CN105771972A - Preparing method of limited-range catalyst modified through atomic layer deposition and application thereof - Google Patents
Preparing method of limited-range catalyst modified through atomic layer deposition and application thereof Download PDFInfo
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- CN105771972A CN105771972A CN201610128733.2A CN201610128733A CN105771972A CN 105771972 A CN105771972 A CN 105771972A CN 201610128733 A CN201610128733 A CN 201610128733A CN 105771972 A CN105771972 A CN 105771972A
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
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- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
Abstract
The invention provides a preparing method of a limited-range catalyst modified through atomic layer deposition and application.The atomic layer deposition technology is utilized, an ultra-thin oxide layer, Pt nanometer particles and a thick oxide layer are deposited on a carbon nanometer fiber template successively, then calcination is carried out in air to remove the carbon nanometer fiber template, and a Pt-based catalyst with oxide ultra-thin modification and the limited range within an oxide nanometer tube is obtained.The prepared catalyst greatly overcomes the defect that the site of a traditional catalyst metal-oxide interface is limited; compared with a limited-range Pt catalyst without ultra-thin modification and a Pt catalyst with the unlimited range, the limited-range Pt catalyst with ultra-thin modification has the best reduction hydrogenation activity to tetranitro-phenol, and the method can be popularized in preparation of other multi-phase catalysts.
Description
Technical field
The present invention relates to the preparation method and application of a kind of catalyst, be that confinement catalyst is carried out ultra-thin by one
Modify with the method carrying high catalytic activity, and the application that this catalyst is in the reduction hydrogenation of tetranitro-phenol.
Background technology
Heterogeneous catalyst generally comprises metal active constituent and oxide carrier.Carrier not only simply increases gold
Belong to decentralization and the heat endurance of component, and by the performance to catalyst that interacts between Metal-Support
Produce important impact.And be correlated with in the interface that the interaction of Metal-Support usually contacts with Metal-Support.
Recent research have also shown that interface has more superior catalytic reaction activity, catalytic process rises important work
With.(Zhang,B.；Chen,Y.；Li,J.W.；Pippel,E.；Yang,H.M.；Gao,Z.；
Qin,Y.High efficiency Cu-ZnO hydrogenation catalyst:the tailoring of
Cu-ZnO interface sites by molecular layer deposition,ACS Catal.,2015,
5,5567-5573. opens refined, Chen Yao, Qin Yong. and molecular-layer deposition regulation and control site, Cu-ZnO interface preparation is efficient
Cu-ZnO hydrogenation catalyst, ACS Catal., 2015,5,5567-5573.) therefore regulate and control metal-oxide
The interfacial structure of thing makes it be fully used, and either has weight in theoretical research or in commercial Application
The meaning wanted.
But, for traditional loaded catalyst, the ratio shared by metal-oxide interface site is limited
, its catalyst performance is difficult to be greatly improved.In recent years, some researchers by oxide supported to metal watch
On face, prepare the novel carried catalyst that falls.There is more metal-oxide interface position in this model catalyst
Point, improves site, interface proportion.Ald (ALD) is a kind of novel film/nanoparticle
Sub-technology of preparing.ALD can facilitate and controllably prepares the nanocatalyst such as nanotube and core shell structure.With
Time, ALD technique be also applied to metallic surface modify in preparation fall supported catalyst, with optimize metal-
The site, interface of oxide.But previous studies is all to concentrate on the metal nanoparticle to non-confinement to carry out
Surface is modified, and still suffers from a lot of problem, such as, after nanocatalyst is carried out the ultra-thin modification of oxide,
The stability of catalyst is the most very poor, and the modified oxide that nanocatalyst carries out thickness can cause it to live
Property reduce.
To be that another alternative improves metal and carrier in metal nanoparticle confinement to nanotube
The strategy of interphase interaction.On the one hand internal metallic can be played space confinement effect by nanotube,
Stop it assemble and come off thus improve stability, on the other hand can improve interior metal particle and nanotube
Interaction.
In sum, traditional catalyst is limited by preparation method, in the site, interface of catalyst and
The accuracy controlling aspect existing defects of appearance structure etc., the stability making catalyst is bad, and hydrogenation activity is low.
Summary of the invention
It is an object of the invention to provide a kind of good stability, the confinement that the ald that hydrogenation activity is high is modified
The preparation method of catalyst, and the application in the reduction hydrogenation of tetranitro-phenol.
