CN105293484B - The preparation method of nitrogen-doped graphene and its supported copper nanocrystalline catalyst - Google Patents
The preparation method of nitrogen-doped graphene and its supported copper nanocrystalline catalyst Download PDFInfo
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- CN105293484B CN105293484B CN201510907159.6A CN201510907159A CN105293484B CN 105293484 B CN105293484 B CN 105293484B CN 201510907159 A CN201510907159 A CN 201510907159A CN 105293484 B CN105293484 B CN 105293484B
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Abstract
The present invention relates to nanometer-material-modified and catalytic field, the preparation method of specifically a kind of nitrogen-doped graphene and its supported copper nanocrystalline catalyst, the present invention has obvious advanced compared with background technology, using nitrogen-doped graphene as carrier, copper nanocrystallite is active component, and catalyst is made using Hummers methods, ultrasonication, microwave calcining and technique for atomic layer deposition.This preparation method is simple to operate, and technique is advanced, and cost of material is low, and data are accurately full and accurate, prepares speed soon, is a kind of very good method of Synthesis of dimethyl carbonate catalyst.The existing graphene good heat conductivity of nitrogen-doped graphene supported copper nanocrystalline catalyst of gained, the advantages of raw material is cheap and easy to get, the advantages of having the high activity that nanocrystal is catalyzed, high selectivity and high stability again, is a kind of good nanocatalyst.
Description
Technical field
The present invention relates to nanometer-material-modified and catalytic field, specifically a kind of nitrogen-doped graphene and its supported copper nanometer
The preparation method of brilliant catalyst.
Background technology
Graphene is the individual layer two dimensional crystal that carbon atom is arranged to make up with sp2 hydridization in honeycomb lattice, with excellent electricity
, optics, calorifics and mechanical performance, are often used as the carrier of catalyst.Graphene-supported copper catalyst is used for carbonate synthesis two
Methyl esters, it has good heat conductivity, the advantages of raw material is cheap and easy to get.Patent CN104399498A is with graphene-supported copper catalysis
Agent can not keep in its building-up process the integrality of graphite-structure in methanol gas-phase oxidation carbonylation synthesis dimethyl carbonate,
Cause its own existing defects position.Therefore can be made up by the nitrogen-atoms that adulterates this defect and change carbon atom spin it is close
Degree and distribution of charges, so that graphenic surface produces " avtive spot ", these avtive spots can directly participate in catalytic reaction,
Improve catalytic activity.To improve the activity of catalyst, patent CN103372428A is but this using noble metal platinum as active component
Method adds production cost, is difficult to be advanced in industrial production.
Nitrogen-doped graphene has the chemism higher than graphene, there is excellent heat conductivility, is a kind of good
Catalyst carrier, the advantages of nanocrystal catalysis has high activity, high selectivity and high stability, therefore nitrogen-doped graphene is negative
Copper-loaded nanocrystalline catalyst has very big potentiality in catalytic field.
The content of the invention
The present invention is intended to provide a kind of good catalyst carrier and urging with high activity, high selectivity and high stability
Agent, the preparation method of specifically a kind of nitrogen-doped graphene and its supported copper nanocrystalline catalyst.
The present invention is achieved by the following technical solutions：A kind of preparation method of nitrogen-doped graphene, the step of this method
Suddenly it is：
1. redox graphene
Dried graphene oxide is placed in micro-wave oven, will be evacuated in micro-wave oven after -0.9MPa, lead to nitrogen to -
0.3MPa, it is above-mentioned to vacuumize and lead to after nitrogen steps are repeated twice, it is evacuated to again after -0.9MPa and leads to nitrogen to -0.5MPa；
Micro-wave oven cooling water circulating device is opened, microwave control switch is opened, regulation microwave power makes in-furnace temperature by room temperature
To 350 DEG C, and constant temperature 60s；
2. nitrogen-doped graphene
Ammonia is passed through into micro-wave oven, microwave switch is then shut off, stops heating, will be evacuated in micro-wave oven-
0.9MPa, cavity temperature is water-cooled to after 50 DEG C with cooling, is closed in cooling water, micro-wave oven and is passed through nitrogen to standard atmospheric pressure
Afterwards, oven door opening, obtains nitrogen-doped graphene.
