ℃ at a speed of 5 ℃/min under the protection of nitrogen, calcining the sample for 4 hours, and then reducing the calcined sample at 250 ℃ for 2 hours in a hydrogen atmosphere; then cooling to room temperature in a nitrogen atmosphere, taking out and placing in a vacuum drying oven to obtain a platinum nanoparticle catalyst loaded inside the 3wt.% Pt-in-MWNT carbon nanotube;
example 4
Preparing a solution with the concentration of 25.19mg/mL from 5g of platinum tetraammine nitrate and 100mL of deionized water at room temperature, and carrying out ultrasonic oscillation for 30min; after the solution is uniform, the solution is put into a refrigerator for storage for later use.
Weighing 950mg of functionalized multi-walled carbon nanotube carrier, uniformly spreading in a mortar, taking 2.0mL of the prepared tetramino platinum nitrate solution, adding deionized water to dilute to 7.5mL, and performing ultrasonic treatment for 15min; after the carbon nano tube carrier is fully dissolved, uniformly dripping the carbon nano tube carrier on the carbon nano tube carrier to completely soak the carbon nano tube carrier; stirring and grinding, wherein the saturated vapor pressure of the liquid in the carbon tube is low, the solution state is always maintained in the tube in the slow evaporation process of the solvent, platinum ions continuously enter the tube cavity of the carbon tube under the drive of concentration difference, and slow drying is controlled, so that enough time is provided for more platinum ions to enter the tube cavity of the carbon tube; transferring to a vacuum drying oven until the catalyst is fully impregnated and the moisture is volatilized, keeping the vacuum degree at 0.08MPa, controlling the temperature to rise slowly, and heating at 60 ℃ for 12 hours to dry the sample;
grinding the dried sample, putting the ground sample into a tube furnace, heating the sample from room temperature to 400 ℃ at the speed of 5 ℃/min under the protection of nitrogen, calcining the sample for 4 hours, and then reducing the calcined sample for 2 hours at 250 ℃ in a hydrogen atmosphere; and then cooling to room temperature in a nitrogen atmosphere, taking out and placing in a vacuum drying oven to obtain the catalyst with the metal platinum nanoparticles loaded in the 5wt.% Pt-in-MWNT carbon nanotube.
Example 5
Preparing a solution with the concentration of 25.19mg/mL from 5g of platinum tetraammine nitrate and 100mL of deionized water at room temperature, and oscillating and ultrasonically treating for 30min; after the solution is uniform, the solution is put into a refrigerator for storage for later use.
Weighing 930mg of functionalized carbon nanotube carrier, uniformly spreading in a mortar, taking 2.8mL of the prepared platinum tetraammine nitrate solution, adding deionized water to dilute to 7.5mL, and performing ultrasonic treatment for 15min; after the carbon nano tube carrier is fully dissolved, uniformly dripping the carbon nano tube carrier on the carbon nano tube carrier to completely soak the carbon nano tube carrier; stirring and grinding, wherein the saturated vapor pressure of the liquid in the carbon tube is low, the solution state is always maintained in the tube in the slow evaporation process of the solvent, platinum ions continuously enter the tube cavity of the carbon tube under the drive of concentration difference, and slow drying is controlled, so that enough time is provided for more platinum ions to enter the tube cavity of the carbon tube; and transferring the catalyst to a vacuum drying oven after the catalyst is fully impregnated and the moisture is volatilized, keeping the vacuum degree at 0.08MPa, controlling the temperature to rise slowly, and heating the catalyst at 60 ℃ for 12 hours to dry the sample.
Grinding the dried sample, putting the ground sample into a tube furnace, heating the sample from room temperature to 400 ℃ at the speed of 5 ℃/min under the protection of nitrogen, calcining the sample for 4 hours, and then reducing the calcined sample for 2 hours at 250 ℃ in a hydrogen atmosphere; and then cooling to room temperature in a nitrogen atmosphere, taking out and placing in a vacuum drying oven to obtain the catalyst with the metal platinum nanoparticles loaded in the 7wt.% Pt-in-MWNT carbon nanotube.
Example 6
Preparing a solution with the concentration of 25.19mg/mL from 5g of platinum tetraammine nitrate and 100mL of deionized water at room temperature, and oscillating and ultrasonically treating for 30min; after the solution is uniform, the solution is put into a refrigerator for storage for later use.
