CN101816956B - Method for improving dispersion of nano metal grains on surface of graphitized carbon carrier - Google Patents
Method for improving dispersion of nano metal grains on surface of graphitized carbon carrier Download PDFInfo
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- CN101816956B CN101816956B CN2010101545731A CN201010154573A CN101816956B CN 101816956 B CN101816956 B CN 101816956B CN 2010101545731 A CN2010101545731 A CN 2010101545731A CN 201010154573 A CN201010154573 A CN 201010154573A CN 101816956 B CN101816956 B CN 101816956B
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Abstract
The invention discloses a method for improving dispersion of nano metal grains on the surface of a graphitized carbon carrier by adopting a freeze-drying method. The method comprises the following steps of: fully mixing metallic colloid prepared by using a liquid-phase colloid method and the graphitized carbon carrier uniformly, filtering and washing the mixture, then dispersing the filtrate into deionized water to form stable suspension, putting the prepared suspension into a free dryer, quenching the suspension to 40 DEG C below zero, preserving the heat for 1 to 2 hours, pumping vacuum till air pressure in a drying chamber is less than 100Pa, and drying the quenched suspension for 5 to 10 hours; and keeping the vacuum degree of the drying chamber unchangeable, gradually heating the dried product to room temperature by stages, and drying the product for 1 to 5 hours when reaching each stage of temperature value to obtain dispersed and loose spongy graphitized carbon carrier carried metal powder. The method has simple operation, and does not need to oxidize the graphitized carbon carrier and add adhesive; and the metal nano grains in the prepared sample have uniform grain diameter and good dispersion on the surface of the graphitized carbon carrier.
Description
Technical field
The present invention relates to a kind of metal nanoparticle in the method that carrier surface disperses, be characterized in that carrier is a graphitization inertia carbon carrier.
Technical background
Nano-carbon material has big specific area and electric conductivity preferably, so caused many researchers' attention as metallic catalyst carrier with nano-carbon material.But since some excellent performances, the nano-carbon material surface graphitization of good stability, and as CNT, carbon fiber etc., graphited smooth surface is the structure of inertia, is unfavorable for the support dispersion of metallic on its surface.And the method at graphitized carbon carrier surface carrying metal particle of present most of bibliographical informations mainly contains two kinds, and a kind of is that oxidation processes is carried out on inertia carbon carrier surface, makes its surface produce functional group; Another kind is to add binding agent between graphitized carbon carrier and metal particle.These methods have all increased the cementation between nano-carbon material and the metallic.But strong oxidizer is handled the stability that can destroy carbon carrier, and adds the dispersion that binding agent is unfavorable for carrier carbon material itself, and therefore, it is significant in the dispersion on graphitized carbon carrier surface to find a kind of suitable method to improve metal particle.
Freeze-drying is to utilize the principle of distillation to carry out dry a kind of technology, is the material quick freezing at low temperatures that will be dried, and under suitable vacuum environment, makes the hydrone that freezes be directly sublimed into the process of overflowing into steam then.The products known as lyophilized products (lyophilizer) that freeze drying obtains, this process is called freeze-drying, because it is dry under low temperature, low pressure, so can prevent to be dried composition heated denaturalization or oxidation deterioration in dry run.Simultaneously, in freeze-drying process, material is in low temperature (frozen state) all the time before drying, ice crystal is uniformly distributed in the material, sublimation process can be because of concentration phenomena take place in dehydration, thereby can be good at stoping short grained migration to reunite, thus the powder that can obtain having the high dispersive feature.Therefore in the past few decades in, freeze-drying is as an advanced person's dry technology, production fields such as medicine at home and abroad, food, biological products are widely used, and its range of application and application scale are in continuous expansion.
The present patent application people finds in research process, and nano-metal particle can combine with its carrier in the process of dehydration in position more closely, and freeze-drying process helps grappling and the dispersion of granule at carrier surface.For this reason, the inventor has expected taking freeze-drying to improve metal nanoparticle supporting dispersion at graphitized carbon carrier.