The problem of nitrogen-doped graphene that the present invention is prepared can make up the defective bit of prior art presence, and change
Become the spin density and distribution of charges of carbon atom, so that graphenic surface produces " avtive spot ", these avtive spots can be with
Catalytic reaction is directly participated in, catalytic activity is improved.The big I of nitrogen content is adjusted according to the actual requirements in above-mentioned nitrogen-doped graphene
The intake of ammonia is controlled, the control manipulation is what those skilled in the art can realize.Used during practical operation of the present invention
Micro-wave oven is the production of Nanjing Jie Quan microwave equipments Co., Ltd, its model NJZ4-3.
Further, the invention provides the preparation method of nitrogen-doped graphene supported copper nanocrystalline catalyst, the catalysis
Agent is using the nitrogen-doped graphene as carrier, the step of the preparation method of the catalyst：
I, nitrogen-doped graphenes are scattered in ethanol, and ultrasonic agitation is well mixed；
II, drops in said mixture on quartz plate, after being air-dried under air ambient, is put into the heavy of ald reactor
Product intracavitary, and it is closed；
III, extracts deposition chamber air, intracavitary pressure is reached 150Pa；
IV, using gasify (gas shape) acetylacetone copper and hydrogen as precursor, it is 150 DEG C to set precursor temperature,
Depositing temperature is 250 DEG C, and sedimentation time is 10s, and scavenging period is 30s, and it is 100 times to set cycle-index；
After the completion of all parameter settings of V, reactor operation starts deposition, after the completion of operation, natural cooling in deposit cavity
To room temperature, take out and obtain nitrogen-doped graphene supported copper nanocrystalline catalyst.
Color and luster, Chemical Physics performance to the nitrogen-doped graphene supported copper nanocrystalline catalyst of prepared acquisition are examined
Survey, analyze, characterize；Crystal phase analysis is carried out with X-ray powder diffraction instrument；Conclusion：Nitrogen-doped graphene load copper nanocrystallite catalysis
Agent catalyst is black powder, and product purity is up to 99.5%, and reactivity is high, and catalytic performance is good.In addition, the original that the present invention is used
Sublayer deposition reactor is existing apparatus, purchased from the applicant of Application No. 201420771430.9, its specific structure and is used
Method is referring to the patent.
The present invention has obvious advance compared with background technology, and using nitrogen-doped graphene as carrier, copper nanocrystallite is
Active component, catalyst is made using Hummers methods, ultrasonication, microwave calcining and technique for atomic layer deposition.This preparation side
Method is simple to operate, and technique is advanced, and cost of material is low, and data are accurately full and accurate, prepares speed soon, is Synthesis of dimethyl carbonate catalyst
A kind of very good method.The existing graphene heat conductivility of nitrogen-doped graphene supported copper nanocrystalline catalyst of gained
Well, the advantages of the advantages of raw material is cheap and easy to get, the high activity being catalyzed again with nanocrystal, high selectivity and high stability, it is
A kind of good nanocatalyst.
Brief description of the drawings
Fig. 1 is nitrogen-doped graphene supported copper nanocrystalline catalyst X ray diffracting spectrum, in figure：Ordinate is that diffraction is strong
Degree, abscissa is the θ of the angle of diffraction 2,43.157 ° of base peak, 50.346 °, 73.879 ° be copper simple substance characteristic diffraction peak, can be with by figure
Find out that copper nanocrystallite crystalline form is regular, be evenly distributed.
Fig. 2 is to understand in the graph of a relation of space-time yield and cycle-index, table：Nitrogen-doped graphene load copper nanocrystallite catalysis
Agent (Cu/NG) space-time yield change after circulating 5 times is smaller, and catalyst has good stability, not easy in inactivation.
Embodiment
The chemical substance material used during specific implementation is：Graphite, sodium nitrate, potassium permanganate, acetylacetone copper, hydrochloric acid,
The concentrated sulfuric acid, hydrogen peroxide, deionized water, ethanol, nitrogen, ammonia, hydrogen, it prepares consumption with gram, milliliter, centimetre3It is single for metering
Position.
