CN104261382A - Method for preparing mesoporous carbon material rapidly - Google Patents
Method for preparing mesoporous carbon material rapidly Download PDFInfo
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- CN104261382A CN104261382A CN201410345134.7A CN201410345134A CN104261382A CN 104261382 A CN104261382 A CN 104261382A CN 201410345134 A CN201410345134 A CN 201410345134A CN 104261382 A CN104261382 A CN 104261382A
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Abstract
The invention provides a method for preparing a mesoporous carbon material rapidly. The method comprises the following steps of mixing a carbohydrate (or thermosetting resin), sodium silicate, nitric acid and water to prepare a mixture; carrying out microwave treatment on the mixture to nucleate a hexagonal carbon material on a surface of a silica template to obtain a carbon/silicon composite material; adding sodium hydroxide to the carbon/silicon composite material; carrying out microwave treatment on the carbon/silicon composite material; and adding hydrofluoric acid to the carbon/silicon composite material so as to remove the silica template from the carbon/silicon composite material, and thus the mesoporous carbon material is prepared.
Description
Technical field
The present invention about a kind of manufacture method of Hole type carbon material, this method can premised on the quality not affecting product under, promptly prepare Hole type carbon material.
Background technology
Carbon material is divided into huge hole type (macroporous), Hole type (mesoporous) and Micro-v oid type (microporous) according to its mean pore size, wherein the mean pore size of huge hole type carbon material is greater than 50nm, the mean pore size of Hole type carbon material is between 2-50nm, and the mean pore size of Micro-v oid type carbon material is less than 2nm.Different carbon materials possesses different character, similarly is specific surface area, thermal stability, physical strength and conductance, therefore can be applicable to different purposes.For example, Hole type carbon material can in conjunction with the catalyst of metallics (or metal oxide particle) as fuel cell.
The manufacture method of common Hole type carbon material refers to TaiWan, China patent of invention notification number I243507, TaiWan, China patent of invention publication number 201238893, TaiWan, China patent of invention publication number 201121888, China Mechanical Engineering academic periodical, 31st volume, 5th phase, 393-402 page (2010 2010), China Mechanical Engineering academic periodical, 31st volume, 4th phase, 315-324 page (2010 2010).First, in the method that TaiWan, China patent of invention notification number I243507 mentions, the phenol mela mine-formaldehyde resin being dissolved in ethanol is added the Hole material once calcining, then the mixed solution that obtains in stirred at ambient temperature 24 hours.In addition, in the method that TaiWan, China patent of invention publication number 201238893 is mentioned, heating, containing the intermediate product 1 to 3 hour of interfacial agent, carbon source material and silicon oxide template, makes intermediate product carbonization.Moreover, in the method that TaiWan, China patent of invention publication number 201121888 is pointed out, stir phenol mela mine-formaldehyde resin solution 2 to 36 hours, make resin polymerization reaction take place.Then, in China Mechanical Engineering academic periodical, the 31st volume, 5th phase, the method that 393-402 page (2010) adopts, first stirs the mixture containing glucose (or Zulkovsky starch), nitric acid and water glass 24 hours at 100 DEG C, then to be placed in by mixture in 100 DEG C of baking ovens 1 day.Finally, in China Mechanical Engineering academic periodical, 31st volume, 4th phase, the method that 315-324 page (2010) uses, mixture containing phenol mela mine-formaldehyde resin (or aniline formaldehyde resin, urea formaldehyde resin), nitric acid and water glass is stirred 24 hours at 100 DEG C, afterwards mixture to be placed in 100 DEG C of baking ovens 1 day.
To sum up, can recognize that the manufacture method ubiquity of common Hole type carbon material has a so tediously long step, cause these manufacture method too time-consuming.So develop a kind of manufacture method of Hole type carbon material, it does not only affect the quality of carbon material, also can save time, really there are urgent need.
Summary of the invention
An object of the present invention is the manufacture method of the Hole type carbon material proposing a kind of novelty, and this method, except not affecting the quality of the carbon material obtained, also can save the time that processing procedure is spent on the whole.
