CN109659576A - Micro-nano cell catalyst and preparation method and purposes - Google Patents
Micro-nano cell catalyst and preparation method and purposes Download PDFInfo
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- CN109659576A CN109659576A CN201910098152.2A CN201910098152A CN109659576A CN 109659576 A CN109659576 A CN 109659576A CN 201910098152 A CN201910098152 A CN 201910098152A CN 109659576 A CN109659576 A CN 109659576A
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- H01M4/90—Selection of catalytic material
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- H—ELECTRICITY
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- H01M4/90—Selection of catalytic material
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- H—ELECTRICITY
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- 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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Abstract
The invention discloses micro-nano cell catalyst and preparation methods and purposes, the micro-nano cell catalyst is using micro-nano conductive nanometer material as carrier, by introducing the micro-nano active site with different oxidation-reduction potentials and catalytic property on carrier framework, micro-nano cell catalyst is obtained, and is applied to catalysis reaction.When micro-nano cell catalyst is used as catalytic activation hydrogen reducing benzaldehyde, reaction condition is mild, and catalytic activity is high, and stability is good, at low cost, and the conversion ratio of reactant and the selectivity of product are high.
Description
Technical field
The present invention relates to the technical field of catalytic activation hydrogen reducing benzaldehyde more particularly to a kind of micro-nano cell catalysts
And preparation method and purposes.
Background technique
Catalyst is the foundation stone of modern chemical industry, makes to chemically react relatively mild by changing chemical reaction path
Under the conditions of carry out.However by catalyst, theoretical, catalyst material and synthesis are limited with characterization method, current many Industrial Catalysis
Agent generally requires the harsh reaction condition such as high temperature, high pressure when catalytic chemistry reacts, and not only energy consumption is high, and catalytic efficiency is low, and
A large amount of pollutants are generated, biggish environmental problem is caused, also constrain the development of contemporary chemical industry.Therefore, it needs to develop
New catalyst improves catalytic efficiency and selectivity, carries out catalysis reaction under relatively mild conditions, reaches energy-saving and emission-reduction
Purpose.We are based on problems and have invented a kind of micro-nano cell catalyst, are dedicated to improving the catalysis effect of industrial catalyst
Rate realizes that efficient catalytic chemically reacts under temperate condition.
Summary of the invention
It is an object of the invention to current catalyst there are aiming at the problem that, a kind of micro-nano cell catalyst and preparation are provided
Method and purposes.Catalyst provided by the invention can synthesize under the conditions of relatively mild, and synthesis cost is low, synthesis technology letter
Single, environmental-friendly, high catalytic efficiency, especially can solve the existing energy consumption height of traditional industry catalysis and brought environment is asked
Topic.
The purpose of the present invention is achieved through the following technical solutions: a kind of micro-nano cell catalyst, it is mainly by micro-
Receive electrically conductive carrier material, micro-nano cathode and micro-nano anode composition；The micro-nano electrically conductive carrier material is the material that can transmit electronics
Material；Selected from micro-nano carbon material, micro-nano organic conductive polymer material, micro-nano conductive inorganic oxide material.
Further, the micro-nano carbon material includes: carbon quantum dot, graphene, porous carbon materials；Micro-nano organic conductive is poly-
Closing object material includes: polythiophene, polypyrrole, polyaniline；Micro-nano conductive inorganic oxide material includes: zinc oxide, tin oxide, oxygen
Change indium, tin indium oxide.
The present invention also provides a kind of preparation method of above-mentioned micro-nano cell catalyst, this method specifically: first by carbon
Source, nitrogen source, boron source and water were according to molar ratio 2:1:1:500 ultrasonic mixing 30 minutes.Gained mixture is transferred to containing polytetrafluoro
In the reaction kettle of ethylene liner, heating reaction 5 hours under the conditions of 200 DEG C.After temperature naturally cools to room temperature, by gained
Mixture is centrifuged off insoluble matter, obtains orange solution, and vacuum distillation obtains boron and nitrogen under the conditions of 0.001MPa and 60 DEG C
The carbon dots material of codope.Then by carbon dots material and PdCl2It is uniformly mixed with water according to mass ratio 20:1:400, at 100 DEG C
Under the conditions of back flow reaction 18h.After reaction solution is cooled to room temperature, gained mixture is subtracted under the conditions of 0.001MPa and 60 DEG C
Pressure distillation, obtains solid material, as using micro-nano carbon material as the micro-nano cell catalyst of conductive material.The carbon source is preferably
Citric acid, the nitrogen source are preferably Na2EDTA, and the boron source is preferably to Carboxybenzeneboronic acid.