Weighing 900mg of functionalized carbon nanotube carrier, uniformly spreading in a mortar, taking 4.0mL of platinum precursor solution, adding deionized water to dilute to 7.5mL, and performing ultrasonic treatment for 15min; after the carbon nano tube carrier is fully dissolved, uniformly dripping the carbon nano tube carrier on the carbon nano tube carrier to completely soak the carbon nano tube carrier; stirring and grinding, wherein the saturated vapor pressure of the liquid in the carbon tube is low, the solution state is always maintained in the tube in the slow evaporation process of the solvent, platinum ions continuously enter the tube cavity of the carbon tube under the drive of concentration difference, and slow drying is controlled, so that enough time is provided for more platinum ions to enter the tube cavity of the carbon tube; transferring to a vacuum drying oven until the catalyst is fully impregnated and the moisture is volatilized, keeping the vacuum degree at 0.08MPa, controlling the temperature to rise slowly, and heating at 60 ℃ for 12 hours to dry the sample;
grinding the dried sample, putting the ground sample into a tube furnace, heating the sample from room temperature to 400 ℃ at the speed of 5 ℃/min under the protection of nitrogen, calcining the sample for 4 hours, and then reducing the calcined sample for 2 hours at 250 ℃ in a hydrogen atmosphere; and then cooling to room temperature in a nitrogen atmosphere, taking out and placing in a vacuum drying oven to obtain the metal platinum nanoparticle catalyst loaded in the 10wt.% Pt-in-MWNT carbon nanotube.
Example 7: evaluation of catalyst Performance
Dissolving 2mL of furfural serving as a raw material into 55mL of isopropanol serving as a solvent and 0.5mL of ultrapure water, adding 0.57mL of dodecane serving as an internal standard substance to prepare a reaction solution with the mass fraction of 5wt.% of furfural, and injecting the reaction solution by a micro-injection pump. 200mg of 5wt.% Pt-in-MWNT catalyst was weighed and loaded into a quartz tube at a constant temperature. And introducing nitrogen into the reactor to replace the gas for three times, then filling nitrogen with the pressure of 1MPa, and keeping for a certain time for leak detection. The reaction solution was introduced at a flow rate of 2mL/min to soak the catalyst, and after complete soaking, the flow rate was changed to 0.05mL/min. And introducing 20mL/min hydrogen into the reactor by a gas flowmeter, mixing the hydrogen with the reaction liquid, allowing the furfural to pass through a catalyst bed layer, performing catalytic hydrogenation reaction at the reaction temperature of 25 ℃ and the pressure of normal pressure, taking out the reaction liquid from a liquid storage tank every one hour, and analyzing the composition and content of the product by gas chromatography. The conversion of furfural after 10 hours was 90% and the selectivity of furfuryl alcohol was 95%. The average yield of furfuryl alcohol after 100 hours was about 85.5%.
Example 8: comparison of catalytic Effect of catalysts with different platinum loadings
The present example is different from example 7 in that: the catalyst loading was varied and the rest was the same as in example 7.
TABLE 1 comparison of activity of different platinum-loaded catalysts after 10 hours reaction
| Examples | Mass fraction of platinum | Conversion rate | Selectivity is |
| Example 2 | 1％ | 25％ | 71％ |
| Example 3 | 3％ | 60％ | 90％ |
| Example 4 | 5％ | 90％ | 95％ |
| Example 5 | 7％ | 86％ | 90％ |
| Example 6 | 10％ | 85％ | 90％ |
5wt% Pt-in-MWNT catalyst showed the best performance. As Pt loading decreases, FFR conversion and furfuryl alcohol selectivity decrease significantly; when the Pt loading was increased from 5wt%, the reactivity did not increase further.
Comparative example 1
Pretreating the carbon nano tube: 3g of pristine single-walled carbon nanotubes were mixed with 300mL of concentrated nitric acid (68 wt.%), heated with stirring and condensed back into a 120 ℃ oil bath for 4h. Adding 200mL of deionized water, cooling, diluting the acid concentration, filtering, repeatedly washing with deionized water to neutrality, keeping the temperature in a drying oven at 70 ℃ for 12 hours, taking out the dried carbon nanotube, grinding the carbon nanotube in a mortar, and sieving the carbon nanotube by a 100-mesh standard sieve to obtain the functionalized carbon nanotube carrier. Because the diameter is small, the length is long, and the aspect ratio of the single-walled carbon nanotube and the tube bundle thereof is high, the metal ions are difficult to be uniformly dispersed in the tube, and the reaction activity is reduced.
