CN113471456A - Preparation method of size-controllable Pt-based catalyst - Google Patents
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- 238000002360 preparation method Methods 0.000 title claims abstract description 16
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000001816 cooling Methods 0.000 claims abstract description 23
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- KLFRPGNCEJNEKU-FDGPNNRMSA-L (z)-4-oxopent-2-en-2-olate;platinum(2+) Chemical compound [Pt+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O KLFRPGNCEJNEKU-FDGPNNRMSA-L 0.000 description 1
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9041—Metals or alloys
- H01M4/905—Metals or alloys specially used in fuel cell operating at high temperature, e.g. SOFC
- H01M4/9058—Metals or alloys specially used in fuel cell operating at high temperature, e.g. SOFC of noble metals or noble-metal based alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
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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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The invention discloses a preparation method of a size-controllable Pt-based catalyst, which comprises the following steps: drying the carrier in vacuum, and cooling to obtain carrier powder; dissolving glucose in deionized water, and performing ultrasonic dispersion to form a glucose solution; slowly adding the carrier powder into the glucose solution, stirring at room temperature to uniformly distribute the carrier powder, stirring and evaporating to dryness, and then drying in vacuum to obtain a mixed solid; grinding the mixed solid into powder, calcining the powder in an inert atmosphere, and cooling the powder to room temperature to obtain a carbonized carrier; dissolving a Pt precursor in a solvent, and dissolving by ultrasonic to form a metal precursor solution; adding the carbonized carrier into a metal precursor solution, stirring at room temperature, evaporating to dryness, and vacuum drying; grinding into powder, calcining under inert atmosphere, and cooling to obtain the Pt-based catalyst. The particle size of Pt particles in the catalyst obtained by the invention can be effectively controlled within the range of 1-10nm and is uniformly distributed on the surface of the carrier.
Description
Technical Field
The invention belongs to the field of catalyst preparation, and particularly relates to a preparation method of a size-controllable Pt-based catalyst.
Background
The nano-sized metal particles, particularly the particles with the size of 1-10nm, show unique electric, magnetic, optical and thermal properties and catalytic activity different from bulk phase metal due to the quantum size effect, and are novel materials with the most application prospect. Particularly, heterogeneous catalysts loaded with Pt and other noble nano-metals are widely concerned in the chemical fields such as catalytic hydrogenation, dehydrogenation, methane conversion, fuel cells and the like, so that the prepared Pt metal particles with the particle size of 1-10nm have important significance for daily life and production.
Chen et al (Chemical Communications 2015,51,5936-5938) studied the catalytic combustion performance of a series of Pt/ZSM-5 p-toluene particles with Pt particle size of 1.3-2.3 nm, and showed that Pt particles with diameter of 1.9nm showed the best activity due to their higher dispersion and high proportion of Pt (0). Frelink et al (Journal of electrochemical Chemistry 1995,382,65-72) have studied the electrocatalytic oxidation of methanol by a Pt/C catalyst of 1-12 nm, and found that in the range of 1.2-4.5 nm, the methanol oxidation activity decreases with the decrease in Pt size; the catalyst with the activity of more than 4.5nm on methanol oxidation is basically unchanged. Sun et al (Acta scientific statistic 2017,37, 1297) prepared a series of Pt particles (1.41-2.32 nm) with uniform size by a glycol reduction method and loaded on CeO with regular morphology2On the nano rod, the toluene catalytic oxidation activity of the nano rod is firstly increased and then reduced along with the increase of the Pt particle size, wherein Pt-1.79/CeO2The-rod p-toluene has the best catalytic effect.
The above work demonstrates that in different catalytic systems, Pt particles of a specific size are required to have excellent catalytic performance. However, the current preparation method of Pt-based catalysts has drawbacks in that: it is difficult to obtain Pt particles of a specific particle size on an industrial catalyst.
Disclosure of Invention
The invention aims to provide a preparation method of a Pt-based catalyst with controllable size. The method uses the traditional industrial impregnation method, and prepares the Pt-based catalyst with controllable size by controlling the adding amount of glucose or the proportion of solvent deionized water and absolute ethyl alcohol when no glucose exists, and the particle size of Pt particles in the catalyst prepared by the preparation method can be effectively controlled within the range of 1-10nm and is uniformly distributed on the surface of a carrier.
In order to solve the first technical problem, the invention adopts the following technical scheme:
a preparation method of a size-controllable Pt-based catalyst comprises the following steps:
s1, drying the carrier in vacuum, and cooling to obtain carrier powder for later use;
s2, dissolving glucose in deionized water, and performing ultrasonic dispersion to form a glucose solution;
s3, slowly adding the carrier powder into the glucose solution, stirring at room temperature to uniformly distribute the carrier powder, stirring and evaporating to dryness, and then drying in vacuum to obtain a mixed solid;
s4, grinding the mixed solid into powder, calcining in an inert atmosphere, and cooling to room temperature to obtain a carbonized carrier for later use;
s5, dissolving the Pt precursor in a solvent, and ultrasonically dissolving the Pt precursor until the Pt precursor is clear and transparent to form a metal precursor solution;
s6, adding the carbonized carrier into the metal precursor solution, stirring at room temperature to uniformly disperse the carbonized carrier, stirring and evaporating to dryness, and performing vacuum drying to obtain a Pt-based catalyst precursor;
and S7, grinding the Pt-based catalyst precursor into powder, calcining in an inert atmosphere, and cooling to obtain the Pt-based catalyst.