Preparation method is as follows：
(1) graphene oxide, is prepared
1. aqueous hydrochloric acid solution, is configured
Hydrochloric acid 10mL ± 0.001mL, deionized water 190mL ± 0.001mL are measured, is added in beaker, stirring 3min makes to mix
Close uniform, obtain aqueous hydrochloric acid solution；
2. graphite oxide, is prepared
40mL ± 0.001mL concentrated sulfuric acids are measured to add into 250mL beakers, it is stand-by；
2g ± 0.001g graphite powders are weighed, it is stand-by；
1.2g ± 0.001g sodium nitrate is weighed, it is stand-by；
7g ± 0.001g potassium permanganate is weighed, it is stand-by；
The beaker that will be equipped with the concentrated sulfuric acid is placed in ice-water bath and stirred, while it is solid to add load weighted graphite powder and sodium nitrate
Load weighted potassium permanganate solid is slowly added to after body, stirring 5min, control temperature is warming up to after being no more than 20 DEG C, stirring 5min
35 DEG C of constant temperature stir 3h, point 5 addition 250mL deionized waters, are eventually adding mL ± 0.001mL30% hydrogen peroxide, continue to stir
Filtered while hot after 5min；
3., wash, dry graphite oxide
Filter cake is rinsed with aqueous hydrochloric acid solution twice, and after deionized water rinsing three times, filter cake is put into 60 DEG C of vacuum drying
Drying 20h in case；
4. graphene oxide suspension, is prepared
0.2g ± 0.001g graphite oxides are weighed, are put into beaker；
200mL ± 0.001mL deionized waters are measured, addition is placed with the beaker of graphite oxide, is sufficiently stirred for, then ultrasonic wave
Processing 1h obtains graphene oxide suspension；
5., suction filtration, drying
Ultrasonically treated rear oxidation graphene suspension is placed in the Buchner funnel of bottle,suction, with three layers of middling speed qualitative filter paper
Remaining product filter cake on suction filtration, filter paper is carried out, filtrate liquid is evacuated in filter flask；
Filter cake is put into 60 DEG C of vacuum drying chamber and dries 12h；
(2) nitrogen-doped graphene, is prepared
The preparation of nitrogen-doped graphene is completed under conditions of microwave calcining, nitrogen protection, circulating water；①、
Redox graphene
Dried graphene oxide is put into corundum crucible, then corundum crucible is put into insulating brick, is placed in micro-
The intermediate region of ripple stove, adjusting position, until infrared temperature probe measures the maximum temperature point of aggregate sample, is mixed up after bushing position
Close resonance door；
Vavuum pump is opened, will be evacuated in micro-wave oven after -0.9MPa, leads to nitrogen to -0.3MPa, it is above-mentioned to vacuumize and lead to
After nitrogen steps are repeated twice, it is evacuated to again after -0.9MPa and leads to nitrogen to -0.5MPa；
Open micro-wave oven cooling water circulating device, then open microwave control switch, regulation microwave power make in-furnace temperature by
25 DEG C are quickly ramped up to 350 DEG C, constant temperature 60s；
2., nitrogen-doped graphene
Ammonia bottle is opened, with 200cm3/ min speed is passed through ammonia, is passed through after 2s, closes ammonia bottle；
Microwave switch is closed, stops heating, is evacuated to ﹣ 0.9MPa, cavity temperature slowly cools to 50 with recirculated water
After DEG C, recirculated water is closed；
Nitrogen is passed through, when microwave furnace pressure reaches 101325Pa, fire door is automatically opened up, takes out corundum crucible, corundum
Powder in crucible is nitrogen-doped graphene；
3., weigh, count
Nitrogen-doped graphene is put on pan paper, weighed using electronic analytical balance, and record data；
(3) nitrogen-doped graphene supported copper nanocrystalline catalyst, is prepared
Nitrogen-doped graphene supported copper nanocrystalline catalyst is carried out in the ald reactor of closing, with acetyl
Acetone copper and hydrogen are used as presoma；
1., 0.2g ± 0.001g nitrogen-doped graphenes are dispersed in a little ethanol, ultrasonic agitation；
2., said mixture is dropped on quartz plate, after air-drying in atmosphere, is put into deposit cavity, is closed closed；
3. vavuum pump, is opened, deposition chamber air is extracted, intracavitary pressure is reached 150Pa；
4. it is 150 DEG C, to set forerunner's temperature, and depositing temperature is 250 DEG C；
5., sedimentation time is set to be 10s, scavenging period is 30s；
6. it is 100 times, to set cycle-index；
7., by all parameter settings it is good after, start deposition；
8., after end to be deposited, room temperature is cooled to, product is taken out；
9., preserve, record
The nitrogen-doped graphene supported copper nanocrystalline catalyst prepared is fitted into sample sack, label is posted, is placed in
It is closed to preserve in drier；
(4), test, analysis and characterization
The pattern, color and luster, Chemical Physics performance of the nitrogen-doped graphene supported copper nanocrystalline catalyst of preparation are examined
Survey, analyze, characterize；
Crystal phase analysis is carried out with X-ray powder diffraction instrument；
Conclusion：Nitrogen-doped graphene supported copper nanocrystalline catalyst catalyst be black powder, product purity up to 99.5%,
Reactivity is high, and catalytic performance is good；
(5), estimation of stability
Using dimethyl carbonate in liquid phase reaction unit estimation of stability is carried out to catalyst is made.
