CN105727988B - Platinum composite catalyst, preparation method and application - Google Patents
Platinum composite catalyst, preparation method and application Download PDFInfo
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Abstract
The present invention discloses a kind of platinum composite catalyst, preparation method and application, for using platinum particles as core, using mesoporous nickel oxide as the hollow core-shell particle of shell.The preparation method of platinum composite catalyst, to be prepared by self-assembling method using polystyrene sphere as template.Platinum composite catalyst, preparation method and application of the invention has high high-temp stability and high activity, can solve the problems, such as that existing platinum catalyst high temperature is unstable, is easy inactivation.
Description
Technical field
The present invention relates to a kind of precious metal catalyst agent material and its preparation method more particularly to a kind of nano platinum particle catalyst and
Preparation method and application.
Background technique
Platinum nanoparticles are due to becoming the catalyst to have a great attraction with big specific surface area.Moreover, platinum is received
Rice corpuscles shows the unique catalytic performance different from body phase material.After catalysis reaction, the surface atom of high activity often gathers
Collection, leads to the variation of particle size and shape, therefore lead to catalytic activity rapid decrease.In general, nano platinum particle surface is without matching
When body or stabilizer are protected, there are exposed active sites, there is highest catalytic activity.But if without ligand and stabilization
Agent protection, the high surface energy atom of nanoparticle surface are easy to be gathered into body phase material, and nanoparticle cannot be stabilized, in turn
Lose catalytic activity.In addition, nano platinum particle surface ligand influences its catalytic activity and selectivity.Therefore, high activity, length are prepared
Phase stable small size nano platinum particle catalyst is still an important challenge.
To prevent from assembling in nano platinum particle catalytic process or after high-temperature process, generally use two methods: deposition platinum is received
Rice corpuscles is limited in shell with holes on the carrier of high-specific surface area or by nano platinum particle.The prior art such as Chinese patent
CN200510064580.1 discloses a kind of preparation method of carbon supported platinum catalyst, but the platinum catalyst does not have high warm surely
Fixed performance.
Therefore, a kind of platinum composite catalyst for taking into account high-temperature thermal stability and high activity how is developed, this field skill is become
Art personnel's urgent problem to be solved.
Summary of the invention
The purpose of the present invention is to provide a kind of platinum composite catalyst, preparation method and applications, make it have high warm
Stability and high activity solve the problems, such as that existing platinum catalyst high temperature is unstable, is easy inactivation.
To achieve the above object, the present invention provides a kind of platinum composite catalyst (hollow mesoporous Pt/m-NiO composite catalyzing
Agent), for using platinum (Pt) particle as core, with hollow core-shell particle that mesoporous nickel oxide (NiO) is shell (that is, hollow mesoporous
Pt/m-NiO composite construction).
Wherein, in one preferred embodiment of platinum composite catalyst of the invention, the partial size of the Pt particle is 3-5nm.
Wherein, in one preferred embodiment of platinum composite catalyst of the invention, the mesoporous pore size of the NiO shell is 1~
3nm, preferably 2nm.
Wherein, in one preferred embodiment of platinum composite catalyst of the invention, the NiO shell with a thickness of 10~
20nm。
Wherein, in one preferred embodiment of platinum composite catalyst of the invention, it is described using Pt particle as core, with mesoporous
NiO is that the partial size of the hollow core-shell particle (that is, hollow mesoporous Pt/m-NiO composite construction) of shell is 60~80nm.
To achieve the above object, the present invention also provides a kind of preparation method of platinum composite catalyst, to prepare it is above-mentioned with
Pt particle is core, using mesoporous NiO as the hollow core-shell particle of shell.The preparation method is using polystyrene (PS) bead as mould
Plate is prepared by self-assembling method.
The preparation method of platinum composite catalyst of the invention, includes the following steps:
1) platinum (Pt) particle external surface is superscribed into polystyrene (PS) shell, obtains asymmetric Pt/PS core-shell structure；
2) by one kind or two in the asymmetric Pt/PS core-shell structure and Brij-30 or Lutensol AO5 template
Kind mixing (" one or two kinds of mixing in Brij-30 or Lutensol AO5 template " i.e. " single Brij-30 templates
Either single Lutensol AO5 template or Brij-30 and Lutensol AO5 mixed templates "), nickel acetate is added and returns
After stream, obtain Pt/PS/NiO core-shell structure (NiO shell layer in homogeneous thickness wraps up Pt/PS core-shell structure)；
3) the Pt/PS/NiO core-shell structure is calcined 4~6 hours at 300-600 DEG C, a step removes PS and step
2) one or two kinds of mixing in Brij-30 the or Lutensol AO5 template being added in is (that is, what no matter step 2) was added is single
One Brij-30 template, single Lutensol AO5 template or Brij-30 and Lutensol AO5 mixed templates,
It is removed in step 3)).Thus platinum composite catalyst of the invention can be obtained, and (that is, hollow mesoporous Pt/m-NiO is compound
Catalyst), which has the characteristics that high activity, high-temperature thermal stability.
Wherein, described in step 1) in a preferred embodiment of the preparation method of platinum composite catalyst of the invention
The partial size of Pt particle is 3~5nm.
Wherein, described in step 1) in a preferred embodiment of the preparation method of platinum composite catalyst of the invention
The partial size of Pt/PS core-shell structure is 50~60nm.
Wherein, described in step 1) in a preferred embodiment of the preparation method of platinum composite catalyst of the invention
Pt particle preparation method includes: to take 10~60mg polyvinylpyrrolidone, 5~30mg chloroplatinic acid, is dissolved in 1~10mL water and 30
In the mixed solution of~60mL ethyl alcohol；After 60~100 DEG C of heating reflux 1~6 hour, 10~100mL acetone precipitation, then water is added
It washes to obtain Pt particle (nanoparticle).
