CN104998642A - Preparation method for alcohol fuel zincode catalyst Pd-MnO2/GNRs - Google Patents
Preparation method for alcohol fuel zincode catalyst Pd-MnO2/GNRs Download PDFInfo
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Abstract
The invention relates to a preparation method for alcohol fuel zincode catalyst Pd-MnO2/GNRs. The preparation method comprises three steps that a graphene nanoribbon is prepared; the graphene nanoribbon is modified by the MnO2; palladium nanoparticles are loaded bygraphene modified by the MnO2. The alcohol fuel zincode catalyst is prepared through the three steps. Compared with the prior art, the preparation method for the alcohol fuel zincode catalyst Pd-MnO2/GNRs has the advantages that the graphene nanoribbon modified by the MnO2 is used as banding carrier, the morphological property is uniform and regular, the palladium nanoparticles are distributed uniformly and possess a good catalytic performance in alkaline alcohols, and the preparation technology is simple; the preparation method is suitable for industry scale, and a high economic value is possessed.
Description
Technical field
The invention belongs to direct alcohol fuel cell anode catalyst material preparing technical field, especially relate to a kind of alcohols fuel cell anode catalyst Pd-MnO
2the preparation method of/GNRs.
Background technology
Along with the development of current era, direct alcohol fuel cell due to energy density high, the advantages such as product is pollution-free become energy resource crisis generating suitable replacer.As everyone knows, eelctro-catalyst is the core place of fuel cell, and this is also that fuel cell realizes its business-like key point.Direct alcohol fuel cell catalyst is based on platinum base, but because platinum is expensive, reserves are low and be easily subject to the poisoning of reaction intermediate CO, therefore palladium due to price low and in alkaline solution, the advantages such as the anti-poisoning capability of CO is strong are more and more subject to people's attention.Compared to conventional carriers active carbon, carbon ball, CNT is compared with Graphene, getting graphene nanobelt by longitudinal cutting carbon nanotubes, to be about 10nm wide, and have the energy gap band of field-effect, co catalysis is functional, therefore has huge application prospect on a catalyst support.
Chinese patent CN104485463A discloses the preparation of a kind of alloy-oxide complex carbon material carried noble metal eelctro-catalyst, belongs to field of compound material and fuel-cell catalyst field.Obtain alloy-oxide complex carbon material by simple heat treatment process, then by conventional polyol process, noble-metal-supported is obtained in alloy-oxide complex carbon material.Test chart is levyd existing, and coexist in the complex carbon material supported precious metal catalyst that metal alloy and metal oxide are prepared in the present invention, wherein, metal oxide exists with unformed form.In conjunction with alloy and oxide to the cooperative effect of noble metal, effectively improve noble metal electricity and urge performance, in catalyzing alcohols oxidation, there is good electro catalytic activity and stability.This patent is in control graphene nanobelt by cutting multi-wall carbon nano-tube to obtain metal oxide-loaded by reduction transition metal precursor again, supported precious metal palladium again, compared with CN104485463A, carrier is graphene nanobelt, while the graphene nanobelt obtained by oxidation cutting expands specific area, surface has defect, can be convenient to the attachment of metal oxide, it is convenient that the load for metal nanoparticle improves.Simultaneously in alkaline oxidation of alcohols, manganese dioxide forms hydroxyl oxidize manganese, has good co catalysis performance, is conducive to the electroxidation of alcohols.
Summary of the invention
Object of the present invention is exactly provide a kind of good catalytic performance that has, and the simple alcohols fuel cell anode catalyst Pd-MnO of preparation technology to overcome defect that above-mentioned prior art exists
2the preparation method of/GNRs.