ALD technique has obvious advantage at aspects such as the uniformity of sedimentary, controllabilitys, it is possible at atom
The thickness of the rank accuracy controlling sedimentary of layer, can design regulation and control nano-structured calalyst easily, mirror
In the shortcoming of above prior art, the present invention utilizes the advantage of ALD technique, to confinement gold in nanotube
Belong to particle and carry out ultra-thin modification, to maximize the stability that interface raising activity keeps good simultaneously.
The present invention uses ald to synthesize confinement Pt base catalyst in alumina nano tube, makes simultaneously
With ALD alumina flake, it is carried out ultra-thin modification, by regulating and controlling thickness and then the maximization of ultra-thin decorative layer
The interface of heterogeneous catalyst, in order to solve limited the lacking of metal and site, oxide carrier interface in prior art
Fall into.This method can obtain interface on the basis of retaining the stability that confinement catalyst is good further
Maximized heterogeneous catalyst, thus improve hydrogenation activity.
In order to complete above-mentioned task, the technical scheme is that
(1) by the dried carbon nanofiber dispersion for preparing in ethanol, concentration controls at 0.01-0.1g/ml,
Then this liquid is uniformly coated on quartz plate surface, is evaporated, obtain carbon nano-fiber template；
(2) as template, carbon nano-fiber template is placed into former with the carbon nano-fiber of preparation in step (1)
In sublayer deposition vacuum reaction cavity, during deposition of aluminium oxide, the temperature of cavity controls at 100 DEG C-200 DEG C, cavity
Pressure is 10-100Pa；During deposition Pt, the temperature of cavity controls at 250 DEG C-350 DEG C, and chamber pressure is
10-100Pa, with the volume ratio of carrier gas and vacuum reaction cavity as 1/5-1/10min in deposition process-1, to chamber
Body is passed through carrier gas, using water and trimethyl aluminium as presoma depositing Al2O3, with (trimethyl) methyl ring penta 2
Alkene closes platinum and ozone is presoma Deposition of Pt nanoparticles；ALD is utilized first to deposit in carbon nano-fiber template
The ultra-thin Al of 1-5 period2O3Decorative layer, then deposition 10-50 period Pt nano particle, sinks the most again
The Al of long-pending 40-200 period2O3Form alumina nano tube, obtain sample；
(3) carbon nano-fiber template is removed in sample step (2) obtained 450-550 DEG C of calcining in atmosphere,
Obtain Al2O3The confinement of ultra-thin modification is at Al2O3Pt base catalyst in nanotube.
Al as above2O3The confinement of ultra-thin modification is at Al2O3Pt content in Pt base catalyst in nanotube
For 0.1-2wt%.
Present invention application comprises the steps:
Homemade catalyst sample is added with the ratio of 1/1-5/1 (g/mmol) with reactant p-nitrophenol
In reactor, normal pressure and temperature stirring reaction the most under an atmosphere of hydrogen.UV, visible light spectrophotometer is used to exist
In 200-600nm wave-length coverage, the process to reaction detects, when the maximum suction of reactant p-nitrophenol
Receive reaction when peak disappears to terminate, reaction mass is centrifugally separating to obtain solid catalyst to recycle.
The present invention compared with prior art has the advantage that
1, utilize ALD technique by metal nanoparticle confinement in oxide nano, can keep good steady
Qualitative, solve the defect of traditional supported catalysts poor stability in prior art.
2, utilize the advantage of ALD technique, the deposition oxide decorative layer of uniform, controllable, and to confinement in nanometer
Metallic in pipe carries out ultra-thin modification, can maximize interface and carry high catalytic activity, solves existing
There is the defect that in technology, site, traditional supported catalysts interface is limited.
Accompanying drawing explanation
Fig. 1 is comparative example 1, the first order reaction RATES figure of catalyst in 2, and embodiment 2.
Fig. 2 is comparative example 1, in 2, and embodiment 2 catalyst tetranitro-phenol is reduced hydrogenation circulation
Stability diagram.
Fig. 3 is the scanning electron microscope (SEM) photograph of the Pt base catalyst of the non-confinement in comparative example 2.
Fig. 4 is the scanning electron microscope (SEM) photograph of the Pt base catalyst of the confinement in comparative example 1.
Fig. 5 is the scanning electron microscope (SEM) photograph of the confinement Pt base catalyst of the ultra-thin modification in embodiment 2.