So for realizing above-mentioned and/or other object, the present invention adopts following scheme:
First scheme of the present invention is a kind of manufacture method of Hole type carbon material, and it contains following steps: mixing carbohydrate, water glass, nitric acid and water, to be mixed with a mixture; One microwave treatment is carried out to mixture, makes lonsdaleite material nucleation on silicon oxide template surface, to obtain one carbon/silicon composite; Add sodium hydroxide to carbon/silicon composite; Another microwave treatment is carried out to carbon/silicon composite; And add hydrofluoric acid to carbon/silicon composite, and to remove the silicon oxide template in carbon/silicon composite, obtained Hole type carbon material.
Alternative plan of the present invention is a kind of manufacture method of Hole type carbon material, and it comprises the following step: mixture heat curable type resin, water glass, nitric acid and water, to be mixed with a mixture; One microwave treatment is carried out to mixture, makes lonsdaleite material nucleation on silicon oxide template surface, to obtain one carbon/silicon composite; Add sodium hydroxide to carbon/silicon composite; Another microwave treatment is carried out to carbon/silicon composite; And add hydrofluoric acid to carbon/silicon composite, and to remove the silicon oxide template in carbon/silicon composite, obtained Hole type carbon material.
According to the present invention, the method that such scheme is mentioned easily operates and quite saves time.And obtained Hole type carbon material still has close to or is more better than the quality of existing Hole type carbon material.
Accompanying drawing explanation
Fig. 1 is a schema, and the manufacture method of the Hole type carbon material of an embodiment of the present invention is described;
Fig. 2 is a schema, and the manufacture method of the Hole type carbon material of another embodiment of the present invention is described;
Fig. 3 is one scan formula electron micrograph, presents the outward appearance of Hole type carbon material (DMC) of preparation example 1;
Fig. 4 is a transmission electron microscope photo, presents the outward appearance of the catalyst (Pt/DMC) of preparation example 1;
Fig. 5 is one scan formula electron micrograph, presents the outward appearance of Hole type carbon material (SMC) of preparation example 2;
Fig. 6 is a transmission electron microscope photo, presents the outward appearance of the catalyst (Pt/SMC) of preparation example 2;
Fig. 7 is one scan formula electron micrograph, presents the outward appearance of Hole type carbon material (PFMC) of preparation example 3;
Fig. 8 is a transmission electron microscope photo, presents the outward appearance of the catalyst (Pt/PFMC) of preparation example 3;
Fig. 9 is one scan formula electron micrograph, presents the outward appearance of Hole type carbon material (AFMC) of preparation example 4;
Figure 10 is a transmission electron microscope photo, presents the outward appearance of the catalyst (Pt/AFMC) of preparation example 4;
Figure 11 is one scan formula electron micrograph, presents the outward appearance of Hole type carbon material (UFMC) of preparation example 5;
Figure 12 is a transmission electron microscope photo, presents the outward appearance of the catalyst (Pt/UFMC) of preparation example 5;
Figure 13 is an X-ray diffraction analysis instrument collection of illustrative plates, and the composition of Pt/DMC is described;
Figure 14 is an X-ray diffraction analysis instrument collection of illustrative plates, and the composition of Pt/SMC is described;
Figure 15 is an X-ray diffraction analysis instrument collection of illustrative plates, and the composition of Pt/PFMC is described;
Figure 16 is an X-ray diffraction analysis instrument collection of illustrative plates, and the composition of Pt/AFMC is described;
Figure 17 is an X-ray diffraction analysis instrument collection of illustrative plates, and the composition of Pt/UFMC is described;
Figure 18 is an X-ray diffraction analysis instrument collection of illustrative plates, and the composition of the catalyst (Pt/XC-72) of reference examples is described;
Figure 19 is a cyclic voltammetry result figure, and the electrochemical properties of Pt/DMC and Pt/SMC is described;
Figure 20 is a cyclic voltammetry result figure, and the electrochemical properties of Pt/PFMC, Pt/AFMC and Pt/UFMC is described;
Figure 21 is the linear sweep voltammetry result figure of a collocation rotating disk electrode, and the electrochemical properties of Pt/DMC is described;
Figure 22 is the linear sweep voltammetry result figure of a collocation rotating disk electrode, and the electrochemical properties of Pt/SMC is described;
Figure 23 is the linear sweep voltammetry result figure of a collocation rotating disk electrode, and the electrochemical properties of Pt/PFMC is described;
Figure 24 is the linear sweep voltammetry result figure of a collocation rotating disk electrode, and the electrochemical properties of Pt/AFMC is described;
Figure 25 is the linear sweep voltammetry result figure of a collocation rotating disk electrode, and the electrochemical properties of Pt/UFMC is described;
Figure 26 is the linear sweep voltammetry result figure of a collocation rotating disk electrode, and the electrochemical properties of Pt/XC-72 is described;
Figure 27 is a linear sweep voltammetry result figure, and the electrochemical properties of Pt/DMC and Pt/SMC is described;
Figure 28 is a linear sweep voltammetry result figure, and the electrochemical properties of Pt/PFMC, Pt/AFMC and Pt/UFMC is described.