The present invention also provides the preparation method of another above-mentioned micro-nano cell catalyst, this method specifically: first will
Carbon source, nitrogen source, boron source and acetone are uniformly mixed according to mass ratio 10:1:5:300, and stir about 12h is dry up to stirring, by solid powder
It is put in crucible, 800 DEG C of calcining 1h under nitrogen environment, obtain boron and nitrogen co-doped grapheme material in tube furnace.Then
By graphene and PdCl2Back flow reaction 18h under the conditions of 100 DEG C is uniformly mixed according to mass ratio 20:1:400 with water.Work as reaction
Liquid is cooled to after room temperature, and gained mixture is evaporated under reduced pressure under the conditions of 0.001MPa and 60 DEG C, obtains solid material, as
Using micro-nano carbon material as the micro-nano cell catalyst of conductive material.The carbon source is preferably methylcellulose), the nitrogen source is preferred
For urea, the boron source is preferably 4- (1- naphthalene)-phenyl boric acid.
The present invention also provides the preparation method of another above-mentioned micro-nano cell catalyst, this method specifically: by micro-nano
Organic conductive polymer, aluminium salt and water are uniformly mixed according to mass ratio 20:1:100,100 DEG C of reflux 12h, and centrifuge washing is dry
Afterwards, aluminium-organic conductive polymer composite material is obtained；By aluminium-organic conductive polymer composite material and PdCl2With water according to quality
It is uniformly mixed than 20:1:100,100 DEG C of reflux 12h, centrifuge washing is dry to get using micro-nano organic conductive polymer as conduction material
The micro-nano cell catalyst of material.The micro-nano organic conductive polymer is preferably polythiophene, polypyrrole or polyaniline.
The present invention also provides the preparation method of another above-mentioned micro-nano cell catalyst, this method specifically: by oxalic acid
Zinc, tin oxalate or oxalic acid indium calcine 2h at 170 DEG C -190 DEG C to get corresponding conductive inorganic oxide material is arrived in air.
By it by method of chemical immersion carrying transition metal ion, composite material, transition metal ions and conductive inorganic oxide material are obtained
The mass ratio of material is 5:100, and transition metal is selected from manganese, cobalt, iron, copper, aluminium, chromium；Matter is pressed with sodium hypophosphite and above-mentioned composite material
Amount proportion 5:100 is uniformly mixed, and 600 DEG C of calcining 1h, it is compound to obtain phosphating metal-metal oxide under tube furnace nitrogen atmosphere
Material.Configuration concentration is the PdCl of 1mg/mL2Aqueous solution or RuCl3Aqueous solution, according to tenor molar ratio 1:1 by PdCl2It is water-soluble
Liquid or RuCl3Aqueous solution is mixed with phosphating metal-metal oxide composite, stirs 6h, centrifuge washing it is dry to get to
Micro-nano conductive inorganic oxide is the micro-nano cell catalyst of conductive material.
The present invention also provides the purposes that a kind of above-mentioned micro-nano cell catalyst is used to be catalyzed reduction benzaldehyde, purposes tools
Body are as follows: 3800:60:0.3:16:4 sequentially adds acetonitrile, benzaldehyde, micro-nano battery and urges in molar ratio in glass closed reactor
Agent, tetrafluoro boric acid and anhydrous sodium sulfate, using hydrogen balloon as hydrogen source, 25 DEG C constant temperature synthesis under normal pressure 2 hours, reaction mixing
Object passes through the conversion ratio and benzyl alcohol and first of GC-MS calculating benzaldehyde after centrifugation, extraction, drying and excessively miniature silicagel column
The yield of benzene.
The present invention compared with prior art, has following technical effect that
1, micro-nano cell catalyst preparation process of the invention is simple, and stability is good, at low cost；
2, reaction condition is mild, and catalytic activity is high, and stability is high, pollution-free；
3, the yield of catalytic activation hydrogen reducing benzaldehyde synthesis toluene is high, and selectivity is high.