Detailed description of the invention
Embodiment 1: the preparation of the confinement Pt base catalyst of ultra-thin modification
(1) carbon nano-fiber is prepared as template.The dried carbon nanofiber prepared is dissolved in ethanol,
Concentration controls at 0.05g/ml, then this liquid is uniformly coated on glass sheet surface, is placed into atom after being evaporated
In layer deposition vacuum reaction cavity.During deposition of aluminium oxide, the temperature of cavity controls at 150 DEG C, and chamber pressure is
50Pa；During deposition Pt, the temperature of cavity controls at 280 DEG C, and chamber pressure is 50Pa, to carry in deposition process
Gas is 1/8min with the volume ratio of vacuum reaction body of wall-1It is passed through carrier gas to cavity.Using water and trimethyl aluminium as
Presoma depositing Al2O3.Close platinum with (trimethyl) methyl cyclopentadiene and ozone is that presoma deposits Pt nanometer
Particle.
(2) with the carbon nano-fiber of preparation in step (1) as template, utilize ALD with sinking in step (1)
Long-pending condition first deposits the ultra-thin Al of 1 period2O3Decorative layer, then 10 period Pt nanoparticles of deposition
Son, the Al of the most redeposited 40 periods2O3Form alumina nano tube (ANTs).
(3) template of carbon nano-fiber is removed in sample step 2 obtained 450 DEG C of calcinings in atmosphere, obtains
Al2O3The Al modified2O3The Pt base catalyst of nanotube confinement, wherein the content of Pt is 2wt%.At 250mL
There-necked flask in carry out catalyst activity evaluation.50ml p-nitrophenol (0.1mM) is added in there-necked flask,
This catalyst sample of 5mg.Normal temperature and pressure stirring reaction the most under an atmosphere of hydrogen.Use UV, visible light light splitting light
The process of reaction is detected by degree instrument in real time.After reacting eight minutes, the conversion ratio of p-nitrophenol is
99.21%.
Embodiment 2: the preparation of the confinement catalyst of ultra-thin modification
(1) carbon nano-fiber is prepared as template.The dried carbon nanofiber prepared is dissolved in ethanol,
Concentration controls at 0.03g/ml, then this liquid is uniformly coated on glass sheet surface, is placed into atom after being evaporated
In layer deposition vacuum reaction cavity.During deposition of aluminium oxide, the temperature of cavity controls at 180 DEG C, and chamber pressure is
60Pa；During deposition Pt, the temperature of cavity controls at 300 DEG C, and chamber pressure is 60Pa, to carry in deposition process
Gas is 1/8min with the volume ratio of vacuum reaction body of wall-1It is passed through carrier gas to cavity.Using water and trimethyl aluminium as
Presoma depositing Al2O3.Close platinum with (trimethyl) methyl cyclopentadiene and ozone is that presoma deposits Pt nanometer
Particle.
(2) with the carbon nano-fiber of preparation in step (1) as template, utilize ALD with sinking in step (1)
Long-pending condition first deposits the ultra-thin Al of 2 periods2O3Decorative layer, then deposits 20 period Pt nano particles,
The Al of the most redeposited 80 periods2O3Form alumina nano tube.
(3) template of carbon nano-fiber is removed in sample step 2 obtained 500 DEG C of calcinings in atmosphere, obtains
2 periods Al2O3The Al modified2O3The Pt base catalyst of nanotube confinement, is labeled as 2Al-Pt-in-ANTs,
Wherein the content of Pt is 2wt%.From fig. 5, it can be seen that Pt nano particle is uniformly encapsulated in aluminum oxide and is received
In mitron, the diameter of Pt nano particle is 2nm, and the thickness of aluminum oxide tube wall is 10nm.Owing to modifying
Layer thickness is limited, 2Al2O3The Al modified2O3The Pt catalyst phase of the Pt catalyst of nanotube confinement and confinement
Significant difference is not had than pattern.Catalyst activity evaluation is carried out in the there-necked flask of 250mL.In there-necked flask
Add 50ml p-nitrophenol (0.1mM), this catalyst sample of 5mg.Normal temperature the most under an atmosphere of hydrogen
Atmospheric agitation reacts.Use UV, visible light spectrophotometer that the process of reaction is detected in real time.Reaction knot
Shu Hou, is centrifugally separating to obtain solid catalyst by reaction mass, recycles and tests its stability.Reaction eight
After minute, the conversion ratio of p-nitrophenol is 99.15%.Fig. 2 shows, 2Al-Pt-in-ANTs makes in circulation
Being 93.32% with conversion ratio to tetranitro-phenol after four times, conversion ratio declines seldom, illustrates that this catalyst is steady
Qualitative very well.