Wherein, described in step 1) in a preferred embodiment of the preparation method of platinum composite catalyst of the invention
Pt/PS core-shell structure preparation method includes: to take 10~60mg potassium peroxydisulfate, 1~10mg 4- styrene sulfonic acid sodium hydrate, is added
Enter into the mixed solution of 1~10mL water and 10~30mL ethyl alcohol；After being heated to 60~100 DEG C of reflux 1~6 hour, moment adds
Enter styrene/divinyl benzene mixtures of 0.1~0.5mL mixed weight ratio 50:1~1:1,1~after ten minutes, it is added immediately
1.0~10.0mL Pt nanoparticle, then after 60~100 DEG C are heated to reflux 1~10 hour, with the mixed solution of second alcohol and water
Washing 1~5 time, obtains the asymmetry Pt/PS core-shell structure.
Wherein, described in step 2) in a preferred embodiment of the preparation method of platinum composite catalyst of the invention
The partial size of Pt/PS/NiO core-shell structure is 60~80nm.
Wherein, described in step 2) in a preferred embodiment of the preparation method of platinum composite catalyst of the invention
Pt/PS/NiO core-shell structure preparation method includes: by Pt/PS core-shell structure described in 1~10mL, with Brij-30 or Lutensol
One or two are according to 50:1~1:1 (Pt/PS core-shell structure weight: template total weight=50:1~1:1, template in AO5
Mixed proportion does not limit) mixing, it is then added in 10~100mmol nickel acetate, 60~100 DEG C are heated to reflux 1~5 hour
Afterwards, 200~1000 revs/min of centrifuge separations, then with after ethanol washing 1~5 time, 50~100 DEG C drying 1~10 hour, obtain
Pt/PS/NiO core-shell structure.In step 2), being introduced into one or two in a certain amount of Brij-30 or Lutensol AO5 has
Two effects: first, contribute to form the uniform NiO shell layer of thickness；Second, it is provided after high-temperature calcination for the NiO shell layer on surface layer
Mesoporous lamella.
Wherein, right in step 3) in a preferred embodiment of the preparation method of platinum composite catalyst of the invention
Pt/PS/NiO core-shell structure calcination temperature is preferably 400 DEG C, and calcination time is preferably 5 hours.
To achieve the above object, the present invention also provides a kind of applications of above-mentioned platinum composite catalyst: urging above-mentioned platinum is compound
Agent is applied to the Oxidation of Carbon Monoxide reaction of carbon dioxide (Oxidation of Carbon Monoxide at) and p -Chloronitrobenzene hydrogenation reaction is (p-
Chloronitrobenzene adds hydrogen to prepare the reaction of p-chloroaniline) in.
Technical principle and its technical effect enumeration of the invention is as follows:
To realize high catalytic activity, nano platinum particle core should come into full contact with reactant, while the shell of outer surface is answered
With the performance for allowing reactants and products quickly to spread.The nano platinum particle being wrapped in hollow mesoporous lamella, each platinum are received
Rice corpuscles has a homogeneous environment.Mesoporous size is less than the size of nano platinum particle, under the conditions of harsh high-temperature catalytic
Nano platinum particle remains to be stabilized.
Based on the above principles, the present invention provides a kind of monodisperse platinum particles catalyst of hollow mesoporous NiO shell layer package, system
Preparation Method and application, catalyst catalytic activity with higher, higher thermal stability and can be recycled for multiple times
Performance.
The platinum composite catalyst of high-temperature thermal stability provided by the present invention is to be by core, hollow mesoporous NiO of Pt particle
Shell forms Pt/m-NiO structure.Since mesoporous NiO shell layer corner particle also contributes to hydrogenation reaction, acts synergistically, make with Pt
Obtaining platinum composite catalyst of the invention has high catalytic activity；
In addition, the introducing of mesoporous NiO shell, Pt particle size caused by preventing because of high temperature changes, and catalytic activity is caused to reduce.
Therefore, Pt nanoparticle can be effectively protected in mesoporous NiO shell layer, and the thermostabilization of catalytic active center Pt nanoparticle can be improved
Property, so that platinum composite catalyst of the invention is had the characteristics that high-temperature thermal stability.
High activity provided by the invention, high-temperature thermal stability platinum composite catalyst preparation method is using multistep self assembly
Process.The precursor solution mixing for mixing Pt nanoparticle and polystyrene, after being heated to reflux, forms asymmetric Pt/PS core
Shell structure.Above-mentioned asymmetric Pt/PS nucleocapsid bead, with one or two in a certain amount of Brij-30 or Lutensol AO5
After modification, NiO shell layer then is wrapped up in its outer surface.It is calcined 5 hours at 300~600 DEG C, one-step method removes Brij-30 simultaneously
Or it is empty to get the Pt particle wrapped up to the mesoporous NiO shell layer after one or two kinds of and PS bead template in Lutensol AO5
Core structure catalyst (Pt/m-NiO).
The platinum composite catalyst of high-temperature thermal stability of the invention, can be applied to Oxidation of Carbon Monoxide.Since the present invention uses
Mesoporous NiO is shell, and oxidizing carbon monoxide under the conditions of pyroreaction, hollow mesoporous NiO shell is effectively protected platinum nanoparticle
Son avoids losing catalytic activity due to the nano platinum particle change in size caused by high temperature.