At present, Shang Weiyou uses desivac to improve the relevant report that metal nanoparticle disperses on the graphitized carbon carrier surface.
Summary of the invention
The object of the invention aims to provide a kind of method that metal nanoparticle disperses on the graphitized carbon carrier surface that improves.Carrier is a graphitization inertia carbon carrier.
The object of the invention adopts following technical proposals to realize.
A kind of method that improves nano-metal particle in the dispersion of graphitized carbon carrier surface, its method step is followed successively by:
1) the presoma salt with metal mixes with the reducing agent alcohol solution, stirred 20～30 minutes, transferring the solution pH value is 8～12, added hot reflux 60～150 minutes at 90～130 ℃, prepare nano metallic colloid, add ultrasonic scattered graphitized carbon carrier again, (continue whipping step 6～12h), described graphitized carbon carrier is a smooth surface inertia carbon carrier to stir into homogeneous mixture solotion;
2) mixed solution with the step 1) preparation filters, and spends deionised water and is neutral until washing lotion;
3) with step 2) to filter the back resultant that powder adds in the deionized water the ultrasonic suspension that is dispersed into;
4) suspension that will make is above put into freeze drier, is chilled to-40 ℃ and be incubated 1～2 hour, take out very to hothouse air pressure less than 100Pa, dry 4～15 hours; The chamber vacuum that keeps dry again is constant, and segmentation progressively raises temperature until room temperature, and when arriving every section temperature value drying 1～5 hour, disperseed, fluffy spongy graphitized carbon carrier carrying metal powder.
In the step 4) of the present invention, described segmentation temperature can be set arbitrarily in-40 ℃～25 ℃ scopes, but must be in the dry sufficiently long time below 0 ℃, to guarantee that moisture is fully got rid of in the sample.The general segmentation temperature that is adopted is-30 ℃ ,-20 ℃ ,-10 ℃, 0 ℃, 25 ℃.
Wherein said nano-metal particle particle diameter is between 1～100nm, and described metal is metal simple-substance or metal alloy;
Described metal simple-substance is Pt, Ru, Pd, Os, Ir, Fe, Co, Mn, Al, Mg, Sn, Cs, Li, Nb, Ta, Rb etc., described metal alloy is MxNy or MxNyOz, wherein x, y, z are that each metallic atom is counted ratio, its numerical value is respectively the integer in 0～100, and x+y=100 or x+y+z=100, M, N, O are respectively a kind of in the metal simple-substance, and M, N, O are different.
Described alcohol solution be alcohol with the water volume ratio be 0.5～100: 1 solution, wherein alcohol be in methyl alcohol, ethanol, propyl alcohol, the ethylene glycol any.
Described graphitized carbon carrier is any in CNT, carbon fiber, the graphite.
Described carbon fiber, CNT are the prepared product of Chengdu Organical Chemical Co., Ltd., Chinese Academy of Sciences.
Compare with existing background technology, the present invention has the following advantages:
1, simple to operate, do not need carrier is carried out oxidation processes and adds binding agent.
2, owing to directly aqueous water on every side is frozen into solid water, directly become gaseous state at room temperature state then, strengthened grappling effect and the dispersion of metal nanoparticle on the inert carrier surface.
3, prevented because common high temperature drying process metal particle migration aggregation phenomenon.
Description of drawings
The CNT of Fig. 1 embodiment 1 desivac preparation carries the transmission electron microscope picture (TEM) of Pt.
The carbon fiber of Fig. 2 embodiment 2 desivacs preparation carries the transmission electron microscope picture of Pd
The nano-graphite of Fig. 3 embodiment 3 desivacs preparation carries the transmission electron microscope picture of Au
The CNT of Fig. 4 embodiment 4 desivacs preparation carries the transmission electron microscope picture of Pt and Pd
The CNT of Fig. 5 embodiment 5 common oven drying method preparations carries the transmission electron microscope picture of Pt.