As a further improvement of the technical scheme, in the step S1, the carrier is gamma-Al2O3、SiO2Or CeO2(ii) a Preferably, the carrier is γ -Al2O3。
Preferably, in step S1, the temperature of vacuum drying is 90-130 ℃ and the time is 5-12 h.
As a further improvement of the technical proposal, in the step S2, the addition amount of the glucose is 0.15-0.45g corresponding to each gram of the carrier obtained in the step S1.
Preferably, in step S2, the ultrasonic dispersion conditions are: ultrasonic treatment is carried out for 0.5-1.5h under the power of 400W being 40% -80%.
As a further improvement of the technical scheme, in step S3, the stirring speed is 800-1500r/min, and the stirring time is 4-12 h; the temperature for evaporating to dryness is 80-90 ℃; the drying temperature is 70-100 ℃, and the drying time is 8-24 h.
As a further improvement of the technical scheme, in the step S4, the inert atmosphere is Ar or N2。
Preferably, in step S4, the calcination process requires purging the system with an inert gas for 60-120 min.
Preferably, in step S4, the calcination process is performed in two steps: firstly carbonizing at low temperature and then processing at high temperature.
Preferably, in step S4, the low-temperature carbonization step is: raising the temperature to 350-450 ℃ under the condition that the temperature rise gradient is 5-10 ℃/min for carbonization treatment; the high-temperature treatment comprises the following steps: and heating the material subjected to the low-temperature carbonization treatment to 750-850 ℃ again for calcination.
Preferably, in step S4, the time for the low-temperature carbonization is 120-; the time of the high-temperature treatment is 120-240 min.
As a further improvement of the technical solution, in step S5, the Pt precursor is K2PtCl4、Pt(acac)2Or Pt (NH)3)4(NO3)2(ii) a Preferably, the Pt precursor is Pt (acac)2。
Preferably, in step S5, the solvent is absolute ethanol, chloroform or carbon tetrachloride; more preferably, the solvent is absolute ethanol.
Preferably, in step S5, the ultrasonic dissolution conditions are: ultrasonic treatment is carried out for 0.5-1.5h under the power of 400W which is 40% -80%.
As a further improvement of the technical scheme, in step S6, the stirring speed is 800-1500r/min, and the stirring time is 4-12 h; the temperature for evaporating to dryness is 70-90 ℃; the drying temperature is 70-100 ℃, and the drying time is 8-24 h.
As a further improvement of the technical proposal, in the step S7, the loading amount of Pt on the carrier in the Pt-based catalyst is 0.3-1 wt%.
Preferably, in step S7, the inert atmosphere is Ar or N2。
Preferably, in step S7, the calcination process requires purging the system with an inert gas for 60-120 min.
Preferably, in step S7, the temperature of the calcination treatment is 250-350 ℃; the time is 60-180 min.
Preferably, in step S7, the temperature gradient in the calcination treatment is 1-5 ℃/min; more preferably, the ramp is 1-3 deg.C/min.
In another aspect, a method for preparing a size-controllable Pt-based catalyst includes the steps of:
s11, drying the carrier in vacuum, and cooling to obtain carrier powder for later use;
s12, dissolving the Pt precursor in a mixed solvent of deionized water and absolute ethyl alcohol, and ultrasonically dissolving the Pt precursor until the Pt precursor is clear and transparent to form a metal precursor solution;
s13, adding the carrier powder prepared in the step S11 into the metal precursor solution, stirring at room temperature to uniformly disperse the carrier powder, stirring and evaporating to dryness, and performing vacuum drying to obtain a Pt-based catalyst precursor;
and S14, grinding the Pt-based catalyst precursor into powder, calcining in an inert atmosphere, and cooling to obtain the Pt-based catalyst.
As a further improvement of the technical scheme, in the step S11, the carrier is gamma-Al2O3、SiO2Or CeO2(ii) a Preferably, the carrier is γ -Al2O3。
Preferably, in step S11, the temperature of vacuum drying is 90-130 ℃ and the time is 5-12 h.
As a further improvement of the technical solution, in step S12, the Pt precursor is K2PtCl4、Pt(acac)2Or Pt (NH)3)4(NO3)2(ii) a Preferably, the Pt precursor is Pt (acac)2Or K2PtCl4。
Preferably, in step S12, the volume ratio of the solvent deionized water to the absolute ethyl alcohol is 1:24-24: 1.
Preferably, in step S12, the ultrasonic dissolution conditions are: ultrasonic treatment is carried out for 0.5-1.5h under the power of 400W which is 40% -80%.
As a further improvement of the technical scheme, in step S13, the stirring speed is 800-1500r/min, and the stirring time is 4-12 h; the temperature for evaporating to dryness is 70-90 ℃; the drying temperature is 70-100 ℃, and the drying time is 8-24 h.
As a further improvement of the technical proposal, in the step S14, the loading amount of Pt on the carrier in the Pt-based catalyst is 0.3-1 wt%.