High activity platinum composite catalyst of the invention is also suitble to p -Chloronitrobenzene to add the reaction of hydrogen, mesoporous NiO shell layer corner
Particle facilitates hydrogenation reaction, acts synergistically with Pt, so that catalyst has high catalytic activity, conversion ratio reaches 99%；And
After platinum composite catalyst of the invention is using 16 circulations, conversion ratio is held essentially constant, the characteristics of being recycled for multiple times.
Below in conjunction with the drawings and specific embodiments, the present invention will be described in detail, but not as a limitation of the invention.
Detailed description of the invention
Fig. 1 is the preparation process of hollow mesoporous catalyst of the invention, is followed successively by Pt/PS core-shell structure, Pt/ from left to right
PS/NiO core-shell structure, Pt/m-NiO structure；
Fig. 2 is the electromicroscopic photograph of Pt/PS core-shell structure in hollow mesoporous catalyst preparation process of the invention；
Fig. 3 is the electromicroscopic photograph of Pt/m-NiO structure in hollow mesoporous catalyst preparation process of the invention；
Fig. 4 is that the Pt/m-NiO composite catalyst of present pre-ferred embodiments and the Pt particle catalyst of comparative example are catalyzed
The curve synoptic diagram that the conversion ratio of p -Chloronitrobenzene hydrogenation reaction changes with reaction cycle number.
Specific embodiment
Technical solution of the present invention is described in detail below in conjunction with specific embodiment, to be easier to understand the present invention
Purpose, technology contents, feature and performance, and cited embodiment only make illustrate be used, be not intended as limit of the invention
System.
Please refer to figs. 1 to 4.To solve the problems, such as that existing platinum catalyst high temperature is unstable, being easy inactivation, the present invention is provided
A kind of platinum composite catalyst (hollow mesoporous Pt/m-NiO composite catalyst) is using platinum (Pt) particle as core, with mesoporous oxygen
Change the hollow core-shell particle (that is, hollow mesoporous Pt/m-NiO composite construction) that nickel (NiO) is shell.
Wherein, in one preferred embodiment of platinum composite catalyst of the invention, the partial size of the Pt particle is 3~5nm.
Wherein, in one preferred embodiment of platinum composite catalyst of the invention, the mesoporous pore size of the NiO shell is 1~
3nm, preferably 2nm.
Wherein, in one preferred embodiment of platinum composite catalyst of the invention, the NiO shell with a thickness of 10~
20nm。
Wherein, in one preferred embodiment of platinum composite catalyst of the invention, it is described using Pt particle as core, with mesoporous
NiO is that the partial size of the hollow core-shell particle (that is, hollow mesoporous Pt/m-NiO composite construction) of shell is 60~80nm.
The present invention also provides a kind of preparation method of platinum composite catalyst, to prepare it is above-mentioned using Pt particle as core, with
Mesoporous NiO is the hollow core-shell particle of shell.The preparation method is using polystyrene (PS) bead as template, by self assembly side
It is prepared by method.
Fig. 1 to Fig. 3 is please referred to, Fig. 1 is the preparation process of hollow mesoporous catalyst of the invention, is followed successively by from left to right
Pt/PS core-shell structure, Pt/PS/NiO core-shell structure, Pt/m-NiO structure.Fig. 2 is prepared by hollow mesoporous catalyst of the invention
In the process, the electromicroscopic photograph of Pt/PS core-shell structure；Fig. 3 is Pt/m- in hollow mesoporous catalyst preparation process of the invention
The electromicroscopic photograph of NiO structure.
The preparation method of platinum composite catalyst of the invention, includes the following steps:
1) platinum (Pt) particle external surface is superscribed into polystyrene (PS) shell, obtains asymmetric Pt/PS core-shell structure；
2) by one kind or two in the asymmetric Pt/PS core-shell structure and Brij-30 or Lutensol AO5 template
Kind mixing, after nickel acetate reflux is added, obtaining Pt/PS/NiO core-shell structure, (NiO shell layer in homogeneous thickness wraps up Pt/PS nucleocapsid
Structure)；
3) the Pt/PS/NiO core-shell structure is calcined 4-6 hours at 300~600 DEG C, a step removes PS and step
2) one or two kinds of mixing in Brij-30 the or Lutensol AO5 template being added in.Thus platinum of the invention can be obtained
Composite catalyst (that is, hollow mesoporous Pt/m-NiO composite catalyst), the platinum composite catalyst have high activity, high warm steady
Fixed feature.
Wherein, described in step 1) in a preferred embodiment of the preparation method of platinum composite catalyst of the invention
The partial size of Pt particle is 3~5nm.
Wherein, described in step 1) in a preferred embodiment of the preparation method of platinum composite catalyst of the invention
The partial size of Pt/PS core-shell structure is 50~60nm.
Wherein, described in step 1) in a preferred embodiment of the preparation method of platinum composite catalyst of the invention
Pt particle preparation method includes: to take 10~60mg polyvinylpyrrolidone, 5~30mg chloroplatinic acid, is dissolved in 1~10mL water and 30
In the mixed solution of~60mL ethyl alcohol；After 60~100 DEG C of heating reflux 1~6 hour, 10~100mL acetone precipitation, then water is added
It washes to obtain Pt particle (nanoparticle).
Wherein, described in step 1) in a preferred embodiment of the preparation method of platinum composite catalyst of the invention
Pt/PS core-shell structure preparation method includes: to take 10~60mg potassium peroxydisulfate, 1~10mg 4- styrene sulfonic acid sodium hydrate, is added
Enter into the mixed solution of 1~10mL water and 10~30mL ethyl alcohol；After being heated to 60~100 DEG C of reflux 1~6 hour, moment adds
Enter styrene/divinyl benzene mixtures of 0.1~0.5mL mixed weight ratio 50:1~1:1,1~after ten minutes, it is added immediately
1.0~10.0mL Pt nanoparticle, then after 60~100 DEG C are heated to reflux 1~10 hour, with the mixed solution of second alcohol and water
Washing 1~5 time, obtains the asymmetry Pt/PS core-shell structure.