Embodiment 3: the preparation of the confinement Pt base catalyst of ultra-thin modification
(1) carbon nano-fiber is prepared as template.The dried carbon nanofiber prepared is dissolved in ethanol,
Concentration controls at 0.01g/ml, then this liquid is uniformly coated on glass sheet surface, is placed into atom after being evaporated
In layer deposition vacuum reaction cavity.During deposition of aluminium oxide, the temperature of cavity controls at 100 DEG C, and chamber pressure is
10Pa；During deposition Pt, the temperature of cavity controls at 250 DEG C, and chamber pressure is 10Pa, to carry in deposition process
Gas is 1/10min with the volume ratio of vacuum reaction body of wall-1It is passed through carrier gas to cavity.Using water and trimethyl aluminium as
Presoma depositing Al2O3.Close platinum with (trimethyl) methyl cyclopentadiene and ozone is that presoma deposits Pt nanometer
Particle.
(2) with the carbon nano-fiber of preparation in step (1) as template, utilize ALD with sinking in step (1)
Long-pending condition first deposits the ultra-thin Al of 3 periods2O3Decorative layer, then 30 period Pt nanoparticles of deposition
Son, the Al of the most redeposited 120 periods2O3Form alumina nano tube (ANTs).
(3) template of carbon nano-fiber is removed in sample step 2 obtained 520 DEG C of calcinings in atmosphere, obtains
Al2O3The Al modified2O3The Pt base catalyst of nanotube confinement, wherein the content of Pt is 2wt%.At 250mL
There-necked flask in carry out catalyst activity evaluation.50ml p-nitrophenol (0.1mM) is added in there-necked flask,
This catalyst sample of 5mg.Normal temperature and pressure stirring reaction the most under an atmosphere of hydrogen.Use UV, visible light light splitting light
The process of reaction is detected by degree instrument in real time.After reacting eight minutes, the conversion ratio of p-nitrophenol is
98.98%.
Embodiment 4: the preparation of the confinement Pt base catalyst of ultra-thin modification
(1) carbon nano-fiber is prepared as template.The dried carbon nanofiber prepared is dissolved in ethanol,
Concentration controls at 0.08g/ml, then this liquid is uniformly coated on glass sheet surface, is placed into atom after being evaporated
In layer deposition vacuum reaction cavity.During deposition of aluminium oxide, the temperature of cavity controls at 200 DEG C, and chamber pressure is
80Pa；During deposition Pt, the temperature of cavity controls at 320 DEG C, and chamber pressure is 80Pa, to carry in deposition process
Gas is 1/5min with the volume ratio of vacuum reaction body of wall-1It is passed through carrier gas to cavity.Using water and trimethyl aluminium as front
Drive body depositing Al2O3.Close platinum with (trimethyl) methyl cyclopentadiene and ozone is that presoma deposits Pt nanoparticle
Son.
(2) with the carbon nano-fiber of preparation in step (1) as template, utilize ALD with sinking in step (1)
Long-pending condition first deposits the ultra-thin Al of 4 periods2O3Decorative layer, then 40 period Pt nanoparticles of deposition
Son, the Al of the most redeposited 160 periods2O3Form alumina nano tube (ANTs).
(3) template of carbon nano-fiber is removed in sample step 2 obtained 540 DEG C of calcinings in atmosphere, obtains
Al2O3The Al modified2O3The Pt base catalyst of nanotube confinement, wherein the content of Pt is 2wt%.At 250mL
There-necked flask in carry out catalyst activity evaluation.50ml p-nitrophenol (0.1mM) is added in there-necked flask,
This catalyst sample of 5mg.Normal temperature and pressure stirring reaction the most under an atmosphere of hydrogen.Use UV, visible light light splitting light
The process of reaction is detected by degree instrument in real time.After reacting eight minutes, the conversion ratio of p-nitrophenol is
97.65%.
Embodiment 5: the preparation of the confinement Pt base catalyst of ultra-thin modification
(1) carbon nano-fiber is prepared as template.The dried carbon nanofiber prepared is dissolved in ethanol,
Concentration controls at 0.1g/ml, then this liquid is uniformly coated on glass sheet surface, is placed into atomic layer after being evaporated
In deposition vacuum reaction cavity.During deposition of aluminium oxide, the temperature of cavity controls at 200 DEG C, and chamber pressure is
100Pa；Deposition Pt time cavity temperature control at 350 DEG C, chamber pressure is 100Pa, in deposition process with
Carrier gas is 1/5min with the volume ratio of vacuum reaction body of wall-1It is passed through carrier gas to cavity.Using water and trimethyl aluminium as
Presoma depositing Al2O3.Close platinum with (trimethyl) methyl cyclopentadiene and ozone is that presoma deposits Pt nanometer
Particle.