Object of the present invention can be achieved through the following technical solutions:
Alcohols fuel cell anode catalyst Pd-MnO
2the preparation method of/GNRs, adopts following steps:
(1) preparation of graphene nanobelt
Multi-walled carbon nano-tubes is joined in potassium permanganate and the concentrated sulfuric acid, be oxidized under the high temperature conditions, obtain graphene nanobelt through repeatedly eccentric cleaning;
(2) MnO
2grapheme modified nanobelt
After the ultrasonic process of graphene nanobelt, add potassium permanganate and react at 50-120 DEG C, then add reducing agent, obtain the grapheme modified nanobelt of manganese dioxide;
(3) manganese dioxide grapheme modified nanobelt supported palladium nano particle
The graphene nanobelt that manganese dioxide is modified is dissolved in deionized water, adds stabilizing agent and K after ultrasonic process
2pdCl
4, Keep agitation, regulates pH to 8-14, then adds reducing agent slowly with peristaltic pump, Keep agitation, namely obtain alcohols fuel cell anode catalyst Pd-MnO after vacuum drying
2/ GNRs.
In step (1), multi-walled carbon nano-tubes is the 10%-200% of potassium permanganate weight.
In step (2),
Reducing agent is potassium borohydride, sodium borohydride or hydrazine hydrate,
Graphene nanobelt is the 10%-500% of potassium permanganate weight,
Reducing agent is the 200%-1000% of potassium permanganate weight.
In step (3),
Stabilizing agent is trisodium citrate, EDTA, softex kw or urea,
Reducing agent is ethylene glycol, potassium borohydride, sodium borohydride or hydrazine hydrate,
K
2pdCl
4for the 1%-90% of the graphene nanobelt weight that manganese dioxide is modified,
The 500%-1000% of reducing agent and carried metal weight.
The content of the Metal Palladium of the catalyst cupport prepared is 1-90wt%.
The grapheme modified nanobelt of manganese dioxide can also carried noble metal platinum, palladium, gold or silver-colored.
Graphene nanobelt can also be modified through mangano-manganic oxide, tungstic acid, titanium dioxide or molybdenum trioxide.
Prepare catalyst, in alkaline alcohols, there is good catalytic performance.
Described alkaline alcohols is methyl alcohol, ethanol or ethylene glycol.
Compared with prior art, the graphene nanobelt that the present invention modifies with manganese dioxide is for strip-like carrier, shape characteristic is in evenly regular, Pd nano particle is evenly distributed and has good catalytic performance in alkaline alcohols, and preparation technology is simple, be suitable for industrialized scale, there is higher economic worth.
Accompanying drawing explanation
Fig. 1 is that TEM and EDS of the direct alcohol fuel cell anode catalyst material of embodiment 1 gained schemes (a) MnO
2tEM (b) Pd-MnO of/GNRs
2tEM (c) Pd-MnO of/GNRs
2hRTEM (d) Pd-MnO of/GNRs
2the EDS figure of/GNRs
Fig. 2 is the XRD figure of the direct alcohol fuel cell anode catalyst material of embodiment 1 gained;
Fig. 3 is that the direct alcohol fuel cell anode catalyst material of embodiment 1 gained is at 1.0M NaOH+1.0M CH
3cyclic voltammogram in OH;
Fig. 4 is that the direct alcohol fuel cell anode catalyst material of embodiment 1 gained is at 1.0M NaOH+1.0M CH
3time current curve in OH.
Fig. 5 is that the direct alcohol fuel cell anode catalyst material of embodiment 1 gained is at 1.0M NaOH+1.0M CH
3cH
2cyclic voltammogram in OH;
Fig. 6 is that the direct alcohol fuel cell anode catalyst material of embodiment 1 gained is at 1.0M NaOH+1.0M CH
3cH
2time current curve in OH.
Fig. 7 is that the direct alcohol fuel cell anode catalyst material of embodiment 1 gained is at 1.0M NaOH+1.0M C
2h
4(OH)
2in cyclic voltammogram;
Fig. 8 is that the direct alcohol fuel cell anode catalyst material of embodiment 1 gained is at 1.0M NaOH+1.0M C
2h
4(OH)
2in time current curve.
Detailed description of the invention
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
Embodiment 1
A kind of direct alcohol fuel cell anode catalyst carrier material preparation method, described direct alcohol fuel cell anode catalyst material Pd-MnO
2/ GNRs, containing Pd, C, Mn, H and O element.