Specific embodiment
Micro-nano cell catalyst of the present invention mainly consists of three parts, respectively micro-nano electrically conductive carrier material and have difference
The micro-nano cathode and micro-nano anode of oxidation-reduction potential and catalytic property.
Micro-nano electrically conductive carrier material of the present invention is the material that can transmit electronics；Have selected from micro-nano carbon material, micro-nano
Machine conducting polymer materials and micro-nano conductive inorganic oxide material.
Micro-nano carbon material includes: carbon quantum dot, graphene, porous carbon materials, and micro-nano organic conductive polymer material includes:
Polythiophene, polypyrrole, polyaniline, micro-nano conductive inorganic oxide material include: zinc oxide, tin oxide, indium oxide, indium oxide
Tin.
The preparation method of micro-nano cell catalyst of the present invention mainly includes the following steps: regulation synthesis micro-nano conductive carrier material
Then material introduces the micro-nano cathode and anode catalyst with different oxidation-reduction potentials and catalytic property on a support material,
Up to micro-nano cell catalyst.
The present invention is the micro-nano cell catalyst of conductive material the preparation method is as follows: (1) prepares carbon using micro-nano carbon material
Point material: by carbon source (such as citric acid), nitrogen source (such as Na2EDTA), boron source (such as to Carboxybenzeneboronic acid) and water according to
Molar ratio 2:1:1:500 ultrasonic mixing 30 minutes.Gained mixture is transferred in the reaction kettle containing polytetrafluoroethyllining lining,
Heating reaction 5 hours under the conditions of 200 DEG C.After temperature naturally cools to room temperature, gained mixture is centrifuged off insoluble matter,
Orange solution is obtained, vacuum distillation obtains boron and nitrogen co-doped carbon dots material under the conditions of 0.001MPa and 60 DEG C.(2) it makes
Standby graphene: carbon source (such as methylcellulose), nitrogen source (such as urea), boron source (such as 4- (1- naphthalene)-phenyl boric acid) and acetone are pressed
It is uniformly mixed according to mass ratio 10:1:5:300, stir about 12h is dry up to stirring, and solid powder is put in crucible, in tube furnace
The lower 800 DEG C of calcinings 1h of nitrogen environment, obtains boron and nitrogen co-doped grapheme material.(3) take step 1 prepare carbon dots material or
Graphene prepared by step 2, with PdCl2It is uniformly mixed with water according to mass ratio 20:1:400, then flows back under the conditions of 100 DEG C
React 18h.After reaction solution is cooled to room temperature, gained mixture is evaporated under reduced pressure under the conditions of 0.001MPa and 60 DEG C, is obtained
To solid material, as using micro-nano carbon material as the micro-nano cell catalyst of conductive material.The micro-nano cell catalyst passes through powder
Last X-ray diffraction, transmission electron microscope, EDX, differential thermal analysis, elemental analysis, x-ray photoelectron spectroscopy, EPR and infrared spectroscopy
It is characterized.
The present invention is the micro-nano cell catalyst of conductive material the preparation method is as follows: will using micro-nano organic conductive polymer
Micro-nano organic conductive polymer (such as polythiophene, polypyrrole, polyaniline), aluminium salt and water mix equal according to mass ratio 20:1:100
Even, 100 DEG C of reflux 12h obtain aluminium-organic conductive polymer composite material after centrifuge washing is dry；By aluminium-organic conductive polymerization
Object composite material and PdCl2It is uniformly mixed with water according to mass ratio 20:1:100,100 DEG C of reflux 12h, centrifuge washing is dry, i.e.,
It is able to the micro-nano cell catalyst that micro-nano organic conductive polymer is conductive material.The micro-nano cell catalyst is penetrated by powder X-ray-
Line diffraction, transmission electron microscope, EDX, differential thermal analysis, elemental analysis, x-ray photoelectron spectroscopy, EPR and infrared spectroscopy carry out
Characterization.
The present invention is the micro-nano cell catalyst of conductive material the preparation method is as follows: will using micro-nano conductive inorganic oxide
Zinc oxalate, tin oxalate or oxalic acid indium calcine 2h at 170 DEG C -190 DEG C to get corresponding conductive inorganic oxide is arrived in air
Material.By it by method of chemical immersion carrying transition metal ion (such as manganese, cobalt, iron, copper, aluminium, chromic salts), composite material, mistake are obtained
The mass ratio for crossing metal ion and conductive inorganic oxide material is 5:100；Quality is pressed with sodium hypophosphite and above-mentioned composite material
It matches 5:100 to be uniformly mixed, 600 DEG C of calcining 1h, obtain phosphating metal-metal oxide composite wood under tube furnace nitrogen atmosphere.