In summary, the invention provides a method for preparing a catalyst with platinum nanoparticles loaded on the inner wall of a carbon nanotube, which comprises the step of stirring and grinding by external force to enable an organic or inorganic solvent with low surface tension to react with the surface of the carbon nanotube with an opening. In the process of slow evaporation of the solvent, the filled metal precursor is continuously fed into the carbon tube cavity by the solvent under the action of the capillary force of the cavity, and slow drying is controlled, so that enough time is provided for more platinum ions to enter the carbon tube cavity. The method has strong experimental controllability, can selectively control the metal platinum nano particles to be uniformly dispersed on the inner wall of the carbon nano tube, the percentage of the metal particles in the tube can reach 90 percent or more, and the obtained particles have small particle size, narrow distribution (0.5-5 nm) and uniform dispersion, thereby greatly improving the reaction activity. In addition, the filling or loading process is carried out at room temperature, no special equipment requirement exists, the process operation is simple and easy to implement, the damage effect on the tube wall of the carbon nano tube is small, and the further application of the carbon nano tube after the particles are modified is facilitated.
Claims (5)
1. A method for a reaction of furfural hydrogenation by a catalyst with platinum nanoparticles loaded on the inner wall of a carbon nanotube is characterized by comprising the following steps: the method comprises the following steps:
(1) Pretreatment of the multi-wall carbon nano tube: including purification, opening and cutting;
immersing the carbon nano tube by using concentrated nitric acid with the mass concentration of 68wt.%, wherein the average inner diameter is 40-60nm, the outer diameter is 80-100nm, the length is 10-30um, stirring and heating, and carrying out oil bath condensation reflux at 120 ℃ for 4h; adding 200mL of deionized water, cooling, diluting the acid concentration, filtering, and washing with water until the pH value of the filtrate is neutral; purifying, opening, cutting, placing in a 70 ℃ drying oven, keeping the temperature for 12h, taking out the dried multi-walled carbon nanotubes, grinding in a mortar, and sieving with a 100-mesh standard sieve to obtain a functionalized multi-walled carbon nanotube carrier;
(2) Preparing a catalyst with the metal platinum nanoparticles loaded in the carbon nanotube: according to the mass ratio of the carbon nanotube carrier to the metal platinum being 95; then dissolving the weighed precursor salt of the tetraammine platinum nitrate into proper amount of water, and oscillating and ultrasonically treating for 15min; after the carbon nano tube carrier is fully dissolved, uniformly dripping the carbon nano tube carrier on the carbon nano tube carrier to completely soak the carbon nano tube carrier; fully grinding, wherein the saturated vapor pressure of the liquid in the carbon tube is low, the solution state is always maintained in the tube in the slow evaporation process of the solvent, platinum ions continuously enter the tube cavity of the carbon tube under the drive of concentration difference, and slow drying is controlled, so that enough time is provided for more platinum ions to enter the tube cavity of the carbon tube; after the water is volatilized, transferring the water to a vacuum drying oven, keeping the vacuum degree at 0.08MPa, and heating the water at 60 ℃ for 12 hours to dry the sample; placing the dried sample into a tube furnace, heating the sample from room temperature to 400 ℃ at the speed of 5 ℃/min under the protection of nitrogen, calcining the sample for 4 hours, and then reducing the calcined sample for 2 hours at 250 ℃ in a hydrogen atmosphere; then cooling to room temperature in the nitrogen atmosphere, taking out and placing in a vacuum drying oven to obtain a metal platinum nanoparticle catalyst loaded in the 5wt.% Pt-in-MWNT carbon nanotube;
