CN107262095B - Preparation method of copper-doped graphene catalyst - Google Patents
Preparation method of copper-doped graphene catalyst Download PDFInfo
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Abstract
The invention relates to the field of nano material modification and catalysis, in particular to a preparation method of a copper-doped graphene catalyst. The method directly takes the metal copper doped graphene as a catalyst, and prepares the catalyst by adopting a liquid phase method, ultrasonic treatment and roasting in a tubular furnace. The preparation method has the advantages of simple operation, advanced process, low raw material cost, precise and detailed data and high preparation speed, and is an ideal method for synthesizing the dimethyl carbonate catalyst. The obtained copper monoatomic doped graphene catalyst has the advantages of good thermal conductivity of graphene, cheap and easily-obtained raw materials and the like, and also has the advantages of high activity, high selectivity, high stability and the like, so that the copper monoatomic doped graphene catalyst is a good catalyst.
Description
Technical Field
The invention relates to the field of nano material modification and catalysis, in particular to a preparation method of a copper-doped graphene catalyst.
Background
Graphene is a single-layer two-dimensional crystal formed by arranging carbon atoms in a honeycomb lattice by sp2 hybridization, has excellent electrical, optical, thermal and mechanical properties, and is often used as a carrier of a catalyst. The graphene-doped copper catalyst is used for synthesizing dimethyl carbonate, and has the advantages of good heat-conducting property, cheap and easily-obtained raw materials and the like. The graphene has specific surface areas in the upper and lower aspects, is used as a supporting carrier, can provide structural strain for repeated embedding and de-embedding of metal nanoparticles, and can show good cycle performance. Meanwhile, the metal nano particles also have larger specific surface area and strong catalytic performance, so the doping method can obviously increase the specific surface area of the prepared nano composite material, and is more beneficial to the expansion of electron migration or hydrogen storage space and the enhancement of activity. Therefore, the spin density and the charge distribution of carbon atoms can be changed by doping copper, so that 'active sites' are generated on the surface of the graphene, and the active sites can directly participate in catalytic reaction to improve the catalytic activity. In order to improve the activity of the catalyst, the patent CN103372428A takes noble metal platinum as an active component, but the method increases the production cost and is not easy to be promoted to industrial production.
The copper-doped graphene has higher chemical activity than graphene, has excellent heat conductivity, is a good catalyst carrier, and has the advantages of high activity, high selectivity, high stability and the like in the nano-crystal catalysis, so that the copper-doped graphene catalyst has great potential in the field of catalysis.
Disclosure of Invention
The invention provides a preparation method of a copper-doped graphene catalyst, aiming at solving the problems that the production cost is too high and the industrial production is not easy to be promoted in the prior art.
The invention is realized by the following technical scheme: the preparation method of the copper-doped graphene catalyst comprises the following steps:
(1) preparation of copper complexes
Dissolving copper nitrate completely in water, heating, dropwise adding ammonia water under stirring until the precipitate is dissolved, adding NaOH solution, performing suction filtration and washing until NO NO-exists on the surface, thus obtaining copper hydroxide solid and drying; dissolving glycine in water, heating to 65 ℃, stirring at constant temperature, adding newly-prepared copper hydroxide, continuously stirring, heating in a water bath for 15min, filtering and filtering while hot, adding water, heating with direct fire, beginning to separate out scaly crystals at 80 ℃, and increasing the crystal separation speed with the temperature rise to obtain copper glycinate;
(2) copper-doped graphene
① reduction of graphene oxide
Dispersing graphene oxide in an aqueous solution, carrying out ultrasonic treatment for 2 hours, then adding hydrazine hydrate, stirring and heating for 2 hours under the condition of 90 ℃ water bath, carrying out suction filtration, washing with deionized water, and finally drying to obtain graphene powder;
② copper-doped graphene
And mixing the prepared copper glycinate and graphene powder, dissolving in an aqueous solution, carrying out ultrasonic treatment for 2 hours, filtering, drying, and roasting the dried mixture for 2 hours at 230 ℃ in a nitrogen atmosphere to obtain the copper-doped graphene catalyst.
The copper-doped graphene prepared by the invention has ferromagnetic characteristics, and can change the spin density and charge distribution of carbon atoms, so that active sites are generated on the surface of the graphene, and can directly participate in catalytic reaction, thereby improving the catalytic activity.