description of reference numerals
S11-S16: step
S21-S26: step.
Specific embodiment
For above-mentioned and/or other object of the present invention, effect, feature more can be become apparent, better embodiment cited below particularly, elaborates.
Please first consult Fig. 1, in one embodiment of the present invention, disclose a kind of manufacture method of Hole type carbon material, its detailed process is as following:
As shown in step S11, mixing carbohydrate, water glass, nitric acid and water, to be mixed with a mixture.Generally speaking, when carrying out step S11, can stir or not stir the mixture be mixed with; And to save time spent by this manufacture method under condition, preferably do not stir the mixture be mixed with.In addition, the example of carbohydrate, can be but be not limited to glucose or Zulkovsky starch.
As shown in step S12, a microwave treatment is carried out to mixture, make lonsdaleite material nucleation on silicon oxide template surface, to obtain one carbon/silicon composite.In detail, step S12 can impel the nitric acid in mixture that water glass is changed into silicon oxide template, and the lonsdaleite material of carbonized carbonaceous hydrate nucleation on template surface.And the microwave output power of microwave treatment and time are unrestricted in principle, as long as carbon/silicon composite can be formed.In present embodiment, microwave output power is about 300 to 3,000W, and the time is about 3 to 30 minutes.
As shown in step S13, add sodium hydroxide to carbon/silicon composite.
As shown in step S14, another microwave treatment is carried out to carbon/silicon composite.In detail, step S14 can promote the lonsdaleite material in sodium hydroxide etch carbon/silicon composite, allows lonsdaleite material offer hole.Moreover the microwave output power of microwave treatment and time are unrestricted in theory, as long as the object of step 14 can be reached.In present embodiment, microwave output power is about 300 to 3,000W, and the time is about 3 to 30 minutes.
As shown in step S15, add hydrofluoric acid to carbon/silicon composite, to remove the silicon oxide template in carbon/silicon composite, obtained Hole type carbon material.Specifically, hydrofluoric acid can the hole of lonsdaleite material in carbon/silicon composite infiltrate to silicon oxide template, and corrodes and remove silicon oxide template.
As shown in step S16, with water cleaning Hole type carbon material, and dry cleaned Hole type carbon material.Step S16 can promote the purity of Hole type carbon material, and it is non-essential and can optionally implements.
Please referring again to Fig. 2, in another embodiment of the present invention, disclose a kind of manufacture method of Hole type carbon material, its detailed process is as following:
As shown in step S21, mixture heat curable type resin, water glass, nitric acid and water, to be mixed with a mixture.In general, during operation steps S21, can stir or not stir the mixture be mixed with; Suppose under premised on the time saved spent by this manufacture method, preferably do not stir the mixture be mixed with.And the example of heat curing-type resin, can be but be not limited to phenol mela mine-formaldehyde resin, aniline formaldehyde resin or urea formaldehyde resin.
As shown in step S22, a microwave treatment is carried out to mixture, make lonsdaleite material nucleation on silicon oxide template surface, to obtain one carbon/silicon composite.In detail, step S22 can change water glass into silicon oxide template for the nitric acid in mixture, and carbonization thermoset resin becomes the lonsdaleite material of nucleation on template surface.In principle, microwave output power and the time of microwave treatment are unrestricted, as long as can form carbon/silicon composite.In present embodiment, microwave output power is about 300 to 3,000W, and the time is about 3 to 30 minutes.