Configuration concentration is the PdCl of 1mg/mL2Aqueous solution or RuCl3Aqueous solution, according to tenor molar ratio 1:1 by PdCl2Aqueous solution
Or RuCl3Aqueous solution is mixed with phosphating metal-metal oxide composite, stirs 6h, and centrifuge washing is dry to get to micro-
Conductive inorganic oxide of receiving is the micro-nano cell catalyst of conductive material.The micro-nano cell catalyst is spread out by powder X-ray
It penetrates, transmission electron microscope, EDX, differential thermal analysis, elemental analysis, x-ray photoelectron spectroscopy, EPR and infrared spectroscopy are characterized.
Micro-nano cell catalyst prepared by the present invention can be used for being catalyzed reduction benzaldehyde, concrete operations are as follows: closed in glass
In reactor in molar ratio 3800:60:0.3:16:4 sequentially add acetonitrile, benzaldehyde, micro-nano cell catalyst, tetrafluoro boric acid and
Anhydrous sodium sulfate.Using hydrogen balloon as hydrogen source, 25 DEG C constant temperature synthesis under normal pressure 2 hours, reaction mixture through centrifugation, extraction,
After dry and excessively miniature silicagel column, the conversion ratio of benzaldehyde and the yield of benzyl alcohol and toluene are calculated by GC-MS.
The beneficial effects of the present invention are: micro-nano cell catalyst of the present invention, is with micro-nano conductive nanometer material
It is respectively cathode and anode-catalyzed activity with the micro-nano catalyst with different oxidation-reduction potentials and catalytic property for carrier
Center can be applied to catalytic activation hydrogen reducing benzaldehyde.Compared with traditional catalyst, the catalysis of micro-nano cell catalyst is living
Property center be respectively for oxidation half-reaction and reduction half-reaction independent design, can by efficiently act synergistically greatly improve
Catalytic efficiency makes to need the chemical reaction carried out under harsh reaction condition to carry out under relatively mild conditions originally, and catalysis is lived
Property it is high, low energy consumption, and pollutant is few.
Following embodiment will be helpful to understand the present invention, but the scope of protection of the present invention is not limited thereto content:
Embodiment 1
By citric acid (7.65mmol), Na2EDTA (3.825mmol) and to Carboxybenzeneboronic acid
(3.825mmol) is dissolved in 35mL water, then ultrasonic mixing 30 minutes.Gained mixture is transferred to 50mL containing polytetrafluoroethyl-ne
In the autoclave of alkene liner, heating reaction 5 hours under the conditions of 200 DEG C.After temperature naturally cools to room temperature, by institute
It obtains mixture and is centrifuged off insoluble matter, obtain orange solution, boron and nitrogen co-doped carbon dots material are obtained by vacuum distillation,
It is named as BNCD.Gained BNCD material is dissolved in 30mL water, PdCl is added2(0.95mmol), then magnetic under the conditions of 100 DEG C
Power is stirred at reflux reaction 18h.After reaction solution naturally cools to room temperature, gained mixture is evaporated under reduced pressure, brown color is obtained
Solid is named as micro cell catalyst Pd-BNCD.
Embodiment 2
Citric acid (7.65mmol) and Na2EDTA (3.825mmol) are dissolved in 35mL water, then surpassed
Sound mixes 30 minutes.Gained mixture is transferred in autoclave of the 50mL containing polytetrafluoroethyllining lining, in 200 DEG C of conditions
Lower heating is reacted 5 hours.After temperature naturally cools to room temperature, gained mixture is centrifuged off insoluble matter, is obtained orange
Color solution obtains the carbon dots material of N doping by vacuum distillation, is named as NCD.Gained NCD material is dissolved in 30mL, is added
Enter PdCl2(0.95mmol), then magnetic agitation back flow reaction 18h under the conditions of 100 DEG C.When reaction solution naturally cools to room temperature
After, gained mixture is evaporated under reduced pressure, yellow-brown solid is obtained, is named as Pd-NCD.