Detecting, analyzing and representing the color and the chemical and physical properties of the prepared copper-doped graphene catalyst; performing crystal phase analysis by using an X-ray powder diffractometer; and (4) conclusion: the copper-doped graphene catalyst is black powder, the purity of the product reaches 99.5%, the reaction activity is high, and the catalytic performance is good.
Compared with the background technology, the method has obvious advancement, and the catalyst is prepared by doping the graphene with the metal copper, adopting a liquid phase method, carrying out ultrasonic treatment and roasting in a tubular furnace. The preparation method has the advantages of simple operation, advanced process, low raw material cost, precise and detailed data and high preparation speed, and is an ideal method for synthesizing the dimethyl carbonate catalyst. The obtained copper-doped graphene catalyst has the advantages of good graphene heat-conducting property, cheap and easily-obtained raw materials and the like, and also has the advantages of high activity, high selectivity, high stability and the like, so that the copper-doped graphene catalyst is a good catalyst.
Drawings
Fig. 1 is a skeletal model diagram of a copper-doped graphene catalyst. As can be seen from the figure: copper atoms (black regions) are embedded in the graphene skeleton (gray regions) and have protrusions.
Fig. 2 is a transmission electron micrograph of a copper-doped graphene catalyst.
Fig. 3 is an XRD pattern of the copper-doped graphene catalyst.
FIG. 4 is a diagram of a liquid phase reaction apparatus for dimethyl carbonate. In the figure: 1-a pressure gauge, 2-a thermocouple, 3-a gas outlet valve, 4-a reaction kettle, 5-a heat preservation seat, 6-a gas inlet valve, 7-a CO gas cylinder, 8-an oxygen gas cylinder, 9-a display screen, 10-a temperature controller, 11-a rotating speed controller, 12-a CO valve, 13-an exhaust valve, 14-an oxygen valve and 15-a handle.
Fig. 5 is a graph of space time yield versus cycle number for copper doped graphene catalysts. As can be seen from the figure: the catalyst has small change of space-time yield after 5 times of circulation, good stability and difficult inactivation.
Detailed Description
The specific implementation uses the following chemical materials: graphene oxide, hydrazine hydrate, deionized water, ethanol, nitrogen, copper nitrate, ammonia water, sodium hydroxide and glycine, wherein the preparation dosage is measured in grams, milliliters and cubic centimeters.
Graphene oxide solid 20mg +/-10 mg
Hydrazine hydrate: n is a radical of2H4Liquid 30 mL +/-10 mL
Deionized water: h2O liquid 3000 mL +/-50 mL
Ethanol: c2H5OH liquid 500 mL +/-50 mL
Nitrogen gas: n is a radical of2Gas 10000cm3±100cm3
Copper nitrate: cu (NO)3)2Solid 6.3 g. + -. 1.0g
Ammonia water: NH (NH)3·H2O liquid 30 mL +/-10 mL
Sodium hydroxide: NaOH liquid 25 mL. + -. 10mL (0.5 mol/L)
Glycine: c2H5NO2Solid 8 g. + -. 1.0g
The preparation method of the copper-doped graphene catalyst comprises the following steps:
(1) preparation of copper complexes
① 6.3g of copper nitrate was added to 15ml of water, and the mixture was appropriately heated to completely dissolve.
② Ammonia water was added dropwise with stirring and with appropriate heating until the precipitate dissolved.
③ 25ml of NaOH solution are added and stirred.
④ is filtered and washed until no nitrate ion exists, and is dried to obtain Cu (OH)2。
⑤ 80ml water 8g glycine, 65 ℃ stirring, adding fresh Cu (OH)2。
⑥ and heating in water bath for about 15min under continuous stirring, and controlling the temperature at 60-70 deg.C.
⑦ filtering while hot, adding small amount of water, heating with direct fire, and precipitating scale-like crystals at 80 deg.C with the temperature rising.
In the above steps, the "proper heating" in the steps ① and ② means a temperature at which heating is performed at a temperature higher than room temperature and solute in the solution can be dissolved, and does not affect physical and chemical properties of the solution, and the "direct fire" in the step ⑦ means that the outer flame, which is the highest temperature of the flame, contacts the container in the form of a point.
(2) Copper-doped graphene
① reduction of graphene oxide
(1-1) 20mg of graphene oxide was dispersed in 10ml, and sonication was performed for 2 hours.
