CN104001503A - Preparation method of graphene oxide-loaded nano Pd (palladium) hydrogenation catalyst - Google Patents
Preparation method of graphene oxide-loaded nano Pd (palladium) hydrogenation catalyst Download PDFInfo
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Abstract
The invention relates to a preparation method of a graphene oxide-loaded nano Pd (palladium) hydrogenation catalyst. The preparation method is characterized by comprising the following steps: ultrasonically stripping graphite oxide which is adopted as a carrier in a solvent to obtain graphene oxide, adding a certain amount of PdCl2 solution into the graphene oxide, and promoting the interaction between the graphene oxide and Pd ions by utilizing ultrasonic without adding any reducing agent so that Pd ions are uniformly deposited onto the graphene oxide to obtain the loaded Pd nano particle catalyst with high dispersion property. The prepared catalyst is not only simple in preparation method and environment-friendly in preparation process, but also high in stability and reusability. The catalyst has very high catalytic activity when applied to the hydrogenation of olefin, nitrobenzene and cinnamyl aldehyde.
Description
Technical field
The present invention relates to hydrogenation catalyst and preparing technical field thereof, particularly a kind of preparation method of graphene oxide-loaded nano Pd hydrogenation catalyst.
Background technology
Hydrogenation reaction is one of reaction important in Industrial Catalysis.Catalyst for this reaction is mainly the noble metals such as Pd, Pt at present.Metallic catalyst, especially nanometer Pd, because of its excellent catalytic activity with selectively occupy an important position in heterogeneous catalysis field.Nanometer Pd easily reunites, is difficult to stable existence and difficult recovery is the difficult problem running at present, is also the focus of research.By carrier dispersing nanometer Pd, by the active force of carrier and Pd, stop the reunion of nano particle, increasing its rate of recovery is comparatively effective mode.The carrier of research mainly contains at present: Al
2o
3, SiO
2, active carbon, molecular sieve etc.But the existence of carrier can affect the diffusion of reactant and product again, reduce reaction rate.Therefore, if will give full play to unique catalytic performance of nanometer Pd, not only to guarantee the stable existence of the Pd of high dispersive, also will select suitable carrier to be conducive to the carrying out of reaction simultaneously.
Graphene, also can be described as " mono-layer graphite ", is the bi-dimensional cellular shape crystal by the tightly packed one-tenth of monolayer carbon atom, has compared with electric-conductivity heat-conductivity high, large specific area and splendid heat endurance, becomes the excellent carrier of nano metal.And compare with traditional porous material, its two-dimentional lamellar structure can be eliminated reactant and the interior diffusion of product in duct, thereby improve reaction rate.At present, take Graphene as carrier, researchers have prepared various metals nano particle (Pt, Au, Pd, Ag, Fe etc.).These particles not only can be on Graphene high degree of dispersion, can also stop the gathering between graphene sheet layer, in the reactions such as Suzuki coupling, hydrogenation, oxidation, water decomposition, show excellent catalytic activity.But above-mentioned nano metal preparation process is used sodium borohydride or hydrazine hydrate reduction agent mostly, pollute greatlyr, and graphene oxide is also reduced simultaneously, causes and piles up.(Synthesis of " Clean " the and Well-Dispersive Pd Nanoparticles with Excellent Electrocatalytic Property on Graphene Oxide such as the Chen Xi of Xiamen University, J.Am.Chem.Soc.2011,133,3693 – 3695) find PdCl
4 2-different from the oxidation-reduction potential of graphene oxide, by stirring, can make Pd be deposited on graphene oxide, but simple agitation make Pd load factor lower.Therefore, in the urgent need to a kind of simple to operate, environmental friendliness, with low cost, the method that load factor is high is prepared metal nano Pd.
Summary of the invention
The technical problem to be solved in the present invention be for Pd nano particle easily reunite, preparation process pollutes the problem that the aspect such as large, load factor is low exists, and a kind of relatively simple, clean, method of preparing cheaply high-dispersion Pd nano particle/graphene oxide hydrogenation catalyst is provided.