Embodiment 3
It is dissolved in 35mL water by citric acid (7.65mmol) and to Carboxybenzeneboronic acid (3.825mmol), then ultrasound is mixed
It closes 30 minutes.Gained mixture is transferred in autoclave of the 50mL containing polytetrafluoroethyllining lining, is added under the conditions of 200 DEG C
Thermal response 5 hours.After temperature naturally cools to room temperature, gained mixture is centrifuged off insoluble matter, is obtained orange-yellow molten
Liquid obtains boron doped carbon dots material by vacuum distillation, is named as BCD.Gained BCD material is dissolved in 30mL water, is added
PdCl2(0.95mmol), then magnetic agitation back flow reaction 18h under the conditions of 100 DEG C.When reaction solution naturally cool to room temperature with
Afterwards, gained mixture is evaporated under reduced pressure, obtains yellow-brown solid, be named as Pd-BCD.
Embodiment 4
Citric acid (7.65mmol) is dissolved in 35mL water, then ultrasonic mixing 30 minutes.Gained mixture is shifted
Into autoclave of the 50mL containing polytetrafluoroethyllining lining, heating reaction 5 hours under the conditions of 200 DEG C.When temperature is naturally cold
But to after room temperature, gained mixture is centrifuged off insoluble matter, obtains orange solution, carbon dots material is obtained by vacuum distillation
Material, is named as CD.Gained CD material is dissolved in 30mL water, PdCl is added2(0.95mmol), then magnetic under the conditions of 100 DEG C
Power is stirred at reflux reaction 18h.After reaction solution naturally cools to room temperature, gained mixture is evaporated under reduced pressure, brown color is obtained
Solid is named as Pd-CD.
Embodiment 5
Catalyst activity evaluation carries out in the catalyst reaction device with magnetic agitation.In glass closed reactor according to
Secondary addition benzaldehyde (0.3mmol), acetonitrile (1mL), 1 micro-nano cell catalyst Pd-BNCD of embodiment (1.5 μm of ol), HBF4
(0.08mmol) and Na2SO4(0.02mmol).Using hydrogen balloon as hydrogen source, 25 DEG C isothermal reaction 2 hours, reaction mixture
After centrifugation, extraction, drying and excessively miniature silicagel column, the conversion ratio that benzaldehyde is analyzed by GC-MS is > 99% and product first
The selectivity of benzene is 94%.
Embodiment 6
Catalyst activity evaluation carries out in the catalyst reaction device with magnetic agitation.In glass closed reactor according to
Secondary addition benzaldehyde (0.3mmol), acetonitrile (1mL), reference catalyst PdCl2(1.5 μm of ol), HBF4(0.08mmol) and
Na2SO4(0.02mmol).Using hydrogen balloon as hydrogen source, 25 DEG C isothermal reaction 2 hours, reaction mixture through centrifugation, extraction,
After dry and excessively miniature silicagel column, it is 11.2% by the conversion ratio that GC-MS analyzes benzaldehyde, illustrates micro-nano cell catalyst pair
Catalysis reaction plays the role of very important.
Embodiment 7
Catalyst activity evaluation carries out in the catalyst reaction device with magnetic agitation.In glass closed reactor according to
Secondary addition benzaldehyde (0.3mmol), acetonitrile (1mL), 2 catalyst Pd-NCD of embodiment (1.5 μm of ol), HBF4(0.08mmol) and
Na2SO4(0.02mmol).Using hydrogen balloon as hydrogen source, 25 DEG C isothermal reaction 2 hours, reaction mixture through centrifugation, extraction,
It is trace by the conversion ratio that GC-MS analyzes benzaldehyde after dry and excessively miniature silicagel column, illustrates that micro-nano electrode reacts catalysis
Play the role of very important.
Embodiment 8
Catalyst activity evaluation carries out in the catalyst reaction device with magnetic agitation.In glass closed reactor according to
Secondary addition benzaldehyde (0.3mmol), acetonitrile (1mL), 3 catalyst Pd-BCD of embodiment (1.5 μm of ol), HBF4(0.08mmol) and
Na2SO4(0.02mmol).Using hydrogen balloon as hydrogen source, 25 DEG C isothermal reaction 2 hours, reaction mixture through centrifugation, extraction,
It is 7.2% by the conversion ratio that GC-MS analyzes benzaldehyde after dry and excessively miniature silicagel column, illustrates that micro-nano electrode is anti-to being catalyzed
It should play the role of very important.