As shown in step S23, add sodium hydroxide to carbon/silicon composite.
As shown in step S24, another microwave treatment is carried out to carbon/silicon composite.Say further, step S24 can cause the lonsdaleite material in sodium hydroxide etch carbon/silicon composite, makes lonsdaleite material offer hole.In theory, microwave output power and the time of microwave treatment are unrestricted, as long as can reach the object of step 24.In present embodiment, microwave output power is about 300 to 3,000W, and the time is about 3 to 30 minutes.
As shown in step S25, add hydrofluoric acid to carbon/silicon composite, to remove the silicon oxide template in carbon/silicon composite, obtained Hole type carbon material.In special words, the hole of the lonsdaleite material that hydrofluoric acid can pass through in carbon/silicon composite infilters to silicon oxide template, and erosion removes silicon oxide template.
As denoted by step s 26, with water cleaning Hole type carbon material, and cleaned Hole type carbon material is dried.The object of step S26 is in the purity promoting Hole type carbon material, and it is for non-essential and can optionally carry out.
Hereby illustrate embodiments of the present invention further with embodiment hereafter:
" preparation example 1 "
20 grams of glucose, 400 grams of water glass, 120 milliliters of salpeter solutions (molarity 2M) and 300 ml waters are mixed, but do not stir the mixture obtained.Mixture is placed in a microwave oven, and utilizes the microwave treatment mixture 10 minutes of microwave output power 2,500W, on the silicon oxide template surface that the lonsdaleite material nucleation allowing Glucose Carbon change into is reacted in water glass, and obtained one carbon/silicon composite.Add sodium hydroxide solution (molarity 2M) to carbon/silicon composite.Carbon/silicon composite is placed in microwave oven, and utilizes microwave output power 2, the microwave treatment carbon/silicon composite of 500W 10 minutes, make the lonsdaleite material in carbon/silicon composite have hole.Add hydrofluoric acid solution (concentration expressed in percentage by weight 48%) to carbon/silicon composite, remove silicon oxide template wherein and obtain a Hole type carbon material.Finally, clean with water the carbon material that obtains and carbon material is dried.In hereafter, specially represent Hole type carbon material (as Fig. 3) herein with code name " DMC ".
Getting 0.08 gram of DMC and 0.05 gram Platinic chloride and be blended in one in vitro, and dropwise add sodium hydroxide solution (molarity 1M) in vitro, adjusting the pH value of mixing solutions to being greater than 12.After adding 25 milliliters of formaldehyde solutions (concentration expressed in percentage by weight 48%), Keep agitation mixing solutions 12 hours at 100 DEG C.After cooling, in stirred at ambient temperature mixing solutions to overnight.Finally, filter mixing solutions, clean with water the filtration product that obtains and be placed in 160 DEG C of drying in oven products, and obtain a catalyst.As Fig. 4, the catalyst of this preparation example is that platinum supports and formed on DMC, and the rate that supports of platinum is about 20.25%, and particle diameter is about 3nm.In hereafter, special with code name " Pt/DMC " representative catalyst herein.
" preparation example 2 "
20 grams of Zulkovsky starches, 100 grams of water glass, 120 milliliters of salpeter solutions (molarity 2M) and 300 ml waters are mixed, but do not stir the mixture obtained.Mixture is placed in a microwave oven, and utilizes the microwave treatment mixture 10 minutes of microwave output power 2,500W, on the silicon oxide template surface that the lonsdaleite material nucleation allowing Zulkovsky starch carbonization become is reacted in water glass, and obtained one carbon/silicon composite.Add sodium hydroxide solution (molarity 2M) to carbon/silicon composite.Carbon/silicon composite is placed in microwave oven, and utilizes microwave output power 2, the microwave treatment carbon/silicon composite of 500W 10 minutes, make the lonsdaleite material in carbon/silicon composite have hole.Add hydrofluoric acid solution (concentration expressed in percentage by weight 48%) to carbon/silicon composite, remove silicon oxide template wherein and obtain a Hole type carbon material.Finally, clean with water the carbon material that obtains and carbon material is dried.In hereafter, specially represent Hole type carbon material (as Fig. 5) herein with code name " SMC ".