The technical solution adopted for the present invention to solve the technical problems is:
A preparation method for graphene oxide-loaded nano Pd hydrogenation catalyst, this catalyst is to take graphene oxide as carrier, take nanometer Pd as active component, adopts the method for ultrasonic dispersion to obtain.The concrete steps of the method are as follows:
Take graphite oxide and be added in 20mL solvent, making graphite oxide concentration is 1-5mg/mL, is then carried out ultrasonic processing, supersonic frequency is 180W, 50 ℃ of ultrasonic 1.5h, obtain the graphene oxide solution of high degree of dispersion, then to the PdCl that adds 0.5-2mL in this solution
2the aqueous solution (0.02mol/L), and process under certain ultrasound condition, supersonic frequency 120-240W, temperature 10-60 ℃, time 10-60min, finishes rear centrifugation, and with deionized water washing 5 times, 60 ℃ of vacuum drying 2h, obtain described catalyst.
As limitation of the invention, solvent of the present invention is deionized water, ethanol or ethylene glycol.
Find under study for action, in the situation that not adding any reducing agent, by ultrasonication, can promote the effect of Pd ion and graphene oxide, increase the load factor of Pd, thereby can prepare efficiently the Pd/ graphene oxide catalyst of high dispersive.
In addition, the method can prevent graphite oxide being reduced in traditional electronation process effectively, thus the irreversible reunion of avoiding the graphene sheet layer after reduction to cause because of pi-pi accumulation.In addition,, because carrier is graphene oxide, make us in follow-up reaction system, have fabulous dispersiveness by prepared catalyst.
The method is compared with traditional chemical reduction method, simple to operate, and the preparation cost of catalyst is cheap, and the process environment of preparation is friendly, does not produce poisonous compound.
Catalyst of the present invention not only shows good catalytic activity in the hydrogenation reaction of alkene, also can efficient catalytic nitrobenzene and the hydrogenation reaction such as cinnamic acid.
The specific embodiment
The present invention will be described further with regard to following examples, but will be appreciated that, these embodiment are the use for illustrating only, and should not be interpreted as restriction of the invention process.
Embodiment 1
Take 0.02g graphite oxide and add in 20mL deionized water, by its ultrasonic processing, supersonic frequency is 180W, and 50 ℃ of ultrasonic 1.5h, after ultrasonic end, to the PdCl that adds the 0.02mol/L of 1mL in solution
2solution, at 180W, ultrasonic 20min at 20 ℃, reaction finishes rear centrifugation, and with deionized water washing 5 times, 60 ℃ of vacuum drying 2h, obtain described catalyst A.
Embodiment 2
Take 0.1g graphite oxide and add in 20mL ethanol, by its ultrasonic processing, supersonic frequency is 180W, and 50 ℃ of ultrasonic 1.5h, after ultrasonic end, to the PdCl that adds the 0.02mol/L of 0.5mL in solution
2solution, at 120W, ultrasonic 10min at 10 ℃, reaction finishes rear centrifugation, and with deionized water washing 5 times, 60 ℃ of vacuum drying 2h, obtain described catalyst B.
Embodiment 3
Take 0.02g graphite oxide and add in 20ml ethylene glycol, by its ultrasonic processing, supersonic frequency is 180W, and 50 ℃ of ultrasonic 1.5h, after ultrasonic end, to the PdCl that adds the 0.02mol/L of 1mL in solution
2solution, at 180W, ultrasonic 20min at 20 ℃, reaction finishes rear centrifugation, and with deionized water washing 5 times, 60 ℃ of vacuum drying 2h, obtain described catalyst C.
Embodiment 4
Take 0.02g graphite oxide and add in 20mL deionized water, by its ultrasonic processing, supersonic frequency is 180W, and 50 ℃ of ultrasonic 1.5h, after ultrasonic end, to the PdCl that adds the 0.02mol/L of 1mL in solution
2solution, at 240W, ultrasonic 20min at 20 ℃, reaction finishes rear centrifugation, and with deionized water washing 5 times, 60 ℃ of vacuum drying 2h, obtain described catalyst D.
Embodiment 5
Take 0.02g graphite oxide and add in 20mL deionized water, by its ultrasonic processing, supersonic frequency is 180W, and 50 ℃ of ultrasonic 1.5h, after ultrasonic end, to the PdCl that adds the 0.02mol/L of 1mL in solution
2solution, at 180W, ultrasonic 20min at 50 ℃, reaction finishes rear centrifugation, and with deionized water washing 5 times, 60 ℃ of vacuum drying 2h, obtain described catalyst E.