Wherein, described in step 2) in a preferred embodiment of the preparation method of platinum composite catalyst of the invention
The partial size of Pt/PS/NiO core-shell structure is 60~80nm.
Wherein, described in step 2) in a preferred embodiment of the preparation method of platinum composite catalyst of the invention
Pt/PS/NiO core-shell structure preparation method includes: by Pt/PS core-shell structure described in 1~10mL, with Brij-30 or Lutensol
One or two are according to 50:1~1:1 (Pt/PS core-shell structure weight: template total weight=50:1~1:1, template in AO5
Mixed proportion does not limit) mixing, it is then added in 10~100mmol nickel acetate, 60~100 DEG C are heated to reflux 1~5 hour
Afterwards, 200~1000 revs/min of centrifuge separations, then with after ethanol washing 1~5 time, 50~100 DEG C drying 1~10 hour, obtain
Pt/PS/NiO core-shell structure.In step 2), being introduced into one or two in a certain amount of Brij-30 or Lutensol AO5 has
Two effects: first, contribute to form the uniform NiO shell layer of thickness；Second, it is provided after high-temperature calcination for the NiO shell layer on surface layer
Mesoporous lamella.
Wherein, right in step 3) in a preferred embodiment of the preparation method of platinum composite catalyst of the invention
Pt/PS/NiO core-shell structure calcination temperature is preferably 400 DEG C, and calcination time is preferably 5 hours.
The present invention also provides a kind of applications of above-mentioned platinum composite catalyst: above-mentioned platinum composite catalyst is applied to an oxidation
(p -Chloronitrobenzene adds hydrogen to prepare for the oxidation of coal reaction of carbon dioxide (Oxidation of Carbon Monoxide at) and p -Chloronitrobenzene hydrogenation reaction
The reaction of p-chloroaniline) in.
Embodiment a
The present embodiment provides a kind of preparation methods of platinum composite catalyst, include the following steps:
1) the Pt particle external surface that partial size is 3nm is superscribed into PS shell, obtains the asymmetric Pt/PS that partial size is 50nm
Core-shell structure；
The specific preparation method of Pt particle: 10mg polyvinylpyrrolidone, 5mg chloroplatinic acid are taken, 1mL water and 30mL second are dissolved in
In the mixed solution of alcohol；After heating 60 DEG C of reflux 1 hour, 10mL acetone precipitation is added, then wash to obtain Pt particle (nanoparticle
Son)；
The specific preparation method of Pt/PS core-shell structure: 10mg potassium peroxydisulfate, 1mg 4- styrene sulfonic acid sodium hydrate are taken, is added
Enter into the mixed solution of 1mL water and 10mL ethyl alcohol；After being heated to 60 DEG C of reflux 1 hour, 0.1mL mixed weight ratio is added in moment
After 1 minute, 1.0mL Pt nanoparticle is added, then heat back at 60 DEG C in styrene/divinyl benzene mixtures of 1:1 immediately
Stream is washed 1 time with the mixed solution of second alcohol and water after 1 hour, obtains the asymmetry Pt/PS core-shell structure；
2) the asymmetric Pt/PS core-shell structure and Brij-30 template are obtained into grain after nickel acetate reflux is added
The Pt/PS/NiO core-shell structure that diameter is 60nm (NiO shell layer in homogeneous thickness wraps up Pt/PS core-shell structure)；
The specific preparation method of Pt/PS/NiO core-shell structure: by Pt/PS core-shell structure described in 1mL, with Brij-30 or
One or two are mixed according to 1:1 in Lutensol AO5, are then added in 10mmol nickel acetate, and 60 DEG C to be heated to reflux 1 small
Shi Hou, 200 revs/min of centrifuge separations, then with after ethanol washing 1 time, 50 DEG C drying 1 hour, obtain Pt/PS/NiO nucleocapsid knot
Structure；
3) the Pt/PS/NiO core-shell structure is calcined 4 hours at 300 DEG C, a step, which removes in PS and step 2), to be added
The Brij-30 template entered.Thus platinum composite catalyst of the invention can be obtained, and (that is, hollow mesoporous Pt/m-NiO is compound urges
Agent), which has the characteristics that high activity, high-temperature thermal stability.
Via the above method, the present embodiment can provide a kind of platinum composite catalyst (hollow mesoporous Pt/m-NiO composite catalyzing
Agent), for using Pt particle as core, using mesoporous NiO be the hollow core-shell particle of shell (that is, hollow mesoporous Pt/m-NiO is compound
Structure).
Wherein, the partial size of the Pt particle is 3nm；The mesoporous pore size of the NiO shell is 1nm；The thickness of the NiO shell
Degree is 10nm；It is described using Pt particle as core, by the partial size of the hollow core-shell particle of shell of mesoporous NiO be 60nm.
The platinum composite catalyst of the present embodiment can be applied to Oxidation of Carbon Monoxide, and (Oxidation of Carbon Monoxide is at the anti-of carbon dioxide
Answer) and p -Chloronitrobenzene hydrogenation reaction (reaction that p -Chloronitrobenzene adds hydrogen to prepare p-chloroaniline) in.