(2) with the carbon nano-fiber of preparation in step (1) as template, utilize ALD with sinking in step (1)
Long-pending condition first deposits the ultra-thin Al of 5 periods2O3Decorative layer, then 50 period Pt nanoparticles of deposition
Son, the Al of the most redeposited 200 periods2O3Form alumina nano tube (ANTs).
(3) template of carbon nano-fiber is removed in sample step 2 obtained 550 DEG C of calcinings in atmosphere, obtains
Al2O3The Al modified2O3The Pt base catalyst of nanotube confinement, wherein the content of Pt is 2wt%.At 250mL
There-necked flask in carry out catalyst activity evaluation.50ml p-nitrophenol (0.1mM) is added in there-necked flask,
This catalyst sample of 5mg.Normal temperature and pressure stirring reaction the most under an atmosphere of hydrogen.Use UV, visible light light splitting light
The process of reaction is detected by degree instrument in real time.After reacting eight minutes, the conversion ratio of p-nitrophenol is
99.01%.
Embodiment 6: the preparation of the confinement catalyst of ultra-thin modification
(1) carbon nano-fiber is prepared as template.The dried carbon nanofiber prepared is dissolved in ethanol,
Concentration controls at 0.05g/ml, then this liquid is uniformly coated on glass sheet surface, is placed into atom after being evaporated
In layer deposition vacuum reaction cavity.During deposition of aluminium oxide, the temperature of cavity controls at 150 DEG C, and chamber pressure is
50Pa；During deposition Pt, the temperature of cavity controls at 300 DEG C, and chamber pressure is 50Pa, to carry in deposition process
Gas is 1/10min with the volume ratio of vacuum reaction body of wall-1It is passed through carrier gas to cavity.Using water and trimethyl aluminium as
Presoma depositing Al2O3.Close platinum with (trimethyl) methyl cyclopentadiene and ozone is that presoma deposits Pt nanometer
Particle.
(2) as template, ALD is utilized first to deposit the ultra-thin of 1 period with the carbon nano-fiber of preparation in step 1
Al2O3Decorative layer, then deposits 10 period Pt nano particles, the Al of the most redeposited 80 periods2O3
Form alumina nano tube.
(3) template of carbon nano-fiber is removed in sample step 2 obtained 500 DEG C of calcinings in atmosphere, obtains
Al2O3The confinement of ultra-thin modification is at Al2O3Pt base catalyst in nanotube.Wherein the content of Pt is 1%.
Catalyst activity evaluation is carried out in the there-necked flask of 250mL.50ml p-nitrophenol is added in there-necked flask
(0.1mM), this catalyst sample of 10mg.Normal pressure and temperature stirring reaction the most under an atmosphere of hydrogen.Use purple
The process of reaction is detected by outer visible spectrophotometric instrument in real time, after reacting eight minutes, and turning of p-nitrophenol
Rate is 98.63%.
Embodiment 7: the preparation of the confinement catalyst of ultra-thin modification
(1) carbon nano-fiber is prepared as template.The dried carbon nanofiber prepared is dissolved in ethanol,
Concentration controls at 0.05g/ml, then this liquid is uniformly coated on glass sheet surface, is placed into atom after being evaporated
In layer deposition vacuum reaction cavity.During deposition of aluminium oxide, the temperature of cavity controls at 150 DEG C, and chamber pressure is
50Pa；During deposition Pt, the temperature of cavity controls at 300 DEG C, and chamber pressure is 50Pa, to carry in deposition process
Gas is 1/10min with the volume ratio of vacuum reaction body of wall-1It is passed through carrier gas to cavity.Using water and trimethyl aluminium as
Presoma depositing Al2O3.Close platinum with (trimethyl) methyl cyclopentadiene and ozone is that presoma deposits Pt nanometer
Particle.
(2) as template, ALD is utilized first to deposit the ultra-thin of 1 period with the carbon nano-fiber of preparation in step 1
Al2O3Decorative layer, then deposits 1 period Pt nano particle, the Al of the most redeposited 80 periods2O3Shape
Become alumina nano tube.