The specific embodiment
Embodiment 1
Desivac prepares CNT and carries Pt, and preparation process is as follows:
1, the ethylene glycol of 50ml and the deionized water of 50ml are put into there-necked flask stirring at normal temperature 10min, make it form uniform 1: 1 pure water mixed solution; H with 20ml
2PtCl
66H
2O joins in this mixture system, and stirring at normal temperature 5min makes it mix (guaranteeing that each several part acidity is identical), uses 1molL again
-1NaOH solution the pH value of system is transferred to 12, begin water-bath afterwards and be heated to 130 ℃, condensing reflux, insulation; Temperature reaches after 130 ℃ that solution begins blackening by light golden rod yellow behind 30～40min, then continue the about 2h of heating after, become lighttight substantially aterrimus solution, make stable Pt colloidal solution.Take by weighing the carbon nanotube powder of 100mg, join ultrasonic dispersion 20～30min in 60ml alcohol water (volume ratio 1: the 1) mixed solution, then it is joined in the stable Pt colloidal solution, stir 8h, get Pt colloid and CNT mixed solution;
2, Pt colloid and the CNT mixed solution with step 1 preparation filters, washs to PH=7, adds the 20ml deionized water then, the ultrasonic steady suspension that is dispersed into; Then the suspension that makes is put into freeze drier, be cooled to-40 ℃ and be incubated 1 hour, be evacuated to hothouse air pressure, dry 5 hours less than 100Pa; The chamber vacuum that keeps dry again is constant, is warmed up to-30 ℃, dry 4h; Be warmed up to-20 ℃, dry 3h; Be warmed up to-10 ℃, dry 2h; Be warmed up to 0 ℃, dry 1h is warmed up to 25 ℃, dry 1h; Close vacuum system, open the freeze drying intake valve, take out sample, disperseed, fluffy spongy CNT carries the Pt catalyst fines.The transmission electron microscope picture of product as shown in Figure 1, as seen from Figure 1, carbon nano tube surface metal Pt grain diameter is even, disperses better.
Embodiment 2
Desivac prepares carbon fiber and carries Pd, and preparation process is as follows:
1, with 0.1g PdCl
2(contain palladium 2.83 * 10
-4Mol) change into H with dense HCl
2PdCl
4NH
2O adds 20ml water it is dissolved, and adds in the there-necked flask, adds 50ml methyl alcohol and 50ml deionized water again, and in this process, ceaselessly vigorous stirring is used molL
-1NaOH solution transfer pH value to 12, with this solution heating, 130 ℃ of backflow 3h obtain uniform brownish black Pd colloid then; Take by weighing the carbon fiber powder of 100mg, join ultrasonic dispersion 20～30min in 60ml alcohol water (volume ratio 1: the 1) mixed solution, then it is joined with the prepared stable Pd colloidal solution of embodiment 1 same procedure in, stir 10h, Pd colloid and carbon fiber mixing solution;
2, Pd colloid and the carbon fiber mixing solution with step 1 preparation filters, washs to PH=7, adds the 20ml deionized water then, the ultrasonic steady suspension that is dispersed into; Treat that freeze dryer drying box shelf is cooled to about-40 ℃, the suspension that makes is put into wherein, be incubated 2 hours, be evacuated to hothouse air pressure, dry 10 hours less than 100Pa; The chamber vacuum that keeps dry again is constant, is warmed up to-30 ℃, dry 5h; Be warmed up to-20 ℃, dry 4h; Be warmed up to-10 ℃, dry 3h; Be warmed up to 0 ℃, dry 2h is warmed up to 25 ℃, dry 1h; Close vacuum system, open the freeze drying intake valve, take out sample, disperseed, fluffy spongy carbon fiber carries the Pd catalyst fines.The transmission electron microscope picture of product as shown in Figure 2, as seen from Figure 2, carbon fiber surface metal Pd grain diameter is even, disperses better.