Above-mentioned direct alcohol fuel cell anode catalyst material preparation method, specifically comprises the following steps:
(1) preparation of graphene nanobelt
By the multi-walled carbon nano-tubes of 1-5g, add potassium permanganate and the 10-1000ml concentrated sulfuric acid of 0.5-15g, be oxidized under the high temperature conditions, through repeatedly eccentric cleaning, freeze drying obtains graphene nanobelt GNRs
(2) MnO
2grapheme modified nanobelt
Be dissolved in by graphene nanobelt in solution ultrasonic, the potassium permanganate adding 1-100g reacts under normal temperature condition, then adds reducing agent ethylene glycol, obtains the graphene nanobelt that manganese dioxide is modified, i.e. MnO
2/ GNRs
(3) the graphene nanobelt supported palladium nano particle of manganese dioxide modification
The graphene nanobelt that 10-100mg manganese dioxide is modified is dissolved in deionized water, and ultrasonic 30-100 minute, adds stabilizing agent, adds the K of 1-100mg
2pdCl
4, Keep agitation, regulate pH, add reducing agent, Keep agitation, vacuum drying 10 hours, both obtained Pd-MnO
2/ GNRs
The direct alcohol fuel cell anode catalyst carrier material Pd-MnO of above-mentioned gained
2/ GNRs is observed by projection electron microscope, as shown in Figure 1.Can carrier MnO from figure (a)
2the manganese dioxide of/GNRs load is unformed shape, can find out catalyst material Pd-MnO from figure (b)
2/ GNRs is evenly distributed, and Pd Nanoparticle Size is about 5nm, and as can be seen from the HRTEM of figure (c), the lattice of Pd nano particle is 0.224nm, basically identical with 0.225nm in document.As can be seen from the EDS figure of figure (d), Pd-MnO
2/ GNRs contains palladium, manganese, oxygen, carbon, with catalyst material Pd-MnO
2contained by/GNRs, element is consistent.
By the direct alcohol fuel cell anode catalyst carrier material Pd-MnO of above-mentioned gained
2/ GNRs utilizes X-ray diffractometer to scan, and as shown in Figure 2, as can be seen from the figure, bottom is MnO to result
2/ GNRs to the face that should have C (002), MnO
2and (020) face (110), that middle is business BASF Pd/C, the top be Pd-MnO
2/ GNRs.As can be seen from the figure, Pd-MnO
2/ GNRs is consistent with Pd (100) face and (200) face in (110) and (020) face that manganese dioxide is corresponding, so not obvious.Equaling 40.2 ° at 2 θ is corresponding Pd (100) face, equaling 46.8 ° at 2 θ is corresponding Pd (200) face, equaling 68.1 ° at 2 θ is corresponding Pd (220) face, equaling 82.1 ° at 2 θ is corresponding Pd (311) face, consistent with business BASF Pd/C, thus prove that what obtain is also metal Pd.
By the direct alcohol fuel cell anode catalyst carrier material Pd-MnO of above-mentioned gained
2/ GNRs tests chemical property in three-electrode system.
Fig. 3 is corresponding Pd-MnO
2/ GNRs and business BASF Pd/C is at 1.0M NaOH+1.0MCH
3cyclic voltammogram in OH.Find out from figure, compare dark BASF Pd/C, the Pd-MnO of light line representative
2/ GNRs methyl alcohol starts oxidizing potential more early, be approximately oxidized from-0.70V, and business BASFPd/C is oxidized from-0.65V, thus proves at Pd-MnO
2in/GNRs, methyl alcohol is more easily oxidized.In the just inswept journey of CV, the once oxidation peak current of corresponding methyl alcohol reaches 990.7mA/mg, and performance approximately improves 38.15% compared with the 717.1mA/mg that the BASFPd/C of business is corresponding.Thus prove that the present invention is more easily oxidized in basic methanol solution and oxidation activity is better.