(3) template of carbon nano-fiber is removed in sample step 2 obtained 500 DEG C of calcinings in atmosphere, obtains
Al2O3The confinement of ultra-thin modification is at Al2O3Pt base catalyst in nanotube.Wherein the content of Pt is 0.1%.
Catalyst activity evaluation is carried out in the there-necked flask of 250mL.50ml p-nitrophenol is added in there-necked flask
(0.1mM), this catalyst sample of 25mg.Normal pressure and temperature stirring reaction the most under an atmosphere of hydrogen.Use purple
The process of reaction is detected by outer visible spectrophotometric instrument in real time, after reacting eight minutes, and turning of p-nitrophenol
Rate is 97.84%.
In order to verify the catalysis activity that the confinement catalyst of ultra-thin modification strengthens, we are also prepared for the Pt of confinement and urge
Agent, the Pt catalyst of non-confinement, contrast it and tetranitro-phenol is reduced the activity of hydrogenation reaction.Below
The present invention is expanded on further in conjunction with concrete comparative example.
Comparative example one: the preparation of the Pt base catalyst of confinement
(1) carbon nano-fiber is prepared as template.The dried carbon nanofiber prepared is dissolved in ethanol,
Concentration controls at 0.03g/ml, then this liquid is uniformly coated on glass sheet surface, is placed into atom after being evaporated
In layer deposition vacuum reaction cavity.During deposition of aluminium oxide, the temperature of cavity controls at 180 DEG C, and chamber pressure is
60Pa；During deposition Pt, the temperature of cavity controls at 300 DEG C, and chamber pressure is 60Pa, to carry in deposition process
Gas is 1/8min with the volume ratio of vacuum reaction body of wall-1It is passed through carrier gas to cavity.Using water and trimethyl aluminium as front
Drive body depositing Al2O3.Close platinum with (trimethyl) methyl cyclopentadiene and ozone is that presoma deposits Pt nanoparticle
Son.
(2) with the carbon nano-fiber of preparation in step (1) as template, utilize ALD with sinking in step (1)
Long-pending condition deposits 20 period Pt nano particles, the Al of the most redeposited 80 periods2O3Formation aluminum oxide is received
Mitron.
(3) template of carbon nano-fiber is removed in sample step 2 obtained 500 DEG C of calcinings in atmosphere, obtains
Al2O3The Pt base catalyst of nanotube confinement, is labeled as Pt-in-ANTs, is the Pt base catalyst of confinement,
Wherein the content of Pt is 2%.From the TEM of Fig. 4 it can be seen that Pt nano particle is uniformly encapsulated in oxidation
In aluminium nanotube, the diameter of Pt nano particle is 2nm, and the thickness of aluminum oxide tube wall is 10nm.250
The there-necked flask of mL carries out catalyst activity evaluation.50ml p-nitrophenol (0.1 is added in there-necked flask
MM), this catalyst sample of 5mg.Normal pressure and temperature stirring reaction the most under an atmosphere of hydrogen.Use UV, visible light
The process of reaction is detected by spectrophotometer in real time.After reacting eight minutes, the conversion ratio of p-nitrophenol
It is 58.23%.Fig. 2 shows, the conversion ratio of tetranitro-phenol is after recycling four times by Pt-in-ANTs
52.47%, conversion ratio declines seldom, illustrates that this catalyst stability is fine.
Comparative example two: the preparation of the Pt catalyst of non-confinement
Remaining preparation process of this catalyst as comparative example one, simply change in step (2) Pt and
The sedimentary sequence of aluminum oxide, obtains Pt nanometer particle load at Al2O3Catalyst on nanotube outer wall, mark
For Pt-out-ANTs, being the Pt base catalyst of non-confinement, wherein the content of Pt is 2%.From Fig. 3's
TEM is it can be seen that Pt nano particle uniform load is at alumina nano tube outer wall, the diameter of Pt nano particle
Size is 2nm, and the thickness of aluminum oxide tube wall is 10nm.Catalyst activity is carried out in the there-necked flask of 250mL
Evaluate.50ml p-nitrophenol (0.1mM), this catalyst sample of 5mg is added in there-necked flask.Then
Normal pressure and temperature stirring reaction under an atmosphere of hydrogen.Use UV, visible light spectrophotometer that the process of reaction is carried out
Detection in real time.After reacting eight minutes, the conversion ratio of p-nitrophenol is 28.49%.Fig. 2 shows, Pt-out-ANTs
After recycling four times, conversion ratio is only 2.32%.Conversion ratio declines to a great extent, and this catalyst stability is described relatively
Difference.