Embodiment 3
Desivac prepares nano-graphite and carries Au, and preparation process is as follows:
1, gets 50ml ethanol 50ml deionized water and put into there-necked flask stirring at normal temperature 5min; Measure 20ml gold chloride (0.0097mol/L) and add mixed solution continuation stirring 10min; In solution, drip 10ml NaBH
4Solution (0.019mol/L) (excessive), solution becomes redness fast, has formed Au colloidal solution; Take by weighing the nano-graphite powder of 100mg, join ultrasonic dispersion 20～30min in 60ml alcohol water (volume ratio 1: the 1) mixed solution, then it is joined in the top prepared stable Au colloidal solution, stir 12h, get nano-graphite and Au colloid mixed solution;
2 nano-graphite and Au colloid mixed solutions with step 1 preparation filter, wash to PH=7, add the 20ml deionized water then, the ultrasonic steady suspension that is dispersed into; Earlier above-mentioned suspension quick-frozen is become solid-state, put into-40 ℃ drying box again, be incubated 2 hours, be evacuated to hothouse air pressure, dry 10 hours less than 100Pa with liquid nitrogen; The chamber vacuum that keeps dry again is constant, is warmed up to-30 ℃, dry 5h; Be warmed up to-20 ℃, dry 4h; Be warmed up to-10 ℃, dry 3h; Be warmed up to 0 ℃, dry 2h is warmed up to 25 ℃, dry 1h; Close vacuum system, open the freeze drying intake valve, take out sample, disperseed, fluffy spongy nano-graphite carries the Au powder.The transmission electron microscope picture of product as shown in Figure 3, as seen from Figure 3, nano-graphite surface metal Au grain diameter is even, disperses better.
Embodiment 4
Desivac prepares CNT and carries Pt and Pd, and preparation process is as follows:
1, gets the water that 50ml ethanol 50ml deionized water is put into there-necked flask stirring at normal temperature 5min, add the H of 10ml then
2PtCl
66H
2O stirs, and it is dissolved fully, mixes; Add 10ml H again
2PdCl
4The aqueous solution dropwise adds 1molL then
-1The methanol solution of NaOH, in adition process, vigorous stirring ceaselessly; Then with this solution in 130 ℃ add hot reflux 3h after, obtain the stable Pd-Pt bimetallic colloid (being designated as PVP-Pd/Pt) of brownish black; Take by weighing the carbon nanotube powder of 100mg, join ultrasonic dispersion 20～30min in 60ml alcohol water (volume ratio 1: the 1) mixed solution, then it is joined in the stable Pd-Pt bimetallic colloidal solution, stir 8h, obtain CNT and Pd and Pt bimetallic colloid mixed solution.
2, CNT that step 1 is prepared and Pd and Pt bimetallic colloid mixed solution filter, wash to PH=7, add the 20ml deionized water then, the ultrasonic steady suspension that is dispersed into; The suspension that will make is above put into freeze drier then, and pre-freeze is to-40 ℃ and be incubated 1 hour, is evacuated to hothouse air pressure less than 100Pa, dry 5 hours; The chamber vacuum that keeps dry again is constant, is warmed up to-30 ℃, dry 4h; Be warmed up to-20 ℃, dry 3h; Be warmed up to-10 ℃, dry 2h; Be warmed up to 0 ℃, dry 1h is warmed up to 25 ℃, dry 1h; Close vacuum system, open the freeze drying intake valve, take out sample, disperseed, fluffy spongy CNT carries Pd and Pt catalyst fines.The transmission electron microscope picture of product as shown in Figure 4, as seen from Figure 4, carbon nano tube surface metal Pt and Pd altogether grain diameter are even, disperse better.