Fig. 4 is that corresponding Pd-MnO2/GNRs and business BASF Pd/C is at 1.0M NaOH+1.0MCH
3time current curve in OH.Find out from figure, compare dark BASF Pd/C, the time current curve of Pd-MnO2/GNRs in NaOH and methyl alcohol class of light line representative is higher, always on business BASF Pd/C, to this, we have got 4 time points, after 10 seconds, Pd-MnO2/GNRs is 653.5mA/mg and business BASF Pd/C is 311.8mA/mg, after 100 seconds, Pd-MnO2/GNRs is 420.7mA/mg, and business BASF Pd/C is 136.3mA/mg, after 1000 seconds, Pd-MnO2/GNRs is 250.7mA/mg, and business BASF Pd/C is 34.9mA/mg, after 3600 seconds, Pd-MnO2/GNRs is 170.6mA/mg, and business BASF Pd/C is 9.9mA/mg.Thus prove at 1.0M NaOH+1.0M CH
3in the solution of OH, As time goes on, the stability that Pd-MnO2/GNRs compares the BASF Pd/C of business in alkaline methanol catalytic process is better!
Fig. 5 is corresponding Pd-MnO
2/ GNRs and business BASF Pd/C is at 1.0M NaOH+1.0MCH
3cH
2cyclic voltammogram in OH.Find out from figure, compare dark BASF Pd/C, the Pd-MnO of light line table
2/ GNRs ethanol starts oxidizing potential more early, be approximately oxidized from-0.75V, and business BASFPd/C is oxidized from-0.62V, thus proves at Pd-MnO
2in/GNRs, ethanol is more easily oxidized.In the just inswept journey of CV, the once oxidation peak current of corresponding ethanol reaches 2510.4mA/mg, and performance approximately improves 89.25% compared with the 1326.5mA/mg that the BASFPd/C of business is corresponding.Thus prove that the present invention is more easily oxidized in alkaline ethanol solution and oxidation activity is better.
Fig. 6 is that corresponding Pd-MnO2/GNRs and business BASF Pd/C is at 1.0M NaOH+1.0MCH
3cH
2time current curve in OH.Find out from figure, compare dark BASF Pd/C, the time current curve of Pd-MnO2/GNRs in ethanolic solution of light line representative is higher, always on business BASFPd/C, to this, we have got 4 time points, after 10 seconds, Pd-MnO2/GNRs is 1147.5mA/mg, and business BASF Pd/C is 653.5mA/mg, after 100 seconds, Pd-MnO2/GNRs is 922.5mA/mg, and business BASF Pd/C is 420.6mA/mg, after 1000 seconds, Pd-MnO2/GNRs is 683.0mA/mg, and business BASF Pd/C is 250.7mA/mg, after 3600 seconds, Pd-MnO2/GNRs is 513.0mA/mg and business BASF Pd/C is 170.6mA/mg.Thus prove at 1.0M NaOH+1.0M CH
3in the solution of OH, As time goes on, the stability that Pd-MnO2/GNRs compares the BASF Pd/C of business in alkaline ethanol catalytic process is better!
Fig. 7 is corresponding Pd-MnO
2/ GNRs and business BASF Pd/C is at 1.0M NaOH+1.0M C
2h
4(OH)
2in cyclic voltammogram.Find out from figure, compare dark BASF Pd/C, the Pd-MnO of light line representative
2/ GNRs ethylene glycol starts oxidizing potential more early, be approximately oxidized from-0.60V, and business BASFPd/C is oxidized from-0.55V, thus proves at Pd-MnO
2in/GNRs, ethylene glycol is more easily oxidized.In the just inswept journey of CV, the once oxidation peak current of corresponding ethylene glycol reaches 1616.3mA/mg, and performance approximately improves 63.05% compared with the 991.3mA/mg that the BASF Pd/C of business is corresponding.Thus prove that the present invention is more easily oxidized in alkaline ethylene glycol solution and oxidation activity is better.