In above-mentioned comparative example and embodiment, the Catalytic Hydrogenation Properties of tetranitro-phenol is shown by each catalyst, confinement
Pt base catalyst is higher than the catalysis activity of the Pt base catalyst of non-confinement, and Al2O3The confinement of ultra-thin modification is urged
Agent is higher than the activity of the Pt base catalyst of confinement again, because the ultra-thin decorative layer of aluminum oxide drastically increases gold
Site, the interface proportion of genus-oxide, so that hydrogenation activity improves.The embodiment 2 of Fig. 1 matching,
The first order reaction RATES figure of the catalyst of comparative example 1 and comparative example 2 further confirms, expression activitiy
For: 2Al-Pt-in-ANTs > Pt-in-ANTs > Pt-out-ANTs.Fig. 2 shows, 2Al-Pt-in-ANTs
Reduce seldom with Pt-in-ANTs conversion ratio after reusing four times, and Pt-out-ANTs is due to the most outward
The protection of wall alumina nano tube, reuses four rear stabilities and substantially reduces a lot.These results suggest that,
The confinement Pt catalyst of ultra-thin modification has higher activity and remains the stability that confinement catalyst is good.
Claims (3)
1. the preparation method of the confinement catalyst of an ald modification, it is characterised in that comprise the steps:
(1) by dried carbon nanofiber dispersion in ethanol, concentration controls at 0.01-0.1g/ml, then this liquid is uniformly coated on quartz plate surface, is evaporated, and obtains carbon nano-fiber template；
(2), carbon nano-fiber template being placed in ald vacuum reaction cavity as template with the carbon nano-fiber of preparation in step (1), during deposition of aluminium oxide, the temperature of cavity controls at 100 DEG C-200 DEG C, and chamber pressure is 10-100Pa；During deposition Pt, the temperature of cavity controls at 250 DEG C-350 DEG C, and chamber pressure is 10-100Pa, with the volume ratio of carrier gas and vacuum reaction cavity for 1/5-1/10 min in deposition process-1, it is passed through carrier gas to cavity, using water and trimethyl aluminium as presoma depositing Al2O3, close platinum with (trimethyl) methyl cyclopentadiene and ozone be presoma Deposition of Pt nanoparticles；ALD is utilized first to deposit the ultra-thin Al of 1-5 period in carbon nano-fiber template2O3Decorative layer, then deposition 10-50 period Pt nano particle, the Al of last redeposited 40-200 period2O3Form alumina nano tube, obtain sample；
(3) carbon nano-fiber template is removed in sample step (2) obtained 450-550 DEG C of calcining in atmosphere, obtains Al2O3The confinement of ultra-thin modification is at Al2O3Pt base catalyst in nanotube.
The preparation method of the confinement catalyst that a kind of ald the most as claimed in claim 1 is modified, it is characterised in that described Al2O3The confinement of ultra-thin modification is at Al2O3In Pt base catalyst in nanotube, Pt content is 0.1-2wt%.
The application of the confinement catalyst that a kind of ald the most as claimed in claim 3 is modified, it is characterised in that comprise the steps:
Catalyst is added in reactor with reactant p-nitrophenol with the ratio of 1-5g:1mmol, normal pressure and temperature stirring reaction the most under an atmosphere of hydrogen, UV, visible light spectrophotometer is used in 200-600 nm wave-length coverage, the process of reaction to be detected, when the maximum absorption band of reactant p-nitrophenol disappears, reaction terminates, and reaction mass is centrifugally separating to obtain solid catalyst to recycle.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610128733.2A CN105771972B (en) | 2016-03-07 | 2016-03-07 | A kind of preparation method and applications of the confinement catalyst of atomic layer deposition modification |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610128733.2A CN105771972B (en) | 2016-03-07 | 2016-03-07 | A kind of preparation method and applications of the confinement catalyst of atomic layer deposition modification |
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| Publication Number | Publication Date |
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| CN105771972A true CN105771972A (en) | 2016-07-20 |