The comparative example 1
Oven drying method prepares CNT and carries Pt, and preparation process is as follows:
1, the ethylene glycol of 50ml and the deionized water of 50ml are put into there-necked flask stirring at normal temperature 10min, make it form uniform 1: 1 pure water mixed solution; H with 20ml
2PtCl
66H
2O joins in this mixture system, and stirring at normal temperature 5min makes it mix (guaranteeing that each several part acidity is identical), uses 1molL again
-1NaOH solution the pH value of system is transferred to 12, begin water-bath afterwards and be heated to 130 ℃, condensing reflux, insulation, temperature reaches after 130 ℃ that solution begins blackening by light golden rod yellow behind about 40min, after then continuing the about 2h of heating, become lighttight substantially aterrimus solution, make stable Pt colloidal solution; Take by weighing the carbon nanotube powder of 100mg, join ultrasonic dispersion 30min in pure water (volume ratio 1: the 1) mixed solution of 60ml, then it is joined in the stable Pt colloidal solution, stir 8h, Pt colloid and CNT mixed solution;
2, Pt colloid and the CNT mixed solution with step 1 preparation filters, washs to PH=7, put into 80 ℃ of vacuum drying 12h of vacuum drying chamber then, make blocks of solid, grind to form powder, be the prepared CNT of oven drying method and carry the Pt catalyst with agate mortar.The transmission electron microscope picture of product as shown in Figure 5.
As seen from Figure 5, after handling through heating, drying, metal Pt particle agglomeration phenomenon is more serious, in the dispersion of carrier carbon nanotube surface obviously not as the prepared sample of desivac (see figure 1).
Claims (2)
1. one kind is improved nano-metal particle in the method that the graphitized carbon carrier surface disperses, and it is characterized in that method step is followed successively by:
1) the presoma salt with metal mixes with the reducing agent alcohol solution, stirred 20～30 minutes, transferring the pH value of solution value is 8～12, added hot reflux 60～150 minutes at 90～130 ℃, prepare nano metallic colloid, add ultrasonic scattered graphitized carbon carrier again, stir into homogeneous mixture solotion, described alcohol solution be alcohol with the water volume ratio be 0.5～100: 1 solution, wherein alcohol be in methyl alcohol, ethanol, propyl alcohol, the ethylene glycol any; Described graphitized carbon carrier is any in CNT, carbon fiber, the graphite, its smooth surface and be inertia;
2) mixed solution with the step 1) preparation filters, washs, and ultrasonic then being dispersed in becomes steady suspension in the deionized water;
3) with step 2) suspension that makes puts into freeze drier, is chilled to-40 ℃ and be incubated 1～2 hour, is evacuated to hothouse air pressure less than 100Pa, dry 5～10 hours; The chamber vacuum that keeps dry again is constant, segmentation progressively raises temperature until room temperature, be respectively-30 ℃ ,-20 ℃ ,-10 ℃, 0 ℃, 25 ℃, and when arriving every section temperature value drying 1～5 hour, disperseed, fluffy spongy graphitized carbon carrier carrying metal powder.
2. raising nano-metal particle according to claim 1 is characterized in that in the method that the graphitized carbon carrier surface disperses described nano-metal particle, its particle diameter are between 1～100nm, and described metal is metal simple-substance or metal alloy.
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| CN109046429A (en) * | 2018-08-23 | 2018-12-21 | 青岛大学 | Mat gold nano particle/graphite phase carbon nitride composite material electrochemical sensor is detected for chloramphenicol |
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|---|---|---|---|---|
| US6818254B1 (en) * | 1995-01-20 | 2004-11-16 | Engelhard Corporation | Stable slurries of catalytically active materials |
| CN1883807A (en) * | 2004-06-22 | 2006-12-27 | 三星Sdi株式会社 | Method of preparing catalyst for manufacturing carbon nanotubes |
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| CN109046429A (en) * | 2018-08-23 | 2018-12-21 | 青岛大学 | Mat gold nano particle/graphite phase carbon nitride composite material electrochemical sensor is detected for chloramphenicol |
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