Fig. 8 is that corresponding Pd-MnO2/GNRs and business BASF Pd/C is at 1.0M NaOH+1.0MC
2h
4(OH)
2in time current curve.Find out from figure, compare dark BASF Pd/C, the time current curve of Pd-MnO2/GNRs in NaOH and ethylene glycol solution of light line representative is higher, always on business BASF Pd/C, to this, we have got 4 time points, after 10 seconds, Pd-MnO2/GNRs is 1707.5mA/mg, and business BASF Pd/C is 885.0mA/mg, after 100 seconds, Pd-MnO2/GNRs is 1145.0mA/mg, and business BASF Pd/C is 408.4mA/mg, after 1000 seconds, Pd-MnO2/GNRs is 589.5mA/mg, and business BASF Pd/C is 166.5mA/mg, after 3600 seconds, Pd-MnO2/GNRs is 485.4mA/mg, and business BASF Pd/C is 117.8mA/mg.Thus prove at 1.0M NaOH+1.0M C
2h
4(OH)
2solution in, As time goes on, the stability that Pd-MnO2/GNRs compares the BASF Pd/C of business in alkaline ethylene glycol catalytic process is better!
Embodiment 2
A kind of direct alcohol fuel cell anode catalyst carrier material preparation method, described direct alcohol fuel cell anode catalyst material Pt-MnO
2/ GNRs, containing Pt, C, Mn, H and O element.
Above-mentioned direct alcohol fuel cell anode catalyst material preparation method, specifically comprises the following steps:
(1) preparation of graphene nanobelt
By the multi-walled carbon nano-tubes of 1-5g, add potassium permanganate and the 10-1000ml concentrated sulfuric acid of 0.5-15g, be oxidized under the high temperature conditions, through repeatedly eccentric cleaning, freeze drying obtains graphene nanobelt GNRs
(2) MnO
2grapheme modified nanobelt
Just graphene nanobelt is dissolved in solution ultrasonic, and the potassium permanganate adding 1-100g reacts under normal temperature condition, then adds reducing agent ethylene glycol, obtains the graphene nanobelt that manganese dioxide is modified, i.e. MnO
2/ GNRs
(3) the graphene nanobelt supported palladium nano particle of manganese dioxide modification
The graphene nanobelt that the manganese dioxide of 20mg is modified is dissolved in deionized water, and ultrasonic 30min, adds stabilizing agent, adds the K of 1-100mg
2ptCl
6, Keep agitation, regulate pH, add reducing agent, Keep agitation, vacuum drying 10 hours, both obtained Pt-MnO
2/ GNRs
Embodiment 3
A kind of direct alcohol fuel cell anode catalyst carrier material preparation method, described direct alcohol fuel cell anode catalyst material Au-MnO
2/ GNRs, containing Au, C, Mn, H and O element.
Above-mentioned direct alcohol fuel cell anode catalyst material preparation method, specifically comprises the following steps:
(1) preparation of graphene nanobelt
By the multi-walled carbon nano-tubes of 1-5g, add potassium permanganate and the 10-1000ml concentrated sulfuric acid of 0.5-15g, be oxidized under the high temperature conditions, through repeatedly eccentric cleaning, freeze drying obtains graphene nanobelt GNRs
(2) MnO
2grapheme modified nanobelt
Be dissolved in by graphene nanobelt in solution ultrasonic, the potassium permanganate adding 1-100g reacts under normal temperature condition, then adds reducing agent hydrazine hydrate, obtains the graphene nanobelt that manganese dioxide is modified, i.e. MnO
2/ GNRs
(3) the graphene nanobelt supported palladium nano particle of manganese dioxide modification
The graphene nanobelt that the manganese dioxide of 20mg is modified is dissolved in deionized water, and ultrasonic 30min, adds stabilizing agent, adds a certain amount of HAuCl
4, Keep agitation, regulates pH 8-14, adds reducing agent hydrazine hydrate, Keep agitation, vacuum drying, both obtained Au-MnO
2/ GNRs
Embodiment 4
A kind of direct alcohol fuel cell anode catalyst carrier material preparation method, described direct alcohol fuel cell anode catalyst material Pd-TiO
2/ GNRs, containing Pd, C, Ti, H and O element.