Preferably, in step S14, the inert atmosphere is Ar or N2。
Preferably, in step S14, the calcination process requires purging the system with an inert gas for 60-120 min.
Preferably, in step S14, the temperature of the calcination treatment is 250-350 ℃; the time is 60-180 min.
Preferably, in step S14, the temperature gradient in the calcination treatment is 1-5 ℃/min; more preferably, the ramp is 1-3 deg.C/min.
Any range recited herein is intended to include the endpoints and any number between the endpoints and any subrange subsumed therein or defined therein.
The starting materials of the present invention are commercially available, unless otherwise specified, and the equipment used in the present invention may be any equipment conventionally used in the art or may be any equipment known in the art.
Compared with the prior art, the invention has the following beneficial effects:
the method uses the traditional industrial impregnation method, and prepares the Pt-based catalyst with controllable size by controlling the adding amount of glucose or the proportion of solvent deionized water and absolute ethyl alcohol when no glucose exists, and the particle size of Pt particles in the catalyst obtained by the method can be effectively controlled within the range of 1-10nm and is uniformly distributed on the surface of a carrier.
Drawings
The following detailed description of embodiments of the invention is provided in connection with the accompanying drawings
FIG. 1 is a HAADF-STEM graph and a particle size histogram of the Pt-based catalyst obtained in example 1;
FIG. 2 is a HAADF-STEM graph and a particle size histogram of the Pt-based catalyst obtained in example 2;
FIG. 3 is a HAADF-STEM graph and a particle size histogram of the Pt-based catalyst obtained in example 3;
FIG. 4 is a HAADF-STEM graph and a particle size histogram of the Pt-based catalyst obtained in example 4;
FIG. 5 is a graph of HAADF-STEM of the Pt-based catalyst obtained in example 5;
FIG. 6 is a graph of HAADF-STEM and a particle size statistic of the Pt-based catalyst prepared in comparative example 1;
FIG. 7 is a graph of HAADF-STEM and a particle size statistic of the Pt-based catalyst prepared in comparative example 6;
FIG. 8 is a graph of HAADF-STEM and a particle size statistic chart of the Pt-based catalyst obtained in comparative example 7.
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below in connection with preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
As one aspect of the present invention, a method for preparing a size-controllable Pt-based catalyst according to the present invention includes the steps of:
s1, drying the carrier in vacuum, and cooling to obtain carrier powder for later use;
s2, dissolving glucose in deionized water, and performing ultrasonic dispersion to form a glucose solution;
s3, slowly adding the carrier powder into the glucose solution, stirring at room temperature to uniformly distribute the carrier powder, stirring and evaporating to dryness, and then drying in vacuum to obtain a mixed solid;
s4, grinding the mixed solid into powder, calcining in an inert atmosphere, and cooling to room temperature to obtain a carbonized carrier for later use;
s5, dissolving the Pt precursor in a solvent, and ultrasonically dissolving the Pt precursor until the Pt precursor is clear and transparent to form a metal precursor solution;
s6, adding the carbonized carrier into the metal precursor solution, stirring at room temperature to uniformly disperse the carbonized carrier, stirring and evaporating to dryness, and performing vacuum drying to obtain a Pt-based catalyst precursor;
and S7, grinding the Pt-based catalyst precursor into powder, calcining in an inert atmosphere, and cooling to obtain the Pt-based catalyst.
In the above preparation method, since glucose is added, the size-controllable Pt-based catalyst is prepared by controlling the addition ratio of glucose in step S3.
In certain embodiments, in step S1, the support is γ -Al2O3、SiO2Or CeO2；
In certain preferred embodiments, the support is γ -Al2O3。
In some embodiments, in step S1, the vacuum drying temperature is 90-130 ℃ and the time is 5-12 h. Too low drying temperature or too short drying time can result in insufficient removal of water in the carrier pore channels, and influence the subsequent glucose impregnation condition.
In certain embodiments, in step S2, the amount of glucose added is 0.15-0.45g per gram of carrier from step S1. Glucose can form reduced carbon through carbonization, and the reduced carbon reacts with oxygen on the surface of the carrier to form oxygen vacancies, which is favorable for impregnation and dispersion of the metal active component; when the glucose amount is too high, the excessive carbon can coat the formed oxygen vacancy, and the dispersion condition of the subsequent metal active components is influenced.
In certain embodiments, in step S2, the conditions of the ultrasonic dispersion are: ultrasonic treatment is carried out for 0.5-1.5h under the power of 400W being 40% -80%. Too low ultrasonic power or too short ultrasonic time can lead to uneven glucose dissolution and dispersion, and influence on subsequent glucose impregnation.
In some embodiments, in step S3, the stirring speed is 800-1500r/min, and the stirring time is 4-12 h; the temperature for evaporating to dryness is 80-90 ℃; the drying temperature is 70-100 ℃, and the drying time is 8-24 h. Too low stirring speed or too short stirring time can cause insufficient dispersion of glucose on a carrier, and influence the dispersion condition of subsequent metal active components; if the evaporation temperature is too low, deionized water cannot be evaporated to dryness, so that subsequent operation is affected; the drying temperature is too low or the drying time is too short, so that residual moisture in the pore channels of the carrier is difficult to remove, and the formation of oxygen vacancies is influenced.