(1-2) add 2ml hydrazine hydrate, move to 90 ℃ water bath, stir and heat for 2 hours.
(1-3) filtering with suction and repeatedly washing with deionized water, and finally drying.
② copper-doped graphene
(2-1) mixing the prepared copper glycinate complex and graphene, adding the mixture into an aqueous solution, and carrying out ultrasonic treatment for 2 hours.
(2-2) the washed mixture was filtered with suction and dried.
(2-3) the dried product was calcined in a tube furnace at 230 ℃ under a nitrogen atmosphere for 2 hours.
(3) Weighing and counting
Placing the copper-doped graphene on weighing paper, weighing by using an electronic analytical balance, and recording data; filling the prepared copper-doped graphene catalyst into a sample bag, sticking a label, placing the sample bag in a dryer, and sealing and storing the sample bag;
(4) detection, analysis, characterization
Detecting, analyzing and representing the morphology, color and chemical and physical properties of the prepared copper-doped graphene catalyst; performing crystal phase analysis by using an X-ray powder diffractometer;
and (4) conclusion: the copper-doped graphene catalyst is black powder, the purity of the product reaches 99.5%, the reaction activity is high, and the catalytic performance is good.
(5) Evaluation of stability
The stability of the catalyst obtained was evaluated by using a dimethyl carbonate liquid phase reaction apparatus (shown in FIG. 4).
① taking clean and dry reaction kettle, putting catalyst, magneton and methanol into the kettle, installing the device, and checking whether the gas circuit is closed tightly.
② when no gas leakage occurs in the gas path, opening valve 12, flushing the reactor with 2Mpa CO for three times to remove impurity gas, introducing CO to 2Mpa, and opening valve 13 to remove excessive gas in the gas path.
③ then the valve 14 is opened to let oxygen in until the pressure indication is 3Mpa, the valve 14 is closed, and the valve 13 is opened to remove the excess oxygen in the gas path.
④ the air inlet pipe is removed, the power switch is turned on, the temperature, time and speed are set, and the device is started.
By evaluating the activity, the air-time yield was 1800 mg/g.h, and the yield was 99%.
Claims (1)
1. The preparation method of the copper-doped graphene catalyst is characterized by comprising the following steps:
(1) preparation of copper complexes
Dissolving copper nitrate in water, heating while dropping ammonia water while stirring until the precipitate is dissolved, adding NaOH solution, suction filtering and washing until NO NO is on the surface-Thereby obtaining copper hydroxide solid and drying; dissolving glycine in water, heating to 65 ℃, stirring at constant temperature, adding newly-prepared copper hydroxide, continuously stirring, heating in a water bath for 15min, filtering and filtering while hot, adding water, heating with direct fire, beginning to separate out scaly crystals at 80 ℃, and increasing the crystal separation speed with the temperature rise to obtain copper glycinate;
(2) copper-doped graphene
① reduction of graphene oxide
Dispersing graphene oxide in an aqueous solution, carrying out ultrasonic treatment for 2 hours, then adding hydrazine hydrate, stirring and heating for 2 hours under the condition of 90 ℃ water bath, carrying out suction filtration, washing with deionized water, and finally drying to obtain graphene powder;
② copper-doped graphene
And mixing the prepared copper glycinate and graphene powder, dissolving in an aqueous solution, carrying out ultrasonic treatment for 2 hours, filtering, drying, and roasting the dried mixture for 2 hours at 230 ℃ in a nitrogen atmosphere to obtain the copper-doped graphene catalyst.
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| CN109824044B (en) * | 2017-11-23 | 2022-05-31 | 中国科学院金属研究所 | Preparation method of metal monoatomic-doped graphene |
| CN109216648B (en) * | 2018-08-21 | 2021-08-17 | 中国科学院金属研究所 | Intercalation electrode constructed by ion pre-embedding two-dimensional layered material and preparation method and application thereof |
| CN109603831B (en) * | 2018-12-26 | 2021-11-23 | 大连大学 | 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 |
| 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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| CN102600843B (en) * | 2012-01-14 | 2013-07-31 | 太原理工大学 | Preparation method of nanoscale carbon-loaded metallic copper catalyst |
| CN103213974B (en) * | 2013-04-08 | 2015-02-11 | 中国科学院重庆绿色智能技术研究院 | N-doped graphene preparation method and application of N-doped graphene |
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