Above-mentioned direct alcohol fuel cell anode catalyst material preparation method, specifically comprises the following steps:
(1) preparation of graphene nanobelt
By the multi-walled carbon nano-tubes of 1-5g, add potassium permanganate and the 10-1000ml concentrated sulfuric acid of 0.5-15g, be oxidized under the high temperature conditions, through repeatedly eccentric cleaning, freeze drying obtains graphene nanobelt GNRs
(2) TiO
2grapheme modified nanobelt
Graphene nanobelt is dissolved in solution ultrasonic, adds the TiO of 1-100g
2react under normal temperature condition, obtain the graphene nanobelt that titanium dioxide is modified, i.e. TiO
2/ GNRs
(3) the graphene nanobelt supported palladium nano particle of titanium dioxide modification
The graphene nanobelt that 10mg titanium dioxide is modified is dissolved in deionized water, and ultrasonic 10-100 minute, adds stabilizing agent, adds the K of 1-50mg
2pdCl
4, Keep agitation, regulates pH 7-14, adds reducing agent, Keep agitation, vacuum drying, both obtained Pd-TiO
2/ GNRs
Embodiment 5
A kind of direct alcohol fuel cell anode catalyst carrier material preparation method, described direct alcohol fuel cell anode catalyst material Pd-MoO
3/ GNRs, containing Pd, C, Mo, H and O element.
Above-mentioned direct alcohol fuel cell anode catalyst material preparation method, specifically comprises the following steps:
(1) preparation of graphene nanobelt
By the multi-walled carbon nano-tubes of 1-5g, add potassium permanganate and the 10-1000ml concentrated sulfuric acid of 0.5-15g, be oxidized under the high temperature conditions, through repeatedly eccentric cleaning, freeze drying obtains graphene nanobelt GNRs
(2) MoO
3grapheme modified nanobelt
Graphene nanobelt is dissolved in solution ultrasonic, adds the MoO of 1-100g
3react under normal temperature condition, obtain the graphene nanobelt that molybdenum trioxide is modified, i.e. MoO
3/ GNRs
(3) the graphene nanobelt supported palladium nano particle of molybdenum trioxide modification
The graphene nanobelt that 10-100mg molybdenum trioxide is modified is dissolved in deionized water, and ultrasonic certain 10-100 minute, adds stabilizing agent, the K added
2pdCl
4, Keep agitation, regulates pH 8-14, adds reducing agent hydrazine hydrate, Keep agitation, vacuum drying, both obtained Pd-MoO
3/ GNRs
Embodiment 6
A kind of direct alcohol fuel cell anode catalyst carrier material preparation method, described direct alcohol fuel cell anode catalyst material Pd-WO
3/ GNRs, containing Pd, C, W, H and O element.
Above-mentioned direct alcohol fuel cell anode catalyst material preparation method, specifically comprises the following steps:
(1) preparation of graphene nanobelt
By the multi-walled carbon nano-tubes of 10-100mg, add potassium permanganate and the concentrated sulfuric acid of 1-100mg, be oxidized under the high temperature conditions, through repeatedly eccentric cleaning, freeze drying obtains graphene nanobelt GNRs
(2) MoO
3grapheme modified nanobelt
Graphene nanobelt is dissolved in solution ultrasonic, adds the WO of 1-100mg
3react under normal temperature condition, obtain the graphene nanobelt that tungstic acid is modified, i.e. MoO
3/ GNRs
(3) the graphene nanobelt supported palladium nano particle of tungstic acid modification
The graphene nanobelt that the tungstic acid of 1-100mg is modified is dissolved in deionized water, and ultrasonic 10-100 minute, adds stabilizing agent, adds K
2pdCl
4, Keep agitation, regulates pH 8-14, adds borane reducing agent sodium hydride, Keep agitation, vacuum drying, both obtained Pd-WO
3/ GNRs.