In certain embodiments, in step S4, the inert atmosphere is Ar or N2. The invention requires that the sample is carbonized during the calcination process, in order to prevent the carbon from reacting to form carbon dioxide under the oxidizing atmosphere and avoid the reducing atmosphere (such as CO and H)2) The risk of calcination, and calcination under an inert atmosphere is therefore an option.
In some embodiments, in step S4, the calcination process requires purging the system with an inert gas for 60-120 min. Too short a purge time may not adequately remove air from the system, affecting carbonization of glucose on the support, and further affecting the formation of oxygen vacancies on the support.
In certain embodiments, in step S4, the calcination process is performed in two steps: firstly carbonizing at low temperature and then processing at high temperature. In the low-temperature carbonization, the calcination temperature is too low, so that the glucose is incompletely carbonized, and the formation of oxygen vacancies is influenced; in the high-temperature treatment, the calcining temperature is too low, and the formed carbon is not easy to react with oxygen in the carrier, so that oxygen vacancies are difficult to form and the impregnation and dispersion of the subsequent metal are influenced; on the contrary, too high calcination temperature can cause collapse of the carrier pore structure, and affect the performance of the final catalyst.
In certain embodiments, in step S4, the low temperature carbonization step is: raising the temperature to 350-450 ℃ under the condition that the temperature rise gradient is 5-10 ℃/min for carbonization treatment; the high-temperature treatment comprises the following steps: and heating the material subjected to the low-temperature carbonization treatment to 750-850 ℃ again for calcination. The calcination temperature rise rate is too slow, so that the calcination time is too long, and the preparation efficiency of the catalyst is influenced; however, the heating rate is too fast, which may cause non-uniform heating, resulting in incomplete calcination, and the power of the tube furnace is increased too fast, which may reduce the service life of the resistance wire.
In some embodiments, in step S4, the time for the low-temperature carbonization is 120-; the time of the high-temperature treatment is 120-240 min. The low-temperature calcination time is too short, so that the sample is not completely carbonized, and the obtained sample is impure; too short high-temperature calcination time can cause the carrier to be incapable of fully forming oxygen vacancies, and influence the subsequent dispersion condition of the metal active components.
In certain embodiments, in step S5, the Pt precursor is K2PtCl4、Pt(acac)2Or Pt (NH)3)4(NO3)2(ii) a Preferably, the Pt precursor is Pt (acac)2。
In certain embodiments, in step S5, the solvent is absolute ethanol, chloroform, or carbon tetrachloride; more preferably, the solvent is absolute ethanol.
In certain embodiments, in step S5, the conditions of the ultrasonic dissolution are: ultrasonic treatment is carried out for 0.5-1.5h under the power of 400W which is 40% -80%.
In some embodiments, in step S6, the stirring speed is 800-1500r/min, and the stirring time is 4-12 h; the temperature for evaporating to dryness is 70-90 ℃; the drying temperature is 70-100 ℃, and the drying time is 8-24 h. The stirring speed is too low or the stirring time is too short, so that the metal Pt cannot be uniformly dispersed on the carrier, and the impregnation dispersion condition of the metal is influenced; if the evaporation temperature is too low, the solvent cannot be evaporated to dryness, and the subsequent operation is influenced; the drying temperature is too low or the drying time is too short, so that the residual solvent in the pore channels of the carrier is difficult to remove, and the formation of the metal active component is influenced.
In certain embodiments, the Pt-based catalyst has a Pt loading on the support of 0.3 to 1 wt% in step S7. The loading capacity is too low, the dispersion of metal Pt on the catalyst carrier is too high, and larger particles are difficult to form; on the contrary, if the loading is too high and the dispersion degree of the metal Pt is low, small particles are difficult to form, and the size regulation of the metal active component under the same loading is influenced.
In certain embodiments, in step S7, the inert atmosphere is Ar or N2. The invention does not need to carry out oxidation or reduction treatment on the sample in the calcining process, so the calcining under the inert atmosphere is selected to be carried out under Ar or N2Calcination in an atmosphere can result in more uniform dispersion of the metal particles on the support.
In some embodiments, in step S7, the calcination process requires purging the system with an inert gas for 60-120 min. Too short a purge time may result in residual air in the system that does not completely maintain the inert atmosphere.
In some embodiments, the temperature of the calcination process in step S7 is 250-350 ℃; the time is 60-180 min. The calcination temperature is too low, so that metal salt in a sample cannot be decomposed, and a Pt simple substance is difficult to form; the high temperature can cause the agglomeration of the nano particles and the poor stability of the particles. In addition, the calcination time is too short, so that the Pt-based catalyst precursor is not completely decomposed at high temperature, and the obtained Pt-based catalyst is not pure; on the contrary, the calcination time is too long, and the Pt-based catalyst stays for too long at high temperature, so that the particles are agglomerated.
In certain embodiments, in step S7, the temperature gradient during the calcination process is 1-5 ℃/min; more preferably, the ramp is 1-3 deg.C/min. The temperature rising rate during calcination is too fast, so that metal particles are heated unevenly, are easy to agglomerate, have too large size and too wide distribution, and the service life of the resistance wire can be shortened due to too fast increase of the power of the tube furnace.