Getting 0.08 gram of SMC and 0.05 gram Platinic chloride and be blended in one in vitro, and dropwise add sodium hydroxide solution (molarity 1M) in vitro, adjusting the pH value of mixing solutions to being greater than 12.After adding 25 milliliters of formaldehyde solutions (concentration expressed in percentage by weight 48%), Keep agitation mixing solutions 12 hours at 100 DEG C.After cooling, in stirred at ambient temperature mixing solutions to overnight.Finally, filter mixing solutions, clean with water the filtration product that obtains and be placed in 160 DEG C of drying in oven products, and obtain a catalyst.As Fig. 6, the catalyst of this preparation example is that platinum supports and formed on SMC, and the rate that supports of platinum is about 20.04%, and particle diameter is about 3nm.In hereafter, special with code name " Pt/SMC " representative catalyst herein.
" preparation example 3 "
10 grams of phenol are dissolved in 200 ml waters.Dropwise add 80 milliliters of formaldehyde solutions (concentration expressed in percentage by weight 30%) to the aqueous solution, the Keep agitation aqueous solution is until formaldehyde dissolves completely, and an obtained phenol mela mine-formaldehyde resin solution.By 200 grams of water glass, 120 milliliters of salpeter solutions (molarity 2M), mix with phenol mela mine-formaldehyde resin solution, but do not stir the mixture obtained.Mixture is placed in a microwave oven, and utilizes the microwave treatment mixture 10 minutes of microwave output power 2,500W, on the silicon oxide template surface that the lonsdaleite material nucleation allowing the carbonization of phenol mela mine-formaldehyde resin become is reacted in water glass, and obtained one carbon/silicon composite.Add sodium hydroxide solution (molarity 2M) to carbon/silicon composite.Carbon/silicon composite is placed in microwave oven, and utilizes microwave output power 2, the microwave treatment carbon/silicon composite of 500W 10 minutes, make the lonsdaleite material in carbon/silicon composite have hole.Add hydrofluoric acid solution (concentration expressed in percentage by weight 48%) to carbon/silicon composite, remove silicon oxide template wherein and obtain a Hole type carbon material.Finally, clean with water the carbon material that obtains and carbon material is dried.In hereafter, specially represent Hole type carbon material (as Fig. 7) herein with code name " PFMC ".
Getting 0.08 gram of PFMC and 0.05 gram Platinic chloride and be blended in one in vitro, and dropwise add sodium hydroxide solution (molarity 1M) in vitro, adjusting the pH value of mixing solutions to being greater than 12.After adding 25 milliliters of formaldehyde solutions (concentration expressed in percentage by weight 30%), Keep agitation mixing solutions 6 hours at 100 DEG C.After cooling, in stirred at ambient temperature mixing solutions to overnight.Finally, filter mixing solutions, clean with water the filtration product that obtains and be placed in 160 DEG C of drying in oven products, and obtain a catalyst.As Fig. 8, the catalyst of this preparation example is that platinum supports and formed on PFMC, and the rate that supports of platinum is about 20.25%, and particle diameter is about 3nm.In hereafter, special with code name " Pt/PFMC " representative catalyst herein.
