CN107262095A - The preparation method of Copper-cladding Aluminum Bar graphen catalyst - Google Patents
The preparation method of Copper-cladding Aluminum Bar graphen catalyst Download PDFInfo
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- CN107262095A CN107262095A CN201710593704.8A CN201710593704A CN107262095A CN 107262095 A CN107262095 A CN 107262095A CN 201710593704 A CN201710593704 A CN 201710593704A CN 107262095 A CN107262095 A CN 107262095A
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- copper
- graphene
- catalyst
- aluminum bar
- cladding aluminum
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
Abstract
The present invention relates to nanometer-material-modified and catalytic field, specifically a kind of preparation method of Copper-cladding Aluminum Bar graphen catalyst.It is of the invention direct using metallic copper doped graphene as catalyst, it is calcined using liquid phase method, ultrasonically treated and tube furnace and catalyst is made.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 the monatomic doped graphene catalyst of copper of gained, the advantages of raw material is cheap and easy to get, the advantages of having high activity, high selectivity and high stability again, is a kind of good catalyst.
Description
Technical field
The present invention relates to nanometer-material-modified and catalytic field, specifically a kind of preparation side of Copper-cladding Aluminum Bar graphen catalyst
Method.
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 catalyst mixed with copper is used for carbonate synthesis two
Methyl esters, it has good heat conductivity, the advantages of raw material is cheap and easy to get.Graphene has the specific surface area in both up and down face, as
Carrier is supported, is available for metal nanoparticle repeatedly to inlay the structural strain with deintercalation, good cycle performance can be shown.Together
When metal nanoparticle also have larger specific surface area and strong catalytic performance, so this doping method may be such that what is prepared
Nano composite material specific surface area is significantly increased, and is more beneficial for electron transfer or the expansion in hydrogen storage space and the enhancing of activity.Cause
This can change the spin density and distribution of charges of carbon atom by copper doped, so that graphenic surface produces " active sites
Point ", these avtive spots can directly participate in catalytic reaction, improve catalytic activity.To improve the activity of catalyst, patent
CN103372428A is difficult to be advanced to industrial life using noble metal platinum as active component, but such a process increases production cost
In production.
Copper-cladding Aluminum Bar 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 Copper-cladding Aluminum Bar graphene are urged
Agent has very big potentiality in catalytic field.
The content of the invention
The present invention it is too high in order to solve prior art production cost, the problem of being difficult to be advanced in industrial production there is provided
A kind of preparation method of Copper-cladding Aluminum Bar graphen catalyst.
The present invention is achieved by the following technical solutions：The preparation method of Copper-cladding Aluminum Bar graphen catalyst, including it is as follows
Step：
（1）The preparation of copper complex
It is dissolved completely in copper nitrate is molten in water, heats and dropwise addition ammoniacal liquor, to dissolving is precipitated, adds NaOH solution under agitation,
Filtering and washing to surface without NO-, so as to obtain Kocide SD solid and drying；Glycine is dissolved in the water, 65 DEG C are heated to
Constant temperature stirring adds brand-new Kocide SD, is stirred continuously lower heating water bath 15min, and suction filtration is filtered while hot, adds the straight fire heating of water,
Start to separate out flakey crystal at 80 DEG C, accelerate as temperature rises crystal speed of separating out, glycine is made and closes copper；
（2）Copper-cladding Aluminum Bar graphene
1. redox graphene
Graphene oxide is scattered in the aqueous solution and carried out ultrasonically treated 2 hours, hydrazine hydrate is then added thereto, in 90 DEG C of water
Agitating and heating 2 hours, filtered off with suction, are washed with deionized under the conditions of bath, finally dry, and obtain graphene powder；
2. Copper-cladding Aluminum Bar graphene
Obtained glycine is closed into copper and graphene powder mixes and is dissolved in the aqueous solution, is carried out ultrasonically treated 2 hours, then filtering is taken out
Filter and dry, dried mixture is placed under the conditions of 230 DEG C of nitrogen atmosphere and is calcined 2 hours, Copper-cladding Aluminum Bar graphene is obtained and urges
Agent.
The Copper-cladding Aluminum Bar graphene that the present invention is prepared shows ferromagnetism feature, and can change the spin of carbon atom
Density and distribution of charges, so that graphenic surface produces " avtive spot ", it is anti-that these avtive spots can directly participate in catalysis
Should, improve catalytic activity.
Color and luster, Chemical Physics performance to the Copper-cladding Aluminum Bar graphen catalyst of prepared acquisition are detected, analyzed, table
Levy；Crystal phase analysis is carried out with X-ray powder diffraction instrument；Conclusion：Copper-cladding Aluminum Bar graphen catalyst is black powder, product purity
Up to 99.5%, reactivity is high, and catalytic performance is good.