Embodiment 7
Alcohols fuel cell anode catalyst Pd-MnO
2the preparation method of/GNRs, adopts following steps:
(1) preparation of graphene nanobelt
Joined by multi-walled carbon nano-tubes in potassium permanganate and the concentrated sulfuric acid, multi-walled carbon nano-tubes is 10% of potassium permanganate weight, is oxidized under the high temperature conditions, obtains graphene nanobelt through repeatedly eccentric cleaning;
(2) MnO
2grapheme modified nanobelt
After the ultrasonic process of graphene nanobelt, add potassium permanganate to react at 50 DEG C, graphene nanobelt is 10% of potassium permanganate weight, then adds borane reducing agent hydrofining, reducing agent is 200% of potassium permanganate weight, obtains the grapheme modified nanobelt of manganese dioxide;
(3) manganese dioxide grapheme modified nanobelt supported palladium nano particle
The graphene nanobelt that manganese dioxide is modified is dissolved in deionized water, adds stabilizing agent trisodium citrate and K after ultrasonic process
2pdCl
4, K
2pdCl
4for 1% Keep agitation of the graphene nanobelt weight that manganese dioxide is modified, pH is regulated to be adjusted to 8, add reducing agent ethylene glycol slowly with peristaltic pump again, 500% Keep agitation of reducing agent and carried metal weight, namely obtains alcohols fuel cell anode catalyst Pd-MnO after vacuum drying
2/ GNRs, the content of the Metal Palladium of catalyst cupport is 1wt%.
Embodiment 8
Alcohols fuel cell anode catalyst Pd-MnO
2the preparation method of/GNRs, adopts following steps:
(1) preparation of graphene nanobelt
Joined by multi-walled carbon nano-tubes in potassium permanganate and the concentrated sulfuric acid, multi-walled carbon nano-tubes is 100% of potassium permanganate weight, is oxidized under the high temperature conditions, obtains graphene nanobelt through repeatedly eccentric cleaning;
(2) MnO
2grapheme modified nanobelt
After the ultrasonic process of graphene nanobelt, add potassium permanganate to react at 80 DEG C, graphene nanobelt is 100% of potassium permanganate weight, then adds borane reducing agent sodium hydride, reducing agent is 500% of potassium permanganate weight, obtains the grapheme modified nanobelt of manganese dioxide;
(3) manganese dioxide grapheme modified nanobelt supported palladium nano particle
The graphene nanobelt that manganese dioxide is modified is dissolved in deionized water, adds stabilizing agent softex kw and K after ultrasonic process
2pdCl
4, K
2pdCl
4for 50% of the graphene nanobelt weight that manganese dioxide is modified, Keep agitation, regulates pH to be 10, borane reducing agent sodium hydride is added slowly again with peristaltic pump, 700% of reducing agent and carried metal weight, Keep agitation, namely obtains alcohols fuel cell anode catalyst Pd-MnO after vacuum drying
2/ GNRs, the content of the Metal Palladium of catalyst cupport is 50wt%.
Embodiment 9
Alcohols fuel cell anode catalyst Pd-MnO
2the preparation method of/GNRs, adopts following steps:
(1) preparation of graphene nanobelt
Joined by multi-walled carbon nano-tubes in potassium permanganate and the concentrated sulfuric acid, multi-walled carbon nano-tubes is 200% of potassium permanganate weight, is oxidized under the high temperature conditions, obtains graphene nanobelt through repeatedly eccentric cleaning;
(2) MnO
2grapheme modified nanobelt
After the ultrasonic process of graphene nanobelt, add potassium permanganate to react at 120 DEG C, graphene nanobelt is 500% of potassium permanganate weight, then adds reducing agent hydrazine hydrate, reducing agent is 1000% of potassium permanganate weight, obtains the grapheme modified nanobelt of manganese dioxide;
(3) manganese dioxide grapheme modified nanobelt supported palladium nano particle
The graphene nanobelt that manganese dioxide is modified is dissolved in deionized water, adds stabilizing agent urea and K after ultrasonic process
2pdCl
4, K
2pdCl
4for 90% of the graphene nanobelt weight that manganese dioxide is modified, Keep agitation, regulates pH to be 14, reducing agent hydrazine hydrate is added slowly again with peristaltic pump, 1000% of reducing agent and carried metal weight, Keep agitation, namely obtains alcohols fuel cell anode catalyst Pd-MnO after vacuum drying
2/ GNRs, the content of the Metal Palladium of catalyst cupport is 90wt%.