" preparation example 4 "
10 grams of aniline are dissolved in 200 ml waters.Dropwise add 80 milliliters of formaldehyde solutions (concentration expressed in percentage by weight 30%) to the aqueous solution, the Keep agitation aqueous solution is until formaldehyde dissolves completely, and an obtained aniline formaldehyde resin solution.By 200 grams of water glass, 480 milliliters of salpeter solutions (molarity 2M), mix with aniline formaldehyde resin solution, but do not stir the mixture obtained.Mixture is placed in a microwave oven, and utilize microwave output power 2, the microwave treatment mixture of 500W 10 minutes, on the silicon oxide template surface that the lonsdaleite material nucleation allowing the carbonization of aniline formaldehyde resin become is reacted in water glass, and obtained one carbon/silicon composite.Add sodium hydroxide solution (molarity 2M) to carbon/silicon composite.Carbon/silicon composite is placed in microwave oven, and utilizes microwave output power 2, the microwave treatment carbon/silicon composite of 500W 10 minutes, make the lonsdaleite material in carbon/silicon composite have hole.Add hydrofluoric acid solution (concentration expressed in percentage by weight 48%) to carbon/silicon composite, remove silicon oxide template wherein and obtain a Hole type carbon material.Finally, clean with water the carbon material that obtains and carbon material is dried.In hereafter, specially represent Hole type carbon material (as Fig. 9) herein with code name " AFMC ".
Getting 0.08 gram of AFMC and 0.05 gram Platinic chloride and be blended in one in vitro, and dropwise add sodium hydroxide solution (molarity 1M) in vitro, adjusting the pH value of mixing solutions to being greater than 12.After adding 25 milliliters of formaldehyde solutions (concentration expressed in percentage by weight 30%), Keep agitation mixing solutions 6 hours at 100 DEG C.After cooling, in stirred at ambient temperature mixing solutions to overnight.Finally, filter mixing solutions, clean with water the filtration product that obtains and be placed in 160 DEG C of drying in oven products, and obtain a catalyst.As Figure 10, the catalyst of this preparation example is that platinum supports and formed on AFMC, and the rate that supports of platinum is about 20.25%, and particle diameter is about 3nm.In hereafter, special with code name " Pt/AFMC " representative catalyst herein.
" preparation example 5 "
7 grams of urea are dissolved in 200 ml waters.Dropwise add 80 milliliters of formaldehyde solutions (concentration expressed in percentage by weight 30%) to the aqueous solution, the Keep agitation aqueous solution is until formaldehyde dissolves completely, and an obtained urea formaldehyde resin solution.By 200 grams of water glass, 120 milliliters of salpeter solutions (molarity 2M), mix with urea formaldehyde resin solution, but do not stir the mixture obtained.Mixture is placed in a microwave oven, and utilize microwave output power 2, the microwave treatment mixture of 500W 10 minutes, on the silicon oxide template surface that the lonsdaleite material nucleation allowing the carbonization of urea formaldehyde resin become is reacted in water glass, and obtained one carbon/silicon composite.Add sodium hydroxide solution (molarity 2M) to carbon/silicon composite.Carbon/silicon composite is placed in microwave oven, and utilizes microwave output power 2, the microwave treatment carbon/silicon composite of 500W 10 minutes, make the lonsdaleite material in carbon/silicon composite have hole.Add hydrofluoric acid solution (concentration expressed in percentage by weight 48%) to carbon/silicon composite, remove silicon oxide template wherein and obtain a Hole type carbon material.Finally, clean with water the carbon material that obtains and carbon material is dried.In hereafter, specially represent Hole type carbon material (as Figure 11) herein with code name " UFMC ".
Getting 0.08 gram of UFMC and 0.05 gram Platinic chloride and be blended in one in vitro, and dropwise add sodium hydroxide solution (molarity 1M) in vitro, adjusting the pH value of mixing solutions to being greater than 12.After adding 25 milliliters of formaldehyde solutions (concentration expressed in percentage by weight 30%), Keep agitation mixing solutions 6 hours at 100 DEG C.After cooling, in stirred at ambient temperature mixing solutions to overnight.Finally, filter mixing solutions, clean with water the filtration product that obtains and be placed in 160 DEG C of drying in oven products, and obtain a catalyst.As Figure 12, the catalyst of this preparation example is that platinum supports and formed on UFMC, and the rate that supports of platinum is about 20.04%, and particle diameter is about 3nm.In hereafter, special with code name " Pt/UFMC " representative catalyst herein.
" analyzing example 1 "
This analysis is the composition utilizing X-ray diffraction analysis instrument (X-ray diffractomerter, XRD) to confirm the catalyst that preparation example 1 to 5 obtains.In this analysis, adopt each catalyst of Cu K α radiological scans, and the collection of illustrative plates carrying out writing scan obtain with step amplitude velocity rate 2 degrees/min in the scope that 2 θ=10 to 80 are spent.