Claims (1)
1. a kind of preparation method of nitrogen-doped graphene supported copper nanocrystalline catalyst, it is characterised in that
The step of preparation method of the nitrogen-doped graphene is：
1. redox graphene
Dried graphene oxide is placed in micro-wave oven, will be evacuated in micro-wave oven after -0.9MPa, lead to nitrogen to -
0.3MPa, it is above-mentioned to vacuumize and lead to after nitrogen steps are repeated twice, it is evacuated to again after -0.9MPa and leads to nitrogen to -0.5MPa；
Micro-wave oven cooling water circulating device is opened, microwave control switch is opened, regulation microwave power makes in-furnace temperature by room temperature
To 350 DEG C, and constant temperature 60s；
2. nitrogen-doped graphene
Ammonia is passed through into micro-wave oven, microwave switch is then shut off, stops heating, -0.9MPa, stove will be evacuated in micro-wave oven
Chamber temperature is water-cooled to after 50 DEG C with cooling, is closed and is passed through in cooling water, micro-wave oven after nitrogen to standard atmospheric pressure, fire door is beaten
Open, obtain nitrogen-doped graphene；
The catalyst is using above-mentioned nitrogen-doped graphene as carrier, the step of the preparation method of the catalyst：
I, nitrogen-doped graphenes are scattered in ethanol, and ultrasonic agitation is well mixed；
II, drops in said mixture on quartz plate, after being air-dried under air ambient, is put into the deposit cavity of ald reactor
It is interior and closed；
III, extracts deposition chamber air, intracavitary pressure is reached 150Pa；
Acetylacetone coppers and hydrogen of IV, to gasify set precursor temperature for 150 DEG C, depositing temperature is 250 as precursor
DEG C, sedimentation time is 10s, and scavenging period is 30s, and it is 100 times to set cycle-index；
After the completion of all parameter settings of V, reactor operation starts deposition, and after the completion of operation, room is naturally cooled in deposit cavity
Temperature, takes out and obtains nitrogen-doped graphene supported copper nanocrystalline catalyst.
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| CN106987236A (en) * | 2017-05-09 | 2017-07-28 | 德阳中碳新材料科技有限公司 | A kind of preparation method of graphene heat-conductive composite material |
| CN107262095B (en) * | 2017-07-20 | 2020-06-23 | 太原理工大学 | Preparation method of copper-doped graphene catalyst |
| CN107628605B (en) * | 2017-10-27 | 2019-06-14 | 武汉网信安全技术股份有限公司 | A kind of method that three-step approach preparation is not necessarily to the graphene shifted |
| CN110732336A (en) * | 2019-09-30 | 2020-01-31 | 江苏大学 | Method for preparing nitrogen-doped graphene-loaded nano copper composite material by using microwaves |
| CN111974435B (en) * | 2020-08-26 | 2022-04-15 | 太原理工大学 | Preparation method and application of high-stability Cu/N-doped carbon nanosheet catalyst |
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| CN102180462B (en) * | 2011-02-17 | 2013-01-02 | 无锡第六元素高科技发展有限公司 | Method for preparing modified graphene material in controlled atmosphere environment by microwave irradiation |
| CN102302956A (en) * | 2011-07-05 | 2012-01-04 | 南京大学 | Method for preparing nitrogen-doped carbon material rapidly by using microwave |
| KR20140093944A (en) * | 2011-10-07 | 2014-07-29 | 퍼듀 리서치 파운데이션 | Rapid synthesis of graphene and formation of graphene structures |
| CN102896834A (en) * | 2012-10-11 | 2013-01-30 | 湖南大学 | Graphene-copper nanoparticle composite, and preparation and application thereof |
| CN104649254A (en) * | 2014-12-11 | 2015-05-27 | 谢德智 | Method for rapidly preparing nitrogen-doped graphene by utilizing microwave-assisted solid phase method |
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