Embodiment 9
Catalyst activity evaluation carries out in the catalyst reaction device with magnetic agitation.In glass closed reactor according to
Secondary addition benzaldehyde (0.3mmol), acetonitrile (1mL), 4 catalyst Pd-CD of embodiment (1.5 μm of ol), HBF4(0.08mmol) and
Na2SO4(0.02mmol).Using hydrogen balloon as hydrogen source, 25 DEG C isothermal reaction 2 hours, reaction mixture through centrifugation, extraction,
It is 12.9% by the conversion ratio that GC-MS analyzes benzaldehyde after dry and excessively miniature silicagel column, illustrates that micro-nano electrode is anti-to being catalyzed
It should play the role of very important.
Embodiment 10
Catalyst activity evaluation carries out in the catalyst reaction device with magnetic agitation.In glass closed reactor according to
Secondary addition benzaldehyde (0.3mmol), acetonitrile (1mL), 1 micro-nano cell catalyst Pd-BNCD of embodiment (1.5 μm of ol), Na2CO3
(0.01mmol) and Na2SO4(0.02mmol).Using hydrogen balloon as hydrogen source, 25 DEG C isothermal reaction 2 hours, reaction mixture
After centrifugation, extraction, drying and excessively miniature silicagel column, the conversion ratio that benzaldehyde is analyzed by GC-MS is trace, illustrates electrolyte
Play the role of to catalysis reaction very important.
Embodiment 11
Catalyst activity evaluation carries out in the catalyst reaction device with magnetic agitation.In glass closed reactor according to
Secondary addition benzaldehyde (0.3mmol), acetonitrile (1mL), 1 micro-nano cell catalyst Pd-BNCD of embodiment (1.5 μm of ol) and Na2SO4
(0.02mmol).Using hydrogen balloon as hydrogen source, 25 DEG C isothermal reaction 2 hours, reaction mixture is through centrifugation, extraction, drying
It is trace by the conversion ratio that GC-MS analyzes benzaldehyde after crossing miniature silicagel column, illustrates that electrolyte plays catalysis reaction
Very important effect.
Embodiment 12
Methylcellulose (1g), urea (0.5g), 4- (1- naphthalene)-phenyl boric acid (0.1g) are dissolved in acetone (40mL), room
Temperature stirring the straight acetone of 12h volatilize completely, solid powder is put in crucible, in a nitrogen atmosphere 800 DEG C of calcining 1h, obtain boron with
Nitrogen co-doped grapheme material.By boron and nitrogen co-doped grapheme material (500mg) and PdCl2(25mg) is in 10mL water
It is uniformly mixed, then back flow reaction 18h under the conditions of 100 DEG C.After reaction solution is cooled to room temperature, by gained mixture
It is evaporated under reduced pressure under the conditions of 0.001MPa and 60 DEG C, obtains solid material, as using graphene as the micro-nano battery of conductive material
Catalyst is named as Pd-BNGO.
Embodiment 13
Catalyst activity evaluation carries out in the catalyst reaction device with magnetic agitation.In glass closed reactor according to
Secondary addition benzaldehyde (0.3mmol), acetonitrile (1mL), 12 micro-nano cell catalyst Pd-BNGO of embodiment (1.5 μm of ol), HBF4
(0.08mmol) and Na2SO4(0.02mmol).Using hydrogen balloon as hydrogen source, 25 DEG C isothermal reaction 2 hours, reaction mixture
After centrifugation, extraction, drying and excessively miniature silicagel column, benzaldehyde is analyzed by GC-MS and is almost converted.