The present invention has obvious advance compared with background technology, with metallic copper doped graphene, using liquid phase method, surpasses
Catalyst is made in sonication and tube furnace roasting.This preparation method is simple to operate, and technique is advanced, and cost of material is low, and data are accurate
It is full and accurate, prepare speed soon, be a kind of very good method of Synthesis of dimethyl carbonate catalyst.The Copper-cladding Aluminum Bar graphene of gained
The existing graphene good heat conductivity of catalyst, the advantages of raw material is cheap and easy to get has high activity, high selectivity and high stability again
The advantages of, it is a kind of good catalyst.
Brief description of the drawings
Fig. 1 is the skeleton pattern figure of Copper-cladding Aluminum Bar graphen catalyst.As seen from the figure：Copper atom（Black region）Inlay
In graphene skeleton（Gray area）In, and have projection.
Fig. 2 is the transmission electron microscope picture of Copper-cladding Aluminum Bar graphen catalyst.
Fig. 3 is the XRD of Copper-cladding Aluminum Bar graphen catalyst.
Fig. 4 is dimethyl carbonate in liquid phase reaction unit figure.In figure：1- pressure gauges, 2- thermocouples, 3- air outlet valves, 4- reactions
Kettle, 5- thermal insulating seats, 6- intake valves, 7-CO gas cylinders, 8- oxygen gas cylinders, 9- display screens, 10- temperature regulators, 11- rotation speed regulating and controllings
Device, 12-CO valves, 13- drain taps, 14- oxygen valves, 15- handles.
Fig. 5 is the space-time yield of Copper-cladding Aluminum Bar graphen catalyst and the graph of a relation of cycle-index.As seen from the figure：Catalyst exists
Space-time yield change is smaller after circulating 5 times, and catalyst has good stability, not easy in inactivation.
Embodiment
The chemical substance material used during specific implementation is：Graphene oxide, hydrazine hydrate, deionized water, ethanol, nitrogen,
Copper nitrate, ammoniacal liquor, sodium hydroxide and glycine, it is measurement unit with gram, milliliter, cubic centimetre that it, which prepares consumption,.
Graphene oxide solid 20mg ± 10mg
Hydrazine hydrate：N2H4 30 mL of liquid ± 10mL
Deionized water：H2The mL of the mL of O liquid 3000 ± 50
Ethanol：C2H5The mL of the mL of OH liquid 500 ± 50
Nitrogen：N2Gas 10000cm3±100cm3
Copper nitrate：Cu(NO3)2Solid 6.3g ± 1.0g
Ammoniacal liquor：NH3·H230 mL of O liquid ± 10mL
Sodium hydroxide：25 mL of NaOH liquid ± 10mL（0.5mol/L）
Glycine： C2H5NO2Solid 8g ± 1.0g
The preparation method of Copper-cladding Aluminum Bar graphen catalyst, comprises the following steps：
（1）The preparation of copper complex
1. 6.3g copper nitrates are added into 15ml water, is suitably heated to being completely dissolved.
2. suitably heat and stir lower dropwise addition ammoniacal liquor to precipitating dissolving.
3. 25ml NaOH solution and stirring is added.
4. filtering and washing is to without nitrate ion, and dry Cu (OH)2。
5. dissolve and stirred at 8g glycine, 65 DEG C in 80ml water, add brand-new Cu (OH)2。
6. lower heating water bath 15min or so is stirred continuously, control temperature is between 60 DEG C -70 DEG C.
7. filtered off with suction while hot, then adds a small amount of water thereto, straight fire heating, starts to separate out flakey at 80 DEG C brilliant
Body, as temperature rises, crystal speed of separating out is faster.
In above-mentioned steps, step 1. and 2. described in " appropriate heating " refer to being heated at a temperature of more than room temperature
And the temperature for enabling to the solute in solution to dissolve, and physics not on solution and the temperature of chemical property generation influence.Step
Suddenly 7. described in " straight fire " refer to contacting container in dots as the flame envelope of peak flame temperature.
（2）Copper-cladding Aluminum Bar graphene
1. redox graphene
（1-1）20mg graphene oxides are dispersed in 10ml, carried out ultrasonically treated 2 hours.
（1-2）2ml hydrazine hydrates are added, are moved in 90 DEG C of water-baths, agitating and heating 2 hours.
（1-3）Filtered off with suction simultaneously uses deionized water cyclic washing, finally dries.
2. Copper-cladding Aluminum Bar graphene
（2-1）Obtained glycine is closed into copper complex and graphene is mixed to join in the aqueous solution and carried out ultrasonically treated 2 hours.