As another aspect of the present invention, a method for preparing a size-controllable Pt-based catalyst includes the steps of:
s11, drying the carrier in vacuum, and cooling to obtain carrier powder for later use;
s12, dissolving the Pt precursor in a mixed solvent of deionized water and absolute ethyl alcohol, and ultrasonically dissolving the Pt precursor until the Pt precursor is clear and transparent to form a metal precursor solution;
s13, adding the carrier powder prepared in the step S11 into the metal precursor solution, stirring at room temperature to uniformly disperse the carrier powder, stirring and evaporating to dryness, and performing vacuum drying to obtain a Pt-based catalyst precursor;
and S14, grinding the Pt-based catalyst precursor into powder, calcining in an inert atmosphere, and cooling to obtain the Pt-based catalyst.
In the preparation method, since no glucose is added, the addition ratio of the solvent deionized water to the absolute ethyl alcohol in the step S12 is controlled, so that the size-controllable Pt-based catalyst is prepared.
In certain embodiments, in step S11, the support is γ -Al2O3、SiO2Or CeO2；
In certain preferred embodiments, the support is γ -Al2O3。
In some embodiments, in step S11, the vacuum drying temperature is 90-130 ℃ and the time is 5-12 h. Too low drying temperature or too short drying time can cause insufficient removal of water in the pore channels of the carrier, and affect the impregnation condition of the subsequent metal precursor.
In certain embodiments, in step S12, the Pt precursor is K2PtCl4、Pt(acac)2Or Pt (NH)3)4(NO3)2(ii) a Preferably, the Pt precursor is Pt (acac)2Or K2PtCl4。
According to some embodiments of the invention, in step S12, the volume ratio of the solvent deionized water to the absolute ethyl alcohol is 1:24-24: 1. The proportion of the deionized water to the absolute ethyl alcohol is too high, so that the solubility of the potassium platinochloride in a mixed solvent of the deionized water and the absolute ethyl alcohol is higher; on the contrary, the potassium chloroplatinite has lower solubility and even is insoluble, which influences the subsequent metal dispersion condition.
In certain embodiments, in step S12, the conditions of the ultrasonic dissolution are: ultrasonic treatment is carried out for 0.5-1.5h under the power of 400W which is 40% -80%.
In some embodiments, in step S13, the stirring speed is 800-1500r/min, and the stirring time is 4-12 h; the temperature for evaporating to dryness is 70-90 ℃; the drying temperature is 70-100 ℃, and the drying time is 8-24 h. The stirring speed is too low or the stirring time is too short, so that the metal Pt cannot be uniformly dispersed on the carrier, and the impregnation dispersion condition of the metal is influenced; if the evaporation temperature is too low, the solvent cannot be evaporated to dryness, and the subsequent operation is influenced; the drying temperature is too low or the drying time is too short, so that the residual solvent in the pore channels of the carrier is difficult to remove, and the formation of the metal active component is influenced.
In certain embodiments, the Pt-based catalyst has a Pt loading on the support of 0.3 to 1 wt% in step S14. The loading capacity is too low, the dispersion of metal Pt on the catalyst carrier is too high, and larger particles are difficult to form; on the contrary, if the loading is too high and the dispersion degree of the metal Pt is low, small particles are difficult to form, and the size regulation of the metal active component under the same loading is influenced.
In certain embodiments, in step S14, the inert atmosphere is Ar or N2. The invention does not need to carry out oxidation or reduction treatment on the sample in the calcining process, so the calcining under the inert atmosphere is selected to be carried out under Ar or N2Calcination in an atmosphere can result in more uniform dispersion of the metal particles on the support.
In some embodiments, in step S14, the calcination process requires purging the system with an inert gas for 60-120 min. Too short a purge time may result in residual air in the system that does not completely maintain the inert atmosphere.
In some embodiments, the temperature of the calcination process in step S14 is 250-350 ℃; the time is 60-180 min. The calcination temperature is too low, so that metal salt in a sample cannot be decomposed, and a Pt simple substance is difficult to form; the high temperature can cause the agglomeration of the nano particles and the poor stability of the particles. In addition, the calcination time is too short, so that the Pt-based catalyst precursor is not completely decomposed at high temperature, and the obtained Pt-based catalyst is not pure; on the contrary, the calcination time is too long, and the Pt-based catalyst stays for too long at high temperature, so that the particles are agglomerated.
In certain embodiments, in step S14, the temperature gradient during the calcination process is 1-5 ℃/min; more preferably, the ramp is 1-3 deg.C/min. The temperature rising rate during calcination is too fast, so that metal particles are heated unevenly, are easy to agglomerate, have too large size and too wide distribution, and the service life of the resistance wire can be shortened due to too fast increase of the power of the tube furnace.