Embodiment 14
Oxalic acid indium (2g) is calcined to 2h at 170 DEG C to get conductive inorganic oxide material In is arrived in air2O3.According to matter
Amount is than 5% by In2O3(1g)、Co(OAc)2(50mg) is added in 40mL deionized water, and 72h is stirred at room temperature, and centrifuge washing is dry
Afterwards, solid is placed in crucible, 600 DEG C of calcining 1h, obtain Co in air atmosphere3O4/In2O3.Take Co3O4/In2O3(20mg) and
Calcium hypophosphite (21.6mg) is individually placed to porcelain crucible both ends, and calcium hypophosphite is placed in tube furnace air inlet, and in a nitrogen atmosphere 300
DEG C calcining 2h to get CoP/In2O3.Configure PdCl2(0.5mg/mL) aqueous solution, by CoP/In2O35mL PdCl is added in (20mg)2
Solution stirs 6h, and centrifuge washing is dry to get to In2O3For the micro-nano cell catalyst of conductive material, it is named as CoP/
In2O3/PdP。
Embodiment 15
Catalyst activity evaluation carries out in the catalyst reaction device with magnetic agitation.In glass closed reactor according to
Secondary addition benzaldehyde (0.3mmol), acetonitrile (1mL), 14 micro-nano cell catalyst CoP/In of embodiment2O3/ PdP (1.5 μm of ol),
HBF4(0.08mmol) and Na2SO4(0.02mmol).Using hydrogen balloon as hydrogen source, 25 DEG C isothermal reaction 2 hours, reaction is mixed
Object is closed after centrifugation, extraction, drying and excessively miniature silicagel column, benzaldehyde is analyzed by GC-MS and is almost converted.
The micro-nano cell catalyst of above embodiments preparation of the present invention is a kind of novel catalyst, has assembled nanometer material
The advantages of material, self-supported catalyst, monatomic catalyst, homogeneous catalyst, elctro-catalyst, can efficiently overcome traditional catalyst living
Property low, the concerted catalysis low efficiency and big disadvantage of steric hindrance, and then reach the high efficiency of catalysis reaction with it is highly selective, meet
The requirement of atom economy and Green Chemistry, is of great significance to energy-saving and emission-reduction.
Compared to traditional catalyst, micro-nano cell catalyst has a characteristic that micro-nano cathode and anode catalyst are distinguished
For reduction half-reaction and oxidation half-reaction design synthesis, solve in catalytic reaction process between reactant molecule it is existing
Steric hindrance problem improves concerted catalysis efficiency, and active site utilization rate is high, catalysis reaction activity is low, catalysis is lived
The high feature of property.Compared to traditional catalyst, micro-nano cell catalyst has a characteristic that when catalytic chemistry reacts and is being catalyzed
The high activity of different half-reaction catalytic active centers and the different oxidationreductions electricity of micro-nano electrode are made full use of in reaction process
Gesture, by synergistic effect greatly improve catalytic efficiency, reach catalysis reaction high efficiency with it is highly selective.Not with traditional catalyst
Together, micro-nano cell catalyst catalytic chemistry reaction carries out on two different micro-nano electrodes respectively, is conducive to reactant molecule
Activation, and then catalytic efficiency greatly improved.
Claims (10)
1. a kind of micro-nano cell catalyst, which is characterized in that it is mainly by micro-nano electrically conductive carrier material, micro-nano cathode and micro-nano sun
Pole composition；The micro-nano electrically conductive carrier material is the material that can transmit electronics, poly- selected from micro-nano carbon material, micro-nano organic conductive
Close object material, micro-nano conductive inorganic oxide material.
2. micro-nano cell catalyst according to claim 1, which is characterized in that the micro-nano carbon material include: carbon quantum dot,
Graphene, porous carbon materials；Micro-nano organic conductive polymer material includes: polythiophene, polypyrrole, polyaniline；Micro-nano conduction nothing
Machine oxide material includes: zinc oxide, tin oxide, indium oxide, tin indium oxide.
3. the preparation method of micro-nano cell catalyst described in a kind of claim 1, which is characterized in that this method specifically: first
By carbon source, nitrogen source, boron source and water according to molar ratio 2:1:1:500 ultrasonic mixing 30 minutes.Gained mixture is transferred to containing poly-
In the reaction kettle of tetrafluoroethene liner, heating reaction 5 hours under the conditions of 200 DEG C.It, will after temperature naturally cools to room temperature
Gained mixture is centrifuged off insoluble matter, obtains orange solution, and vacuum distillation obtains boron under the conditions of 0.001MPa and 60 DEG C
With nitrogen co-doped carbon dots material.Then by carbon dots material and PdCl2It is uniformly mixed with water according to mass ratio 20:1:400,
Back flow reaction about 18h under the conditions of 100 DEG C.After reaction solution is cooled to room temperature, by gained mixture at 0.001MPa and 60 DEG C
Under the conditions of be evaporated under reduced pressure, solid material is obtained, as using micro-nano carbon material as the micro-nano cell catalyst of conductive material.