The above is only the citing of embodiments of the present invention; it should be pointed out that for those skilled in the art, under the prerequisite not departing from the technology of the present invention principle; can also make some improvement and modification, these improve and modification also should be considered as protection scope of the present invention.
Claims (9)
1. alcohols fuel cell anode catalyst Pd-MnO
2the preparation method of/GNRs, is characterized in that, the method adopts following steps:
(1) preparation of graphene nanobelt
Multi-walled carbon nano-tubes is joined in potassium permanganate and the concentrated sulfuric acid, be oxidized under the high temperature conditions, obtain graphene nanobelt through repeatedly eccentric cleaning;
(2) MnO
2grapheme modified nanobelt
After the ultrasonic process of graphene nanobelt, add potassium permanganate and react at 50-120 DEG C, then add reducing agent, obtain the grapheme modified nanobelt of manganese dioxide;
(3) manganese dioxide grapheme modified nanobelt supported palladium nano particle
The graphene nanobelt that manganese dioxide is modified is dissolved in deionized water, adds stabilizing agent and K after ultrasonic process
2pdCl
4, Keep agitation, adjustment pH is 8-14, then adds reducing agent slowly with peristaltic pump, Keep agitation, namely obtains alcohols fuel cell anode catalyst Pd-MnO after vacuum drying
2/ GNRs.
2. alcohols fuel cell anode catalyst Pd-MnO according to claim 1
2the preparation method of/GNRs, is characterized in that, the multi-walled carbon nano-tubes described in step (1) is the 10%-200% of potassium permanganate weight.
3. alcohols fuel cell anode catalyst Pd-MnO according to claim 1
2the preparation method of/GNRs, is characterized in that, in step (2)
Reducing agent is potassium borohydride, sodium borohydride or hydrazine hydrate,
Graphene nanobelt is the 10%-500% of potassium permanganate weight,
Reducing agent is the 200%-1000% of potassium permanganate weight.
4. alcohols fuel cell anode catalyst Pd-MnO according to claim 1
2the preparation method of/GNRs, is characterized in that, in step (3)
Stabilizing agent is trisodium citrate, EDTA, softex kw or urea,
Reducing agent is ethylene glycol, potassium borohydride, sodium borohydride or hydrazine hydrate,
K
2pdCl
4for the 1%-90% of the graphene nanobelt weight that manganese dioxide is modified,
The 500%-1000% of reducing agent and carried metal weight.
5. alcohols fuel cell anode catalyst Pd-MnO according to claim 1
2the preparation method of/GNRs, is characterized in that, the content of the Metal Palladium of the catalyst cupport prepared is 1-90wt%.
6. alcohols fuel cell anode catalyst Pd-MnO according to claim 1
2the preparation method of/GNRs, is characterized in that, the grapheme modified nanobelt of manganese dioxide can also carried noble metal platinum, palladium, gold or silver-colored.
7. alcohols fuel cell anode catalyst Pd-MnO according to claim 1
2the preparation method of/GNRs, is characterized in that, graphene nanobelt can also be modified through mangano-manganic oxide, tungstic acid, titanium dioxide or molybdenum trioxide.
8. alcohols fuel cell anode catalyst Pd-MnO according to claim 1
2the preparation method of/GNRs, is characterized in that, prepares catalyst and have good catalytic performance in alkaline alcohols.
9. alcohols fuel cell anode catalyst Pd-MnO according to claim 8
2the preparation method of/GNRs, is characterized in that, described alkaline alcohols is methyl alcohol, ethanol or ethylene glycol.
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