Embodiment b
The present embodiment provides a kind of preparation methods of platinum composite catalyst, include the following steps:
1) the Pt particle external surface that partial size is 5nm is superscribed into PS shell, obtains the asymmetric Pt/PS that partial size is 60nm
Core-shell structure；
The specific preparation method of Pt particle: 60mg polyvinylpyrrolidone, 30mg chloroplatinic acid are taken, 10mL water and 60mL are dissolved in
In the mixed solution of ethyl alcohol；After heating 100 DEG C of reflux 6 hours, 100mL acetone precipitation is added, then wash to obtain Pt particle (nanometer
Particle)；
The specific preparation method of Pt/PS core-shell structure: 60mg potassium peroxydisulfate, 10mg 4- styrene sulfonic acid sodium hydrate are taken, is added
Enter into the mixed solution of 10mL water and 30mL ethyl alcohol；After being heated to 100 DEG C of reflux 6 hours, 0.5mL mixed weight is added in moment
After ten minutes 10.0mL Pt nanoparticle is added, then at 100 DEG C in styrene/divinyl benzene mixtures than 50:1 immediately
After being heated to reflux 10 hours, is washed 5 times with the mixed solution of second alcohol and water, obtain the asymmetry Pt/PS core-shell structure；
2) the asymmetric Pt/PS core-shell structure and Lutensol AO5 template are obtained after nickel acetate reflux is added
To the Pt/PS/NiO core-shell structure that partial size is 80nm (NiO shell layer in homogeneous thickness wraps up Pt/PS core-shell structure)；
The specific preparation method of Pt/PS/NiO core-shell structure: by Pt/PS core-shell structure described in 10mL, with Brij-30 or
One or two are mixed according to 50:1 in Lutensol AO5, are then added in 100mmol nickel acetate, and 100 DEG C are heated to reflux 5
After hour, 1000 revs/min of centrifuge separations, then with after ethanol washing 5 times, 100 DEG C drying 10 hours, obtain Pt/PS/NiO core
Shell structure.
3) the Pt/PS/NiO core-shell structure is calcined 6 hours at 600 DEG C, a step, which removes in PS and step 2), to be added
The Lutensol AO5 template entered.Thus platinum composite catalyst of the invention (that is, hollow mesoporous Pt/m-NiO can be obtained
Composite catalyst), which has the characteristics that high activity, high-temperature thermal stability.
Via the above method, the present embodiment can provide a kind of platinum composite catalyst (hollow mesoporous Pt/m-NiO composite catalyzing
Agent), for using Pt particle as core, using mesoporous NiO be the hollow core-shell particle of shell (that is, hollow mesoporous Pt/m-NiO is compound
Structure).
Wherein, the partial size of the Pt particle is 5nm；The mesoporous pore size of the NiO shell is 3nm；The thickness of the NiO shell
Degree is 20nm；It is described using Pt particle as core, by the partial size of the hollow core-shell particle of shell of mesoporous NiO be 80nm.
The platinum composite catalyst of the present embodiment can be applied to Oxidation of Carbon Monoxide, and (Oxidation of Carbon Monoxide is at the anti-of carbon dioxide
Answer) and p -Chloronitrobenzene hydrogenation reaction (reaction that p -Chloronitrobenzene adds hydrogen to prepare p-chloroaniline) in.
Embodiment c
The present embodiment provides a kind of preparation methods of platinum composite catalyst, include the following steps:
1) the Pt particle external surface that partial size is 4nm is superscribed into PS shell, obtains the asymmetric Pt/PS that partial size is 55nm
Core-shell structure；
The specific preparation method of Pt particle: 30mg polyvinylpyrrolidone, 20mg chloroplatinic acid are taken, 5mL water and 45mL are dissolved in
In the mixed solution of ethyl alcohol；After heating 90 DEG C of reflux 4 hours, 70mL acetone precipitation is added, then wash to obtain Pt particle (nanoparticle
Son)；
The specific preparation method of Pt/PS core-shell structure: 30mg potassium peroxydisulfate, 5mg 4- styrene sulfonic acid sodium hydrate are taken, is added
Enter into the mixed solution of 5mL water and 20mL ethyl alcohol；After being heated to 80 DEG C of reflux 3 hours, 0.3mL mixed weight ratio is added in moment
After five minutes 5mL Pt nanoparticle is added, then be heated to reflux at 80 DEG C in styrene/divinyl benzene mixtures of 25:1 immediately
After 5 hours, is washed 3 times with the mixed solution of second alcohol and water, obtain the asymmetry Pt/PS core-shell structure；
2) the asymmetric Pt/PS core-shell structure and Brij-30 template are obtained into grain after nickel acetate reflux is added
The Pt/PS/NiO core-shell structure that diameter is 70nm (NiO shell layer in homogeneous thickness wraps up Pt/PS core-shell structure)；
The specific preparation method of Pt/PS/NiO core-shell structure: by Pt/PS core-shell structure described in 5mL, with Brij-30 or
One or two are mixed according to 25:1 in Lutensol AO5, are then added in 50mmol nickel acetate, and 80 DEG C to be heated to reflux 3 small
Shi Hou, 500 revs/min of centrifuge separations, then with after ethanol washing 3 times, 80 DEG C drying 5 hours, obtain Pt/PS/NiO nucleocapsid knot
Structure；
3) the Pt/PS/NiO core-shell structure is calcined 5 hours at 400 DEG C, a step, which removes in PS and step 2), to be added
The Brij-30 template entered.Thus platinum composite catalyst of the invention can be obtained, and (that is, hollow mesoporous Pt/m-NiO is compound urges
Agent), which has the characteristics that high activity, high-temperature thermal stability.