4. the preparation method of micro-nano cell catalyst according to claim 3, which is characterized in that the carbon source is preferably lemon
Acid, the nitrogen source are preferably Na2EDTA, and the boron source is preferably to Carboxybenzeneboronic acid.
5. the preparation method of micro-nano cell catalyst described in a kind of claim 1, which is characterized in that this method specifically: first
Carbon source, nitrogen source, boron source and acetone are uniformly mixed according to mass ratio 10:1:5:300, stir about 12h is dry up to stirring, by solid powder
End is put in crucible, and 800 DEG C of calcining 1h under nitrogen environment, obtain boron and nitrogen co-doped grapheme material in tube furnace.So
Afterwards by graphene and PdCl2Back flow reaction 18h under the conditions of 100 DEG C is uniformly mixed according to mass ratio 20:1:400 with water.When anti-
It answers liquid to be cooled to after room temperature, gained mixture is evaporated under reduced pressure under the conditions of 0.001MPa and 60 DEG C, obtains solid material, i.e.,
For using micro-nano carbon material as the micro-nano cell catalyst of conductive material.
6. the preparation method of micro-nano cell catalyst according to claim 5, which is characterized in that the carbon source is preferably methyl
Cellulose), the nitrogen source is preferably urea, and the boron source is preferably 4- (1- naphthalene)-phenyl boric acid.
7. the preparation method of micro-nano cell catalyst described in a kind of claim 1, which is characterized in that this method specifically: will be micro-
Receive organic conductive polymer, aluminium salt and water according to mass ratio 20:1:100 be uniformly mixed, 100 DEG C of reflux 12h, centrifuge washing dry
Afterwards, aluminium-organic conductive polymer composite material is obtained；By aluminium-organic conductive polymer composite material and PdCl2With water according to quality
It is uniformly mixed than 20:1:100,100 DEG C of reflux 12h, centrifuge washing is dry to get using micro-nano organic conductive polymer as conduction material
The micro-nano cell catalyst of material.
8. the preparation method of micro-nano cell catalyst according to claim 7, which is characterized in that the micro-nano organic conductive is poly-
Closing object is preferably polythiophene, polypyrrole or polyaniline.
9. the preparation method of micro-nano cell catalyst described in a kind of claim 1, which is characterized in that this method specifically: will be careless
Sour zinc, tin oxalate or oxalic acid indium calcine 2h at 170 DEG C -190 DEG C to get corresponding conductive inorganic oxide material is arrived in air
Material.By it by method of chemical immersion carrying transition metal ion, composite material, transition metal ions and conductive inorganic oxide are obtained
The mass ratio of material is 5:100, and transition metal is selected from manganese, cobalt, iron, copper, aluminium, chromium；It is pressed with sodium hypophosphite and above-mentioned composite material
Quality proportioning 5:100 is uniformly mixed, and 600 DEG C of calcining 1h, it is compound to obtain phosphating metal-metal oxide under tube furnace nitrogen atmosphere
Material.Configuration concentration is the PdCl of 1mg/mL2Aqueous solution or RuCl3Aqueous solution, according to tenor molar ratio 1:1 by PdCl2It is water-soluble
Liquid or RuCl3Aqueous solution is mixed with phosphating metal-metal oxide composite, stirs 6h, centrifuge washing it is dry to get to
Micro-nano conductive inorganic oxide is the micro-nano cell catalyst of conductive material.
10. the purposes that micro-nano cell catalyst described in a kind of claim 1 is used to be catalyzed reduction benzaldehyde, which is characterized in that should
Purposes specifically: 3800:60:0.3:16:4 sequentially adds acetonitrile, benzaldehyde, micro-nano in molar ratio in glass closed reactor
Cell catalyst, tetrafluoro boric acid and anhydrous sodium sulfate, using hydrogen balloon as hydrogen source, 25 DEG C constant temperature synthesis under normal pressure 2 hours, instead
It answers mixture after centrifugation, extraction, drying and excessively miniature silicagel column, the conversion ratio and benzene first of benzaldehyde is calculated by GC-MS
The yield of pure and mild toluene.
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