As Figure 13-17, all can see be positioned at 2 θ=39.7 degree, 46.2 degree, 67.4 degree with the characteristic peak of 81.3 degree, these characteristic peaks correspond to (111) crystal face, (200) crystal face, (220) crystal face and (311) crystal face separately.Therefore, these collection of illustrative plates confirm that Pt/DMC, Pt/SMC, Pt/PFMC, Pt/AFMC and Pt/UFMC are all containing platinum.And for example Figure 13-17, all can see not obvious and about be positioned at the characteristic peak of 2 θ=25 degree, this characteristic peak correspond to the carbon of carbonization.Therefore, prove that Pt/DMC, Pt/SMC, Pt/PFMC, Pt/AFMC and Pt/UFMC are all containing carbon material.
For verifying the above results further, in Figure 18, propose the XRD figure spectrum of the catalyst (representing with code name " Pt/XC-72 ") of reference examples, wherein Pt/XC-72 is that platinum to support on commercial carbon material XC-72 formation.After comparison diagram 13-18, more confirm that Pt/DMC, Pt/SMC, Pt/PFMC, Pt/AFMC and Pt/UFMC are platinum and support and to be formed on carbon material.
" analyzing example 2 "
This analysis is the electrochemical properties taking cyclic voltammetry (cyclic voltammogram) to assess the catalyst that preparation example 1 to 5 obtains.Before carrying out this method, catalyst and Nafion solution (available from DuPont company, weight concentration is 5%) are mixed, then with the mixed solution that ultrasonic vibrating obtains; Then, mixed solution is coated an area and be about 0.066cm
2glassy carbon electrode; Finally, the glassy carbon electrode after drying coated, with fixing catalyst in glassy carbon electrode.When carrying out this method, employing glassy carbon electrode is working electrode, and platinum line is supporting electrode, and silver/silver chloride is reference electrode.And this method is carry out in the 80 milliliters of sulphuric acid solns (molarity is 0.5M) under being full of nitrogen atmosphere.
Please refer to Figure 19, these three catalyst do not have specific oxidation current peak and reduction current peak, but in this three, the peak current of Pt/SMC is maximum, represents it and has the most excellent electro catalytic activity.
Please referring again to Figure 20, these four catalyst do not have specific oxidation current peak and reduction current peak; But in this, the peak current of Pt/AFMC is maximum, represents that it has the most excellent electro catalytic activity.
" analyzing example 3 "
The electrochemical properties of the catalyst that linear sweep voltammetry (line sweep voltammogram) the further assessment preparation example 1 to 5 that this analysis is through collocation rotating disk electrode (rotating disk electrode) obtains.During analysis, adopt the glassy carbon electrode as analyzed example 2 to be working electrode, platinum line is supporting electrode, and silver/silver chloride is reference electrode.This method is carried out in the sulphuric acid soln (molarity is 0.5M) of 80 milliliters under being full of oxygen atmosphere, and the scanning speed of this method is 1mV/s, and scanning direction is negative.
Please refer to Figure 21, Figure 22 and Figure 26, Pt/SMC and Pt/XC-72 has the reduction current high relative to Pt/DMC, illustrates that the reduction reaction catalytic activity of Pt/SMC and Pt/XC-72 is good compared with the reduction reaction catalytic activity of Pt/DMC.
Please separately have compared to the high reduction current of Pt/UFMC referring to Figure 23-26, Pt/PFMC, Pt/AFMC and Pt/XC-72, this illustrates that the reduction reaction catalytic activity of Pt/PFMC, Pt/AFMC and Pt/XC-72 is excellent compared with the reduction reaction catalytic activity of Pt/UFMC.
" analyzing example 4 "
This analysis is the electrochemical properties adopting linear sweep voltammetry further to assess the catalyst that preparation example 1 to 5 obtains.During analysis, adopt the glassy carbon electrode as analyzed example 2 to be working electrode, platinum line is supporting electrode, and silver/silver chloride is reference electrode.This method is carried out in the sulfuric acid/acetum (molarity of the two is 0.5M) of 80 milliliters under being full of nitrogen atmosphere, and the scanning speed of this method is 20mV/s, and scanning direction is negative.