Via the above method, the present embodiment can provide a kind of platinum composite catalyst (hollow mesoporous Pt/m-NiO composite catalyzing
Agent), for using Pt particle as core, using mesoporous NiO be the hollow core-shell particle of shell (that is, hollow mesoporous Pt/m-NiO is compound
Structure).
Wherein, the partial size of the Pt particle is 4nm；The mesoporous pore size of the NiO shell is 2nm；The thickness of the NiO shell
Degree is 15nm；It is described using Pt particle as core, by the partial size of the hollow core-shell particle of shell of mesoporous NiO be 70nm.
The platinum composite catalyst of the present embodiment can be applied to Oxidation of Carbon Monoxide, and (Oxidation of Carbon Monoxide is at the anti-of carbon dioxide
Answer) and p -Chloronitrobenzene hydrogenation reaction (reaction that p -Chloronitrobenzene adds hydrogen to prepare p-chloroaniline) in.
Embodiment d
The present embodiment provides a kind of preparation methods of platinum composite catalyst, include the following steps:
1) the Pt particle external surface that partial size is 4.5nm is superscribed into PS shell, obtains the asymmetric Pt/ that partial size is 57nm
PS core-shell structure；
The specific preparation method of Pt particle: 40mg polyvinylpyrrolidone, 25mg chloroplatinic acid are taken, 6mL water and 50mL are dissolved in
In the mixed solution of ethyl alcohol；After heating 95 DEG C of reflux 5 hours, 80mL acetone precipitation is added, then wash to obtain Pt particle (nanoparticle
Son)；
The specific preparation method of Pt/PS core-shell structure: 40mg potassium peroxydisulfate, 6mg 4- styrene sulfonic acid sodium hydrate are taken, is added
Enter into the mixed solution of 6mL water and 25mL ethyl alcohol；After being heated to 90 DEG C of reflux 4 hours, 0.4mL mixed weight ratio is added in moment
After 6 minutes, 6mL Pt nanoparticle is added, then be heated to reflux at 90 DEG C in styrene/divinyl benzene mixtures of 30:1 immediately
After 6 hours, is washed 4 times with the mixed solution of second alcohol and water, obtain the asymmetry Pt/PS core-shell structure；
2) the asymmetric Pt/PS core-shell structure and Lutensol AO5 template are obtained after nickel acetate reflux is added
To the Pt/PS/NiO core-shell structure that partial size is 75nm (NiO shell layer in homogeneous thickness wraps up Pt/PS core-shell structure)；
The specific preparation method of Pt/PS/NiO core-shell structure: by Pt/PS core-shell structure described in 6mL, with Brij-30 or
One or two are mixed according to 30:1 in Lutensol AO5, are then added in 60mmol nickel acetate, and 90 DEG C to be heated to reflux 4 small
Shi Hou, 800 revs/min of centrifuge separations, then with after ethanol washing 4 times, 90 DEG C drying 6 hours, obtain Pt/PS/NiO nucleocapsid knot
Structure.
3) the Pt/PS/NiO core-shell structure is calcined 5 hours at 500 DEG C, a step, which removes in PS and step 2), to be added
The Lutensol AO5 template entered.Thus platinum composite catalyst of the invention (that is, hollow mesoporous Pt/m-NiO can be obtained
Composite catalyst), which has the characteristics that high activity, high-temperature thermal stability.
Via the above method, the present embodiment can provide a kind of platinum composite catalyst (hollow mesoporous Pt/m-NiO composite catalyzing
Agent), for using Pt particle as core, using mesoporous NiO be the hollow core-shell particle of shell (that is, hollow mesoporous Pt/m-NiO is compound
Structure).
Wherein, the partial size of the Pt particle is 4.5nm；The mesoporous pore size of the NiO shell is 2.5nm；The NiO shell
With a thickness of 18nm；It is described using Pt particle as core, by the partial size of the hollow core-shell particle of shell of mesoporous NiO be 75nm.
The platinum composite catalyst of the present embodiment can be applied to Oxidation of Carbon Monoxide, and (Oxidation of Carbon Monoxide is at the anti-of carbon dioxide
Answer) and p -Chloronitrobenzene hydrogenation reaction (reaction that p -Chloronitrobenzene adds hydrogen to prepare p-chloroaniline) in.
Technical principle and its technical effect enumeration of the invention is as follows:
To realize high catalytic activity, nano platinum particle core should come into full contact with reactant, while the shell of outer surface is answered
With the performance for allowing reactants and products quickly to spread.The nano platinum particle being wrapped in hollow mesoporous lamella, each platinum are received
Rice corpuscles has a homogeneous environment.Mesoporous size is less than the size of nano platinum particle, under the conditions of harsh high-temperature catalytic
Nano platinum particle remains to be stabilized.
Based on the above principles, the present invention provides a kind of monodisperse platinum particles catalyst of hollow mesoporous NiO shell layer package, system
Preparation Method and application, catalyst catalytic activity with higher, higher thermal stability and can be recycled for multiple times
Performance.
The platinum composite catalyst of high-temperature thermal stability provided by the present invention is to be by core, hollow mesoporous NiO of Pt particle
Shell forms Pt/m-NiO structure.Since mesoporous NiO shell layer corner particle also contributes to hydrogenation reaction, acts synergistically, make with Pt
Obtaining platinum composite catalyst of the invention has high catalytic activity；
In addition, the introducing of mesoporous NiO shell, Pt particle size caused by preventing because of high temperature changes, and catalytic activity is caused to reduce.
Therefore, Pt nanoparticle can be effectively protected in mesoporous NiO shell layer, and the thermostabilization of catalytic active center Pt nanoparticle can be improved
Property, so that platinum composite catalyst of the invention is had the characteristics that high-temperature thermal stability.