Embodiment 6
Take 0.02g graphite oxide and add in 20mL deionized water, by its ultrasonic processing, supersonic frequency is 180W, and 50 ℃ of ultrasonic 1.5h, after ultrasonic end, to the PdCl that adds the 0.02mol/L of 1mL in solution
2solution, at 180W, ultrasonic 60min at 60 ℃, reaction finishes rear centrifugation, and with deionized water washing 5 times, 60 ℃ of vacuum drying 2h, obtain described catalyst F.
Embodiment 7
Take 0.06g graphite oxide and add in 20mL deionized water, by its ultrasonic processing, supersonic frequency is 180W, and 50 ℃ of ultrasonic 1.5h, after ultrasonic end, to the PdCl that adds the 0.02mol/L of 1mL in solution
2solution, at 180W, ultrasonic 20min at 20 ℃, reaction finishes rear centrifugation, and with deionized water washing 5 times, 60 ℃ of vacuum drying 2h, obtain described catalyst G.
Embodiment 8
Take 0.02g graphite oxide and add in 20mL deionized water, by its ultrasonic processing, supersonic frequency is 180W, and 50 ℃ of ultrasonic 1.5h, after ultrasonic end, to the PdCl that adds the 0.02mol/L of 2mL in solution
2solution, at 180W, ultrasonic 20min at 20 ℃, reaction finishes rear centrifugation, and with deionized water washing 5 times, 60 ℃ of vacuum drying 2h, obtain described catalyst H.
Catalyst in above-described embodiment is applied in cyclohexene hydrogenation process, and reaction condition is as follows:
Solvent: ethanol; Cyclohexene/Pd (mol/mol): 30; Hydrogen Vapor Pressure: 1.0MPa; Reaction temperature: 20 ℃; Reaction time: 0.5h
Its catalytic performance is as shown in table 1:
The catalytic performance of catalyst
| Catalyst | Cyclohexene conversion rate (%) | Cyclohexane selective (%) |
| A | 96.8 | 100 |
| B | 81.4 | 100 |
| C | 93.5 | 100 |
| D | 99.7 | 100 |
| E | 89.6 | 100 |
| F | 87.7 | 100 |
| G | 95.5 | 100 |
| H | 99.8 | 100 |
As can be seen from the above table, the hydrogenation by catalyst of the present invention for cyclohexene, at 20 ℃, maximum conversion can reach 99.8%, far exceeds the activity of Supported Pd-Catalyst that report in document and business.And method for preparing catalyst of the present invention is simple, clean, with low cost.
The above-mentioned foundation desirable embodiment of the present invention of take is enlightenment, and by above-mentioned description, relevant staff can, within not departing from the scope of this invention technological thought, carry out various change and modification completely.The technical scope of this invention is not limited to the content on description, must determine its technical scope according to claim scope.
Claims (4)
1. a preparation method for graphene oxide-loaded nano Pd hydrogenation catalyst, is characterized in that this catalyst is to take graphene oxide as carrier, take nanometer Pd as active component, adopts the method for ultrasonic dispersion to obtain.
2. the preparation method of a kind of graphene oxide-loaded nano Pd hydrogenation catalyst according to claim 1, is characterized in that what the method was carried out according to following step:
(1) take a certain amount of graphite oxide and be added in 20mL solvent, making graphite oxide concentration is 1-5mg/mL, and then, by its ultrasonic 1.5h at 50 ℃, supersonic frequency is 180W, obtains the graphene oxide solution of high degree of dispersion;
(2) to the 0.02mol/L PdCl that adds 0.5-2mL in the solution of step (1) gained
2the aqueous solution is processed this solution under certain ultrasound condition, after ultrasonic end, solution centrifugal is separated, and with deionized water washing 5 times, 60 ℃ of vacuum drying 2h, obtain described catalyst.
3. the preparation method of a kind of graphene oxide-loaded nano Pd hydrogenation catalyst according to claim 2, is characterized in that the solvent described in step (1) is deionized water, ethanol or ethylene glycol.