Example 1
A preparation method of a size-controllable Pt-based catalyst comprises the following steps:
s1, taking a proper amount of gamma-Al2O3Placing in a beaker 1, vacuum drying at 110 ℃ for 10h, and cooling for later use;
s2, weighing 0.25g of glucose in a beaker 2, dissolving the glucose in 50mL of deionized water, sealing the beaker by using a film to prevent dust in the air from polluting a sample, and performing ultrasonic dissolution and dispersion for 1h at 80% of 400W power;
s3, weighing 1g of dried gamma-Al2O3Slowly adding the carrier into the glucose solution, stirring at room temperature for 5h to uniformly distribute the carrier, stirring at 90 ℃ and evaporating to dryness, and then vacuum-drying at 80 ℃ for 12h to obtain a mixed solid;
s4, grinding the cooled mixed solid into powder, placing the powder in a porcelain boat, calcining the powder by using a tube furnace, and using N2Purge system for 90min, then at N2Calcining at 400 deg.C for 180min under atmosphere, heating to 800 deg.C, calcining for 180min, heating at gradient of 5 deg.C/min, and cooling to room temperature to obtain C-Al2O3A carrier;
s5, weighing 5.04mg Pt (acac) in beaker 32Dissolving in 25mL of absolute ethyl alcohol, sealing the beaker by using a film to prevent dust in the air from polluting a sample, and performing dissolution and dispersion by performing ultrasonic treatment for 1h at 80% of 400W power;
s6, weighing 0.5g C-Al2O3Slow addition of Pt (acac)2Stirring at room temperature for 5h at 1200r/min for uniform dispersion, stirring at 80 deg.C for drying, drying in a vacuum drying oven at 80 deg.C for 12h to obtain Pt-based catalyst precursor;
s7, grinding the cooled Pt-based catalyst precursor into powder, calcining the powder by using a tube furnace, and carrying out N treatment on the calcined powder2Purge system for 90min, then at N2Calcining for 2h at 300 ℃ in the atmosphere, raising the temperature gradient to 2 ℃/min, and cooling to room temperature to obtain the Pt-based catalyst.
FIG. 1 is a graph and a particle size histogram of the Pt-based catalyst HAADF-STEM prepared in this example. As can be seen from the figure, the Pt particle size of the Pt-based catalyst is 0.98nm, and the catalyst has good dispersibility.
Example 2
Example 1 was repeated with the only difference that: the amount of glucose was replaced with 0.15g for 0.25 g. FIG. 2 is a graph and a particle size histogram of the Pt-based catalyst HAADF-STEM prepared in this example. As can be seen from the figure, the Pt particle size of the Pt-based catalyst is 1.49nm and is uniformly distributed on the surface of the carrier.
Example 3
Example 1 was repeated with the only difference that: the amount of glucose was replaced with 0.45g for 0.25 g. FIG. 3 is a graph of HAADF-STEM and a particle size histogram of the Pt-based catalyst prepared in this example. As can be seen from the figure, the Pt particle size of the Pt-based catalyst is 2.18nm and the distribution is uniform.
Example 4
Example 1 was repeated with the only difference that: and adjusting the volume ratio of the solvent deionized water to the absolute ethyl alcohol without adding glucose. The method comprises the following specific steps:
s11, taking a proper amount of gamma-Al2O3Placing in a beaker 1, vacuum drying at 110 ℃ for 10h, and cooling for later use;
s12, weighing 5.34mg of potassium platinochloride in a beaker 2, dissolving the potassium platinochloride in a mixed solvent of deionized water and absolute ethyl alcohol in a volume ratio of 1:19, sealing the beaker by using a film to prevent dust in the air from polluting a sample, and performing ultrasonic dissolution and dispersion for 1h at 80% of 400W power;
s13, weighing 0.5g of dried gamma-Al2O3Slowly adding the carrier into the potassium platinochloride solution, stirring at room temperature for 5h at 1200r/min to uniformly distribute the carrier, stirring at 90 ℃ to dry, and then vacuum-drying at 80 ℃ for 12h to obtain a Pt-based catalyst precursor;
s14, grinding the cooled Pt-based catalyst precursor into powder, calcining the powder by using a tube furnace, and carrying out N treatment on the calcined powder2Purge system for 90min, then at N2Calcining for 2h at 300 ℃ in the atmosphere, raising the temperature gradient to 2 ℃/min, and cooling to room temperature to obtain the Pt-based catalyst.
FIG. 4 is a graph and a particle size histogram of the Pt-based catalyst HAADF-STEM prepared in this example. As can be seen from the figure, the Pt particle size of the Pt-based catalyst is 1.74nm, and has good dispersibility.
Example 5
Example 4 was repeated, with the only difference that: the volume ratio of the solvent deionized water to the absolute ethyl alcohol is 5:15 instead of 1: 19. FIG. 5 is a graph of the HAADF-STEM catalyst prepared in this example. Since the Pt loading amount is 0.5 wt%, the loading amount is too low, and the Pt particles are too small in amount due to too large size, so that the particle size statistics cannot be carried out. As can be seen from the figure, the Pt particles are about 4nm in size and relatively uniform in size.
Comparative example 1
Example 1 was repeated with the only difference that: in step S2, the amount of glucose was replaced with 0.25g by 0.65 g. FIG. 6 is a graph of HAADF-STEM and a particle size statistic chart of the Pt-based catalyst prepared in this comparative example. As can be seen from the figure, the Pt particle size of the Pt-based catalyst is 1.94nm, and although the particle size is the same as that of the Pt particles in the range of 0.15-0.45g of glucose, the Pt particles with other sizes can not be further changed, and the explanation effect is repeated in the range of 0.15-0.45g of glucose.