High activity provided by the invention, high-temperature thermal stability platinum composite catalyst preparation method is using multistep self assembly
Process.The precursor solution mixing for mixing Pt nanoparticle and polystyrene, after being heated to reflux, forms asymmetric Pt/PS core
Shell structure.Above-mentioned asymmetric Pt/PS nucleocapsid bead, with one or two in a certain amount of Brij-30 or Lutensol AO5
After modification, NiO shell layer then is wrapped up in its outer surface.It is calcined 5 hours at 300~600 DEG C, one-step method removes Brij-30 simultaneously
Or it is empty to get the Pt particle wrapped up to the mesoporous NiO shell layer after one or two kinds of and PS bead template in Lutensol AO5
Core structure catalyst (Pt/m-NiO).
The platinum composite catalyst of high-temperature thermal stability of the invention, can be applied to Oxidation of Carbon Monoxide.Since the present invention uses
Mesoporous NiO is shell, and oxidizing carbon monoxide under the conditions of pyroreaction, hollow mesoporous NiO shell is effectively protected platinum nanoparticle
Son avoids losing catalytic activity due to the nano platinum particle change in size caused by high temperature.
High activity platinum composite catalyst of the invention is also suitble to p -Chloronitrobenzene to add the reaction of hydrogen, mesoporous NiO shell layer corner
Particle facilitates hydrogenation reaction, acts synergistically with Pt, so that catalyst has high catalytic activity, conversion ratio reaches 99%；And
After platinum composite catalyst of the invention is using 16 circulations, conversion ratio is held essentially constant, the characteristics of being recycled for multiple times.
Below by embodiment, comparative example and its experimental data under different technology conditions to platinum composite catalyzing of the invention
Agent and preparation method thereof is described further, to clearly show that its technical effect.
Embodiment 1
It is using Pt particle as core, using hollow mesoporous NiO as shell the present embodiment provides a kind of platinum composite catalyst
Core-shell particles.The preparation method of the catalyst the following steps are included:
(1) 50mg potassium peroxydisulfate, 5mg 4- styrene sulfonic acid sodium hydrate, is added to 5mL water and the mixing of 16mL ethyl alcohol is molten
In liquid, it is heated to 60-100 DEG C of reflux.A certain proportion of styrene/the divinyl benzene mixtures of 0.2mL are added in moment.2 minutes
Afterwards, 3.0mL Pt nanoparticle, after 60-100 DEG C is heated to reflux 4 hours, the mixed solution of product second alcohol and water are added immediately
Washing 3 times.Obtain the bead of Pt/PS unsymmetric kernel shell structure.
The preparation of Pt nanoparticle is as follows: 50mg polyvinylpyrrolidone, 15mg chloroplatinic acid are dissolved in 5mL water and 45mL ethyl alcohol
In, mixture is heated to reflux 3 hours.After acetone precipitation is added, washing obtains Pt nanoparticle.
(2) the above-mentioned Pt/PS core-shell structure of 2mL, it is one or two kinds of in a certain amount of Brij-30 or Lutensol AO5, add
Enter into 50mmol nickel acetate, after being heated to reflux 2 hours, is centrifugated, after ethanol washing 2 times, Pt/PS/NiO is obtained after drying
Structure.
(3) it will be calcined 5 hours at described 300~600 DEG C of Pt/PS/NiO nucleocapsid bead, remove polyethylene pellets and Brij-
To get the hollow catalyst (Pt/m- of Pt particle wrapped up to mesoporous NiO shell layer after one or two in 30 or Lutensol AO5
NiO), which can be used for Oxidation of Carbon Monoxide and p -Chloronitrobenzene hydrogenation reaction, have high activity, high-temperature thermal stability and
The performance that can be recycled for multiple times.
Comparative example 1
This comparative example provides a kind of nano platinum particle catalyst.The catalyst the preparation method is as follows: 50mg polyethylene pyrrole
Pyrrolidone, 15mg chloroplatinic acid are dissolved in 5mL water and 45mL ethyl alcohol, and mixture is heated to reflux 3 hours.After acetone precipitation is added,
Washing obtains Pt nanoparticle.
Catalyst performance evaluation
Embodiment 1 and the platinum composite catalyst that comparative example 1 provides are applied to Oxidation of Carbon Monoxide into the anti-of carbon dioxide
Hydrogen should be added to prepare the reaction of p-chloroaniline with p -Chloronitrobenzene.Oxidation of Carbon Monoxide reacts the oxygen mistake in ultrahigh vacuum room
It is carried out under the conditions of amount.By 10mg platinum composite catalyst and 40torr carbon monoxide, 100torr oxygen and Balance Air 620torr helium
Gas mixes, and is reacted in 320-500 DEG C of temperature range.The platinum composite catalyst of embodiment 1 and comparative example 1 can make an oxidation
Oxidation of coal reaches 99% conversion ratio.When reaction temperature reaches 420 DEG C, after the platinum catalyst of embodiment 1 repeatedly recycles, catalysis is lived
Property is almost unchanged.And the Pt particle in comparative example 1 is after 420 DEG C of catalysis are reacted, and after 2 circulations, catalytic activity inactivation.It can be seen that reality
Applying Pt/m-NiO catalyst in example 1 has high high-temp stability.