| CN105771972B CN105771972B (en) | 2018-07-20 |
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| CN107376918A (en) * | 2017-06-22 | 2017-11-24 | 上海师范大学 | High heat stability alundum (Al2O3)/nickel/alundum (Al2O3) sandwich catalyst and preparation method and application |
| CN107519936A (en) * | 2017-09-05 | 2017-12-29 | 中国科学院山西煤炭化学研究所 | A kind of method for encapsulating homogeneous catalyst in mesopore molecular sieve duct |
| CN109589973A (en) * | 2018-12-22 | 2019-04-09 | 中国科学院山西煤炭化学研究所 | A method of preparing stable mono-dispersed nano catalyst |
| CN109675609A (en) * | 2019-01-18 | 2019-04-26 | 太原科技大学 | A kind of preparation method and applications of the nano-pore Au-based catalyst of the ultra-thin modified titanium dioxide of atomic layer deposition |
| CN109847739A (en) * | 2019-03-26 | 2019-06-07 | 福州大学 | A kind of method of modifying of Pd/ γ-aluminum trioxide catalyst |
| CN110038590A (en) * | 2019-05-14 | 2019-07-23 | 中国科学院山西煤炭化学研究所 | A kind of more interlayer composite catalysts and its preparation method and application |
| CN110193365A (en) * | 2019-07-04 | 2019-09-03 | 中国科学院大连化学物理研究所 | A kind of method that technique for atomic layer deposition prepares platinum based catalyst and its application in dehydrogenating propane reaction |
| CN110694615A (en) * | 2019-10-15 | 2020-01-17 | 中国科学院山西煤炭化学研究所 | Preparation method of Pt-based catalyst with adjustable pore diameter and limited titanium oxide nanotube and application of Pt-based catalyst prepared by preparation method |
| CN110878344A (en) * | 2019-12-17 | 2020-03-13 | 臻准生物科技（上海）有限公司 | Method for shortening PCR amplification time |
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| CN113181907A (en) * | 2021-04-28 | 2021-07-30 | 中国科学院山西煤炭化学研究所 | Sandwich structure catalyst, space separation double-promoter structure photocatalyst, preparation method and application |
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| CN107519936A (en) * | 2017-09-05 | 2017-12-29 | 中国科学院山西煤炭化学研究所 | A kind of method for encapsulating homogeneous catalyst in mesopore molecular sieve duct |
| CN109589973A (en) * | 2018-12-22 | 2019-04-09 | 中国科学院山西煤炭化学研究所 | A method of preparing stable mono-dispersed nano catalyst |
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| CN110038590A (en) * | 2019-05-14 | 2019-07-23 | 中国科学院山西煤炭化学研究所 | A kind of more interlayer composite catalysts and its preparation method and application |
| CN110038590B (en) * | 2019-05-14 | 2020-06-30 | 中国科学院山西煤炭化学研究所 | Multi-interlayer composite catalyst and preparation method and application thereof |
| WO2020228779A1 (en) * | 2019-05-14 | 2020-11-19 | 中国科学院山西煤炭化学研究所 | Multi-sandwich composite catalyst, preparation method therefor and application thereof |
| US11642667B2 (en) | 2019-05-14 | 2023-05-09 | Institute Of Coal Chemistry, Chinese Academy Of Sciences | Multi-sandwich composite catalyst and preparation method and application thereof |
| CN110193365A (en) * | 2019-07-04 | 2019-09-03 | 中国科学院大连化学物理研究所 | A kind of method that technique for atomic layer deposition prepares platinum based catalyst and its application in dehydrogenating propane reaction |
| CN110694615A (en) * | 2019-10-15 | 2020-01-17 | 中国科学院山西煤炭化学研究所 | Preparation method of Pt-based catalyst with adjustable pore diameter and limited titanium oxide nanotube and application of Pt-based catalyst prepared by preparation method |
| CN110878344A (en) * | 2019-12-17 | 2020-03-13 | 臻准生物科技（上海）有限公司 | Method for shortening PCR amplification time |
| CN113058591A (en) * | 2021-03-25 | 2021-07-02 | 太原科技大学 | Preparation method and application of titanium oxide nanotube-confined platinum-based catalyst |
| CN113181907A (en) * | 2021-04-28 | 2021-07-30 | 中国科学院山西煤炭化学研究所 | Sandwich structure catalyst, space separation double-promoter structure photocatalyst, preparation method and application |
| CN113181907B (en) * | 2021-04-28 | 2022-11-08 | 中国科学院山西煤炭化学研究所 | Sandwich structure catalyst, space separation double-promoter structure photocatalyst, preparation method and application |
| WO2024080789A1 (en) * | 2022-10-13 | 2024-04-18 | 주식회사 엘지화학 | Catalyst for producing carbon nanotube |
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