（2-2）Filtered off with suction washs mixture, and dries.
（2-3）Gains will be dried and be placed in tube furnace progress roasting 2 hours under 230 DEG C and nitrogen atmosphere.
（3）Weigh, count
Copper-cladding Aluminum Bar graphene is put on pan paper, weighed using electronic analytical balance, and record data；By the copper prepared
Doped graphene catalyst is fitted into sample sack, posts label, is placed in drier, closed to preserve；
（4）Test, analysis and characterization
Test, analysis and characterization are carried out to the pattern, color and luster, Chemical Physics performance of the Copper-cladding Aluminum Bar graphen catalyst of preparation；Use X-
Ray powder diffractometer carries out crystal phase analysis；
Conclusion：Copper-cladding Aluminum Bar graphen catalyst is black powder, and product purity is up to 99.5%, and reactivity is high, and catalytic performance is good.
（5）Estimation of stability
Use dimethyl carbonate in liquid phase reaction unit（As shown in Figure 4）Estimation of stability is carried out to catalyst is made.
1. clean dried reactor is taken, catalyst, magneton and methanol are put into inside, device is installed, and check gas circuit
Whether fasten.
2. determine that gas circuit there is not after gas leakage, first opens valve 12, reactor is rinsed three times with 2Mpa CO, to exclude
Miscellaneous gas, logical CO is to 2Mpa afterwards, and opens the excessive gas in the exclusion gas circuit of valve 13.
3. it is 3Mpa then to open valve 14 and be passed through oxygen to pressure registration, closes valve 14, and open valve 13 and exclude
Unnecessary oxygen in gas circuit.
4. after said process terminates, air inlet pipeline is laid down.Turn on the power switch, temperature, time and rotating speed are set, finally opened
Beginning running gear.
By to its active evaluation, it is found that its space-time yield is 1800mg/gh, yield is 99%.
Claims (1)
1. the preparation method of Copper-cladding Aluminum Bar graphen catalyst, it is characterised in that comprise the following steps：
（1）The preparation of copper complex
It is dissolved completely in copper nitrate is molten in water, heats and dropwise addition ammoniacal liquor, to dissolving is precipitated, adds NaOH solution under agitation,
Filtering and washing to surface without NO-, so as to obtain Kocide SD solid and drying；Glycine is dissolved in the water, 65 DEG C are heated to
Constant temperature stirring adds brand-new Kocide SD, is stirred continuously lower heating water bath 15min, and suction filtration is filtered while hot, adds the straight fire heating of water,
Start to separate out flakey crystal at 80 DEG C, accelerate as temperature rises crystal speed of separating out, glycine is made and closes copper；
（2）Copper-cladding Aluminum Bar graphene
1. redox graphene
Graphene oxide is scattered in the aqueous solution and carried out ultrasonically treated 2 hours, hydrazine hydrate is then added thereto, in 90 DEG C of water
Agitating and heating 2 hours, filtered off with suction, are washed with deionized under the conditions of bath, finally dry, and obtain graphene powder；
2. Copper-cladding Aluminum Bar graphene
Obtained glycine is closed into copper and graphene powder mixes and is dissolved in the aqueous solution, is carried out ultrasonically treated 2 hours, then filtering is taken out
Filter and dry, dried mixture is placed under the conditions of 230 DEG C of nitrogen atmosphere and is calcined 2 hours, Copper-cladding Aluminum Bar graphene is obtained and urges
Agent.
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| CN109216648A (en) * | 2018-08-21 | 2019-01-15 | 中国科学院金属研究所 | Ion is embedded in the intercalation electrode and its preparation method and application that two-dimensional layer material is constructed in advance |
| CN109603831A (en) * | 2018-12-26 | 2019-04-12 | 大连大学 | A kind of cobalt and graphene composite nano material catalyst and preparation method thereof |
| CN109806867A (en) * | 2019-02-27 | 2019-05-28 | 中国科学院金属研究所 | Nano-sized carbon loads atom level dispersion copper-based catalysts and its preparation method and application |
| CN109824044A (en) * | 2017-11-23 | 2019-05-31 | 中国科学院金属研究所 | A kind of preparation method of the monatomic doped graphene of metal |
| CN113996325A (en) * | 2021-10-21 | 2022-02-01 | 常州大学 | Nitrogen-doped graphene copper-based bimetallic monatomic catalyst and preparation method and application thereof |
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| CN113996325B (en) * | 2021-10-21 | 2022-07-01 | 常州大学 | Nitrogen-doped graphene copper-based bimetallic monatomic catalyst and preparation method and application thereof |
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