Referring to FIG. 4, Fig. 4 is the platinum composite catalyst catalysis p -Chloronitrobenzene hydrogenation reaction of embodiment 1 and comparative example 1
The curve that changes with reaction cycle number of conversion ratio (embodiment 1 and comparative example 1 are referred to as embodiment and comparison by legend in figure
Example).After the platinum composite catalyst of embodiment 1 is using 16 circulations, conversion ratio is held essentially constant, and the platinum particles of comparative example 1
After catalyst is using 16 circulations, conversion ratio is reduced to 10% or less.This shows in the platinum composite catalyst of embodiment 1, is situated between
Hole NiO shell layer is effectively protected nano platinum particle, it is made still to keep catalytic activity after multiple circular response.Therefore, implement
The performance that the platinum composite catalyst of example 1 has high catalytic activity and can be recycled for multiple times.
Certainly, the present invention can also have other various embodiments, without deviating from the spirit and substance of the present invention, ripe
Various corresponding changes and modifications, but these corresponding changes and modifications can be made according to the present invention by knowing those skilled in the art
It all should belong to the protection scope of the claims in the present invention.
Claims (12)
1. a kind of platinum composite catalyst, which is characterized in that it is using platinum particles as core, using mesoporous nickel oxide as the hollow of shell
Core-shell particles；The partial size of the platinum particles is 3-5nm, and the mesoporous pore size of the nickel oxide shell is 1~3nm；The platinum is compound
The preparation method of catalyst is first to make Pt/PS core-shell structure, then Pt/PS core-shell structure is mixed with template, and acetic acid is added
Pt/PS/NiO core-shell structure is generated after nickel reflux, then hollow Jie of Pt@NiO is generated using one-step calcination method removal PS and template
Hole core-shell structure.
2. platinum composite catalyst according to claim 1, which is characterized in that the nickel oxide shell with a thickness of 10~
20nm。
3. platinum composite catalyst according to claim 1, which is characterized in that it is described using platinum particles as core, with mesoporous oxygen
The partial size for changing the hollow core-shell particle that nickel is shell is 60~80nm.
4. a kind of preparation method of platinum composite catalyst, which comprises the steps of:
1) platinum particles outer surface is superscribed into polystyrene shell, obtains asymmetric Pt/PS core-shell structure；
It 2) will be one or two kinds of mixed in the asymmetric Pt/PS core-shell structure and Brij-30 or Lutensol AO5 template
It closes, after nickel acetate reflux is added, obtains Pt/PS/NiO core-shell structure；
3) the Pt/PS/NiO core-shell structure is calcined 4~6 hours at 300~600 DEG C, a step removes PS and step 2)
One or two kinds of mixing in Brij-30 the or Lutensol AO5 template of middle addition.
5. the preparation method of platinum composite catalyst according to claim 4, which is characterized in that the partial size of the platinum particles is
3~5nm.
6. the preparation method of platinum composite catalyst according to claim 4, which is characterized in that the Pt particle preparation method
Include: to take 10~60mg polyvinylpyrrolidone, 5~30mg chloroplatinic acid, is dissolved in the mixed of 1~10mL water and 30~60mL ethyl alcohol
It closes in solution；After 60~100 DEG C of heating reflux 1~6 hour, 10~100mL acetone precipitation is added, then wash to obtain Pt particle.
7. the preparation method of platinum composite catalyst according to claim 4, which is characterized in that the Pt/PS core-shell structure
Partial size be 50~60nm.
8. the preparation method of platinum composite catalyst according to claim 4, which is characterized in that the Pt/PS core-shell structure
Preparation method includes: to take 10~60mg potassium peroxydisulfate, 1~10mg 4- styrene sulfonic acid sodium hydrate, is added to 1~10mL water
In the mixed solution of 10~30mL ethyl alcohol；After being heated to 60~100 DEG C of reflux 1~6 hour, it is mixed that 0.1~0.5mL is added in moment
Styrene/divinyl benzene mixtures of conjunction weight ratio 50:1~1:1,1~after ten minutes, 1.0~10.0mL Pt is added immediately
Nanoparticle, then after 60~100 DEG C are heated to reflux 1~10 hour, are washed 1~5 time, obtained with the mixed solution of second alcohol and water
The asymmetry Pt/PS core-shell structure.
9. the preparation method of platinum composite catalyst according to claim 4, which is characterized in that the Pt/PS/NiO nucleocapsid
The partial size of structure is 60~80nm.
10. the preparation method of platinum composite catalyst according to claim 4, which is characterized in that step 3) is to Pt/PS/NiO
Core-shell structure calcination temperature is 400 DEG C.
11. the preparation method of platinum composite catalyst according to claim 4, which is characterized in that the Pt/PS/NiO nucleocapsid
Structure preparation method includes: by Pt/PS core-shell structure described in 1~10mL, with one kind or two in Brij-30 or Lutensol AO5
Kind is mixed according to 50:1~1:1, is then added in 10~100mmol nickel acetate, 60~100 DEG C are heated to reflux 1~5 hour
Afterwards, 200~1000 revs/min of centrifuge separations, then with after ethanol washing 1~5 time, 50~100 DEG C drying 1~10 hour, obtain
Pt/PS/NiO core-shell structure.
12. a kind of application of platinum composite catalyst described in claim 1, which is characterized in that by above-mentioned platinum composite catalyst application
In Oxidation of Carbon Monoxide and p -Chloronitrobenzene hydrogenation reaction.
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| CN110013823B (en) * | 2018-01-10 | 2021-05-11 | 中国科学院福建物质结构研究所 | Noble metal-transition metal oxide composite material and preparation method and application thereof |
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| CN109453785A (en) * | 2018-11-27 | 2019-03-12 | 浙江工业大学 | A kind of meso-porous nano platinum nickel oxygen reduction electro-catalyst and preparation method thereof |
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