Please refer to Figure 27, Pt/DMC has compared to the little peak current density of Pt/SMC and Pt/XC-72, mean that the reduction reaction poor catalytic activity of reduction reaction catalytic activity compared with Pt/SMC and Pt/XC-72 of Pt/DMC.
Please referring again to Figure 28, Pt/UFMC, there is the peak current density little relative to Pt/PFMC, Pt/AFMC and Pt/XC-72, illustrate that the reduction reaction catalytic activity of Pt/UFMC is not good compared with the reduction reaction catalytic activity of Pt/PFMC, Pt/AFMC and Pt/XC-72.
Comprehensive above-described embodiment, the manufacture method of embodiment of the present invention not only easily operates and quite saves time, and expends the preparation that about six to six ten minutes just can complete Hole type carbon material the soonest.In addition, when the carbon material obtained is in conjunction with the catalyst of platinum as fuel cell, this catalyst still has close to or is better than the electrochemical properties of the catalyst that commercial carbon material XC-72 makes in conjunction with platinum, and therefore the method for embodiment of the present invention also can not affect the quality of the carbon material obtained.
Only as described above, be only preferred embodiment of the present invention, but can not limit scope of the invention process with this; Therefore all simple equivalences done according to the present patent application the scope of the claims and description of the invention content change and modify, and all still remain within the scope of the patent.
Claims (10)
1. a manufacture method for Hole type carbon material, is characterized in that, comprising:
Mixing carbohydrate, water glass, nitric acid and water, to be mixed with a mixture;
One microwave treatment is carried out to this mixture, makes lonsdaleite material nucleation on silicon oxide template surface, to obtain one carbon/silicon composite;
Add sodium hydroxide to this carbon/silicon composite;
Another microwave treatment is carried out to this carbon/silicon composite; And
Add hydrofluoric acid to this carbon/silicon composite, to remove the silicon oxide template in this carbon/silicon composite, this Hole type carbon material obtained.
2. manufacture method as claimed in claim 1, is characterized in that, more comprise:
This Hole type carbon material is cleaned with water; And
Dry this Hole type carbon material.
3. manufacture method as claimed in claim 1, it is characterized in that, the microwave output power of those microwave treatment is 300 to 3,000W, and the time is 3 to 30 minutes.
4. manufacture method as claimed in claim 1, it is characterized in that, this carbohydrate is selected from the group be made up of glucose and Zulkovsky starch.
5. manufacture method as claimed in claim 1, it is characterized in that, this mixing step does not comprise: stir this mixture.
6. a manufacture method for Hole type carbon material, is characterized in that, comprising:
Mixture heat curable type resin, water glass, nitric acid and water, to be mixed with a mixture;
One microwave treatment is carried out to this mixture, makes lonsdaleite material nucleation on silicon oxide template surface, to obtain one carbon/silicon composite;
Add sodium hydroxide to this carbon/silicon composite;
Another microwave treatment is carried out to this carbon/silicon composite; And
Add hydrofluoric acid to this carbon/silicon composite, to remove the silicon oxide template in this carbon/silicon composite, this Hole type carbon material obtained.
7. manufacture method as claimed in claim 6, is characterized in that, more comprise:
This Hole type carbon material is cleaned with water; And
Dry this Hole type carbon material.
8. manufacture method as claimed in claim 6, it is characterized in that, the microwave output power of those microwave treatment is 300 to 3,000W, and the time is 3 to 30 minutes.
9. manufacture method as claimed in claim 6, it is characterized in that, this heat curing-type resin is selected from the group be made up of phenol mela mine-formaldehyde resin, aniline formaldehyde resin and urea formaldehyde resin.
10. manufacture method as claimed in claim 6, it is characterized in that, this mixing step does not comprise: stir this mixture.
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| CN110479212A (en) * | 2019-09-12 | 2019-11-22 | 苏州科技大学 | A kind of preparation method and applications of unordered mesoporous carbon adsorbing material |
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