4. the preparation method of a kind of graphene oxide-loaded nano Pd hydrogenation catalyst according to claim 2, is characterized in that the ultrasound condition described in step (2) is: supersonic frequency 120-240W, temperature 10-60 ℃, time 10-60min.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108144654A (en) * | 2018-01-30 | 2018-06-12 | 常州大学 | A kind of phenolic aldehyde cross-linking method prepares three-dimensional grapheme load nano Pd catalyst and its application in hydrogenation of chloronitrobenzene |
| CN108295843A (en) * | 2018-01-19 | 2018-07-20 | 常州大学 | A kind of soft template method prepares three-dimensional grapheme load nano Pd catalyst and its application in hydrogenation of chloronitrobenzene |
| CN109599568A (en) * | 2018-11-30 | 2019-04-09 | 上海师范大学 | A kind of preparation method and applications of palladium/graphene composite material |
| CN109663591A (en) * | 2019-01-23 | 2019-04-23 | 常州大学 | A kind of methods and applications of the low-high temperature continuous aqueous phase immersion reduction method preparation graphene oxide-loaded noble metal catalyst of thermal response |
| CN111604049A (en) * | 2020-06-05 | 2020-09-01 | 黑龙江省科学院石油化学研究院 | Reduced graphene oxide loaded two-dimensional coral sheet-shaped palladium nano-catalyst and preparation method thereof |
| CN112090434A (en) * | 2020-09-16 | 2020-12-18 | 常州大学 | Preparation method of supported nickel phosphide for catalyzing selective hydrogenation of furfural to prepare furfuryl alcohol |
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Cited By (12)
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| CN108295843A (en) * | 2018-01-19 | 2018-07-20 | 常州大学 | A kind of soft template method prepares three-dimensional grapheme load nano Pd catalyst and its application in hydrogenation of chloronitrobenzene |
| CN108295843B (en) * | 2018-01-19 | 2020-05-26 | 常州大学 | Three-dimensional graphene loaded nano Pd catalyst prepared by soft template method and application of catalyst in nitrobenzene hydrogenation |
| CN108144654A (en) * | 2018-01-30 | 2018-06-12 | 常州大学 | A kind of phenolic aldehyde cross-linking method prepares three-dimensional grapheme load nano Pd catalyst and its application in hydrogenation of chloronitrobenzene |
| CN108144654B (en) * | 2018-01-30 | 2020-02-14 | 常州大学 | Three-dimensional graphene-loaded nano Pd catalyst prepared by phenolic crosslinking method and application of catalyst in nitrobenzene hydrogenation |
| CN109599568A (en) * | 2018-11-30 | 2019-04-09 | 上海师范大学 | A kind of preparation method and applications of palladium/graphene composite material |
| CN109599568B (en) * | 2018-11-30 | 2021-11-23 | 上海师范大学 | Preparation method and application of palladium/graphene composite material |
| CN109663591A (en) * | 2019-01-23 | 2019-04-23 | 常州大学 | A kind of methods and applications of the low-high temperature continuous aqueous phase immersion reduction method preparation graphene oxide-loaded noble metal catalyst of thermal response |
| CN109663591B (en) * | 2019-01-23 | 2020-08-14 | 常州大学 | Method for preparing thermal response graphene oxide supported noble metal catalyst by low-high temperature continuous aqueous phase impregnation reduction method and application |
| CN111604049A (en) * | 2020-06-05 | 2020-09-01 | 黑龙江省科学院石油化学研究院 | Reduced graphene oxide loaded two-dimensional coral sheet-shaped palladium nano-catalyst and preparation method thereof |
| CN111604049B (en) * | 2020-06-05 | 2022-07-08 | 黑龙江省科学院石油化学研究院 | Reduced graphene oxide loaded two-dimensional coral sheet-shaped palladium nano-catalyst and preparation method thereof |
| CN112090434A (en) * | 2020-09-16 | 2020-12-18 | 常州大学 | Preparation method of supported nickel phosphide for catalyzing selective hydrogenation of furfural to prepare furfuryl alcohol |
| CN112090434B (en) * | 2020-09-16 | 2023-05-23 | 常州大学 | Preparation method of supported nickel phosphide for preparing furfuryl alcohol by catalyzing selective hydrogenation of furfural |
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