Comparative example 2
Example 1 was repeated with the only difference that: in step S3, the drying time is 5 hours, and after drying, grinding obviously fails to grind into powder, and the powder still has viscosity under the action of a small amount of residual moisture.
Comparative example 3
Example 1 was repeated with the only difference that: in step S4, the calcination temperature was changed to 800 ℃ by 1000 ℃ to obtain gamma-Al in the sample2O3Crystal transformation can occur to form alpha-Al2O3Obviously changing the structure of the catalyst.
Comparative example 4
Example 4 was repeated with the only difference that: in step S12, the volume ratio of the solvent deionized water to the absolute ethyl alcohol is 25:0, and through ultrasonic dissolution and dispersion treatment, the platinum acetylacetonate remains in powder form and sinks to the bottom of the beaker, so that a clear and transparent solution cannot be formed.
Comparative example 5
Example 1 was repeated with the only difference that: in the step S6, the stirring speed is 500r/min, the stirring speed is too low, the metal salt cannot be fully impregnated on the surface of the carrier, and the Pt content of the obtained Pt-based catalyst is only 0.23 wt% and is far lower than the theoretical loading amount through ICP-OES detection.
Comparative example 6
Example 3 was repeated with the only difference that: in step S7, the temperature of the calcination treatment is 800 ℃. FIG. 7 is a HAADF-STEM graph and a particle size histogram of the Pt-based catalyst prepared in this comparative example, in which it can be seen that although the average particle size of Pt particles is 1.47nm, the particle size histogram is not normally distributed, which indicates that the particle size is not uniform and the dispersion is not uniform, and further, that at a lower loading amount, the metal Pt is too highly dispersed to form large particles.
Comparative example 7
Example 1 was repeated with the only difference that: in step S7, the calcination time is 5 h. FIG. 8 is a HAADF-STEM graph and a particle size statistic graph of the Pt-based catalyst prepared in this comparative example, and it can be seen that the particle size of Pt particles increases from 0.98nm to 1.50nm, and a certain agglomeration phenomenon occurs.
Comparative example 8
Example 1 was repeated with the only difference that: in step S7, the temperature gradient is 10 ℃/min, the metal particles are heated unevenly, and the size distribution is wide.
In summary, according to the preparation method of the size-controllable Pt-based catalyst, the addition amount of glucose or the ratio of the solvent deionized water to the absolute ethyl alcohol when no glucose is present has the greatest influence on the particle size of the final Pt-based catalyst, and in addition, a complete technical scheme is formed by mutually coordinating and matching the vacuum condition, the ultrasonic condition, the calcination temperature rise rate, the calcination time, the calcination temperature, the calcination treatment atmosphere and the like, so that the Pt particles with controllable particle size required by the invention can be more finely prepared.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. Not all embodiments are exhaustive. All obvious changes and modifications which are obvious to the technical scheme of the invention are covered by the protection scope of the invention.
Claims (10)
1. A preparation method of a size-controllable Pt-based catalyst is characterized by comprising the following steps:
s1, drying the carrier in vacuum, and cooling to obtain carrier powder for later use;
s2, dissolving glucose in deionized water, and performing ultrasonic dispersion to form a glucose solution;
s3, slowly adding the carrier powder into the glucose solution, stirring at room temperature to uniformly distribute the carrier powder, stirring and evaporating to dryness, and then drying in vacuum to obtain a mixed solid;
s4, grinding the mixed solid into powder, calcining in an inert atmosphere, and cooling to room temperature to obtain a carbonized carrier for later use;
s5, dissolving the Pt precursor in a solvent, and ultrasonically dissolving the Pt precursor until the Pt precursor is clear and transparent to form a metal precursor solution;
s6, adding the carbonized carrier into the metal precursor solution, stirring at room temperature to uniformly disperse the carbonized carrier, stirring and evaporating to dryness, and performing vacuum drying to obtain a Pt-based catalyst precursor;
and S7, grinding the Pt-based catalyst precursor into powder, calcining in an inert atmosphere, and cooling to obtain the Pt-based catalyst.
2. The method of preparing a size-controllable Pt-based catalyst according to claim 1, wherein: in step S1, the carrier is gamma-Al2O3、SiO2Or CeO2(ii) a Preferably, the carrier is γ -Al2O3。
3. The method of preparing a size-controllable Pt-based catalyst according to claim 1, wherein: in step S1, the temperature of vacuum drying is 90-130 ℃, and the time is 5-12 h.
4. The method of preparing a size-controllable Pt-based catalyst according to claim 1, wherein: in the step S2, the addition amount of the glucose is 0.15-0.45g corresponding to each gram of the carrier obtained in the step S1;
preferably, in step S2, the ultrasonic dispersion conditions are: ultrasonic treatment is carried out for 0.5-1.5h under the power of 400W being 40% -80%.
5. The method of preparing a size-controllable Pt-based catalyst according to claim 1, wherein: in step S3, the stirring speed is 800-1500r/min, and the stirring time is 4-12 h; the temperature for evaporating to dryness is 80-90 ℃; the drying temperature is 70-100 ℃, and the drying time is 8-24 h.