(3) The reaction for preparing furfuryl alcohol by catalytic hydrogenation of furfural: dissolving 2mL of furfural serving as a raw material into 55mL of isopropanol serving as a solvent and 0.5mL of ultrapure water, adding 0.57mL of dodecane serving as an internal standard substance to prepare a reaction solution with the mass fraction of 5wt.% of furfural, and injecting the reaction solution by a micro-injection pump; weighing 200mg of 5wt.% Pt-in-MWNT catalyst, and filling the catalyst into a constant-temperature part in a quartz tube; introducing nitrogen into the reactor to replace the tertiary gas, then filling nitrogen with the pressure of 1MPa, and keeping for a certain time for leak detection; introducing a reaction solution at a flow rate of 2mL/min to soak the catalyst, and changing the flow rate to 0.05mL/min after soaking completely; introducing hydrogen into the reactor at a flow meter of 20mL/min, mixing the hydrogen with a reaction solution, and allowing the mixture to pass through a catalyst bed layer, so that the furfural is subjected to a catalytic hydrogenation reaction at a reaction temperature of 25 ℃ and under normal pressure, taking out the reaction solution from a liquid storage tank at an interval of one hour every time, and analyzing the composition and content of a product by gas chromatography to obtain the furfural with a conversion rate of 90% after 10 hours, a furfuryl alcohol selectivity of 95% and an average yield of about 85.5% after 100 hours; the specific reaction route is as follows:
2. the method for the reaction of furfural hydrogenation by using the carbon nanotube inner wall supported platinum nanoparticle catalyst according to claim 1, characterized in that: in the step (1), in the pretreatment process of the carbon nano tubes, concentrated nitric acid is added according to the proportion of adding 100ml nitric acid into each gram of carbon nano tubes.
3. The method for the reaction of furfural hydrogenation by using the catalyst with platinum nanoparticles supported on the inner wall of the carbon nanotube according to claim 1, characterized in that: and (2) purifying the carbon nano tube in the step (1) to remove impurities, cutting, opening, washing, drying, grinding, and sieving by a 100-mesh standard sieve to obtain the functionalized carbon nano tube carrier.
4. The method for the reaction of furfural hydrogenation by using the catalyst with platinum nanoparticles supported on the inner wall of the carbon nanotube according to claim 1, characterized in that: and (3) in the step (2), the volume of the prepared metal salt solution is required to be completely soaked and fully ground, and in the process of slowly evaporating the solvent, enough time is controlled by virtue of capillary action to allow more metal salt solution to enter the carbon nanotubes.
5. The method for the reaction of furfural hydrogenation by using the catalyst of the platinum nanoparticles supported on the inner wall of the carbon nanotube according to claim 1, characterized in that: and (3) grinding the carbon nano tube soaked by the metal salt solution in the step (2) until the moisture is volatilized, transferring the carbon nano tube to a vacuum drying oven, keeping the vacuum degree at 0.08MPa, controlling the temperature to rise slowly, and heating the carbon nano tube at 60 ℃ for 12 hours to dry the sample.
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| US20100298125A1 (en) * | 2009-05-20 | 2010-11-25 | Korea Institute Of Energy Research | Carbon nanotube catalysts having metal catalyst nano-particles supported on inner channel of carbon nanotube and preparation method thereof |
| CN105056941A (en) * | 2015-07-23 | 2015-11-18 | 浙江大学 | Preparation of platinum/carbon nanotube catalyst and application of catalyst to furfural catalytic hydrogenation |
| CN106732566A (en) * | 2017-02-07 | 2017-05-31 | 西北师范大学 | A kind of preparation method of carbon nanotube loaded metal Ru nano-particle catalyst |
| CN113457672A (en) * | 2021-08-18 | 2021-10-01 | 南京工业大学 | Multi-walled carbon nanotube supported platinum-based catalyst and preparation method and application thereof |
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| US20100298125A1 (en) * | 2009-05-20 | 2010-11-25 | Korea Institute Of Energy Research | Carbon nanotube catalysts having metal catalyst nano-particles supported on inner channel of carbon nanotube and preparation method thereof |
| CN105056941A (en) * | 2015-07-23 | 2015-11-18 | 浙江大学 | Preparation of platinum/carbon nanotube catalyst and application of catalyst to furfural catalytic hydrogenation |
| CN106732566A (en) * | 2017-02-07 | 2017-05-31 | 西北师范大学 | A kind of preparation method of carbon nanotube loaded metal Ru nano-particle catalyst |
| CN113457672A (en) * | 2021-08-18 | 2021-10-01 | 南京工业大学 | Multi-walled carbon nanotube supported platinum-based catalyst and preparation method and application thereof |
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