6. The method of preparing a size-controllable Pt-based catalyst according to claim 1, wherein: in step S4, the inert atmosphere is Ar or N2；
Preferably, in step S4, the calcination process requires purging the system with an inert gas for 60-120 min.
7. The method of preparing a size-controllable Pt-based catalyst according to claim 1, wherein: in step S4, the calcination process is performed in two steps: firstly carbonizing at low temperature and then processing at high temperature;
preferably, in step S4, the low-temperature carbonization step is: raising the temperature to 350-450 ℃ under the condition that the temperature rise gradient is 5-10 ℃/min for carbonization treatment; the high-temperature treatment comprises the following steps: heating the material subjected to low-temperature carbonization to 750-850 ℃ again for calcination;
preferably, in step S4, the time for the low-temperature carbonization is 120-; the time of the high-temperature treatment is 120-240 min.
8. The method of preparing a size-controllable Pt-based catalyst according to claim 1, whichIs characterized in that: in step S5, the Pt precursor is K2PtCl4、Pt(acac)2Or Pt (NH)3)4(NO3)2(ii) a Preferably, the Pt precursor is Pt (acac)2；
Preferably, in step S5, the solvent is absolute ethanol, chloroform or carbon tetrachloride; more preferably, the solvent is absolute ethanol;
preferably, in step S5, the ultrasonic dissolution conditions are: ultrasonic treatment is carried out for 0.5-1.5h under the power of 400W which is 40% -80%.
9. The method of preparing a size-controllable Pt-based catalyst according to claim 1, wherein: in step S6, the stirring speed is 800-1500r/min, and the stirring time is 4-12 h; the temperature for evaporating to dryness is 70-90 ℃; the drying temperature is 70-100 ℃, and the drying time is 8-24 h;
preferably, in step S7, the supported amount of Pt on the support in the Pt-based catalyst is 0.3 to 1 wt%;
preferably, in step S7, the inert atmosphere is Ar or N2；
Preferably, in step S7, the calcining treatment requires purging the system with an inert gas for 60-120 min;
preferably, in step S7, the temperature of the calcination treatment is 250-350 ℃; the time is 60-180 min;
preferably, in step S7, the temperature gradient in the calcination treatment is 1-5 ℃/min; more preferably, the ramp is 1-3 deg.C/min.
10. A preparation method of a size-controllable Pt-based catalyst is characterized by comprising the following steps:
s11, drying the carrier in vacuum, and cooling to obtain carrier powder for later use;
s12, dissolving the Pt precursor in a mixed solvent of deionized water and absolute ethyl alcohol, and ultrasonically dissolving the Pt precursor until the Pt precursor is clear and transparent to form a metal precursor solution;
s13, adding the carrier powder prepared in the step S11 into the metal precursor solution, stirring at room temperature to uniformly disperse the carrier powder, stirring and evaporating to dryness, and performing vacuum drying to obtain a Pt-based catalyst precursor;
s14, grinding the Pt-based catalyst precursor into powder, calcining in an inert atmosphere, and cooling to obtain the Pt-based catalyst;
preferably, in step S11, the carrier is γ -Al2O3、SiO2Or CeO2(ii) a More preferably, the carrier is γ -Al2O3；
Preferably, in step S11, the temperature of vacuum drying is 90-130 ℃ and the time is 5-12 h;
preferably, in step S12, the Pt precursor is K2PtCl4、Pt(acac)2Or Pt (NH)3)4(NO3)2(ii) a Preferably, the Pt precursor is Pt (acac)2Or K2PtCl4；
Preferably, in step S12, the volume ratio of the solvent deionized water to the absolute ethyl alcohol is 1:24-24: 1;
preferably, in step S12, the ultrasonic dissolution conditions are: ultrasonic treatment is carried out for 0.5-1.5h under the power of 400W being 40% -80%;
preferably, in step S13, the stirring speed is 800-; the temperature for evaporating to dryness is 70-90 ℃; the drying temperature is 70-100 ℃, and the drying time is 8-24 h;
preferably, in step S14, the supported amount of Pt on the support in the Pt-based catalyst is 0.3 to 1 wt%;
preferably, in step S14, the inert atmosphere is Ar or N2；
Preferably, in step S14, the calcining treatment requires purging the system with an inert gas for 60-120 min;
preferably, in step S14, the temperature of the calcination treatment is 250-350 ℃; the time is 60-180 min;
preferably, in step S14, the temperature gradient in the calcination treatment is 1-5 ℃/min; more preferably, the ramp is 1-3 deg.C/min.
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| CN112676571A (en) * | 2020-12-14 | 2021-04-20 | 北京化工大学 | Preparation method of supported PdW bimetallic elementary substance nanoparticles |
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| CN114471540A (en) * | 2022-02-22 | 2022-05-13 | 北京化工大学 | Sub-nano Pt selective hydrogenation catalyst, preparation method and application thereof |
| CN114471540B (en) * | 2022-02-22 | 2023-08-08 | 北京化工大学 | Sub-nanometer Pt selective hydrogenation catalyst, preparation method and application thereof |
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