CN103456969B - Preparation method of Pt-Co/C-single-layer graphene for fuel cell - Google Patents
Preparation method of Pt-Co/C-single-layer graphene for fuel cell Download PDFInfo
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Abstract
The invention discloses a preparation method of Pt-Co/C-single-layer graphene for a fuel cell, belongs to the chemical synthesis field, and relates to a preparation method of graphene. The Pt-Co/C-single-layer graphene for the fuel cell is prepared by the following steps: (1), preparation of graphite oxide; (2), pre-treatment of active carbon XC-72; and (3), preparation of an rGO-XC-72 composite carrier-loaded Pt-Co alloy nano particle. The metal alloy nano particle-graphene and XC-72 active carbon composite catalyst prepared by utilizing a microwave ethylene glycol auxiliary reduction method is simple and easy to implement, and is high in efficiency. Moreover, the obtained graphene has a single-layer structure and the alloy particle has uniform particle diameter distribution and an average particle diameter of 1.5 nm. The catalytic activity of the nano particle can be improved by interaction with the XC-72 active carbon as well as electronic modification to the metal nano particle. And obtained catalyst has excellent oxygen-reduction electro-catalysis performances.
Description
Technical field
The invention belongs to the field of chemical synthesis, relate to a kind of preparation method of Graphene.
Background technology
Graphene (Graphene), be a kind ofly be derived from the two-dimensional structure new material that graphite material has single or multiple lift atomic structure of carbon, it is made up of the atomic structure of carbon being arranged in regular hexagon structure.Graphene is as a kind of special material of 21 century, and the Graphene thickness of single layer structure only has 0.335nm, is to find the thinnest material in the world at present.Relative to other carbon-based supports, the single-layer graphene of perfect structure has larger theoretical specific surface area and (is about 2630m
2g
-1) and better electronic conduction ability (be about 2 × 105cm
2v
-1s
-1), the fields such as electronics, chemistry, machinery can be widely used in.Nearest progress shows that the storage of graphene-based material to electronics and photoelectronic device, chemical sensor, nano composite material and energy has very far-reaching influence (Virendra S, Daeha J, Lei Z, et al. Graphene based materials:Past, present and future [J]. Progress in Materials Science, 2011,56 (8): 1178-1271.).
As everyone knows, Pt base nano-catalyst is modal fuel-cell catalyst, wherein platinum particles normally load on the carriers such as carbon black, gnf, carbon nano-tube.In recent years, the uniqueness showed as catalyst carrier due to Graphene and the physical and chemical performance of brilliance, thus cause the great interest of people.
But due to the expensive of precious metals pt and scarcity of resources, hinder the industrial production of fuel cell.At present, on the research of the fuel-cell catalyst carrier that mainly concentrates on catalyst and composite catalyst.In order to reduce the consumption of precious metals pt, it is a kind of method effectively reducing noble metal dosage, improve catalyst activity that people attempt Pt and other transition metal (as: Fe, Co, Ni, Cr, Cu etc.) to form alloy.Wherein, because Pt-Co alloy easily obtains, become the most frequently used Pt-M alloy.In carried noble metal is catalyst based, carrier plays vital effect.The carrier being generally applicable to fuel-cell catalyst should possess the condition of following several aspect: (l) has good electric conductivity, the electronics of timely iontophoresis electrode reaction needed, the electronics that leadout electrode reaction produces; (2) rational in infrastructure, stable; (3) there is larger specific area, to reduce the use amount of noble metal and to increase the decentralization of catalyst; (4) resistance to corrosion is good, can sustain electrolyte to its produce corrosion failure effect (Jiang Quantong. the preparation of graphene-based fuel-cell catalyst, sign and performance study [D]. Qingdao: Qingdao University of Science and Technology, 2011.).Carbon-based supports, as carbon black, acetylene black, carbon nano-tube etc., wherein carbon nano-tube has because of it ideal chose that good transmission electronic ability and structural stability become fuel-cell catalyst carrier, but Graphene production cost is lower, and performance is more excellent, become the focus of research at present.
Summary of the invention
For improving the catalytic activity of catalyst, Graphene is often difficult to the Graphene that preparation has single layer structure while load alloy.Complex carrier can increase more adsorption site relative to single carrier in theory, increases specific area.XC-72 is combined with two-dimensional graphene, can increases and more adsorb duct.The present invention prepares single-layer graphene catalyst carrier by selecting active carbon XC-72 to assist, reach the object improving catalyst activity, and then a kind of single-layer graphene catalyst preparing support type is provided, and technique simple, benefit batch production, based on chemical stripping legal system for the method for fuel cell with Pt-Co/C-single-layer graphene.
The present invention prepares fuel cell Pt-Co/C-single-layer graphene in accordance with the following steps:
(1) preparation of graphite oxide.Take natural flake graphite as raw material, be oxidized by Hummers method and obtain graphite oxide.This method has done following improvement based on Hummers method: join in 25mL concentrated sulfuric acid flask by potassium peroxydisulfate and each 2.5g of phosphorus pentoxide, at oil bath 40-180 DEG C, stirring and refluxing is after it dissolves, slowly add 1.0-5g graphite powder, stirring reaction heating 2-10h, carry out preliminary treatment to natural flake graphite, filtered water obtains the graphite processed after being washed till neutrality; By the graphite processed, put into the 50-200g concentrated sulfuric acid and stir at ice bath, slowly add 8-30gKMnO
4after in ice bath, stir 1-10h; Proceed in the oil bath pan of 35 ± 3 DEG C, stir 20-120min, then 100-300mL distilled water is slowly added drop-wise in said mixture; Thing to be mixed is cool to room temperature, takes out and puts into 2-5L large beaker, add 500-1500mL distilled water and 5-60mLH
2o
2, continuing to be stirred to does not have bubble to produce, and mixed liquor becomes golden yellow from atropurpureus; Leave standstill 5-48h, abandoning supernatant, mixture volume ratio is HCl and the water centrifuge washing repeatedly of 0.1-2:10, obtains the colloid substance of brown; Colloid substance vacuumize at 30-80 DEG C, grinding obtains dark brown solid, i.e. graphite oxide.
(2) preliminary treatment of active carbon XC-72: adopt red fuming nitric acid (RFNA) acidifying and H
2o
2the processing method combined carries out preliminary treatment to active carbon XC-72, that is: acidification 10-24h after washing is to neutral in 80-120 DEG C of red fuming nitric acid (RFNA) to take 100-200mgXC-72, and 40-60 DEG C of vacuumize, obtains the XC-72 of acidifying; Then by XC-72 good for acidifying at H
2o
2middle ice-bath ultrasonic 20-40min, washing filtering, vacuumize 4-12h.
(3) preparation of rGO-XC-72 composite carrier load Pt-Co alloy nano particle: take 20-50mg graphite oxide powder, add in the mixed solution of 50-100mL ethylene glycol and 10-30mL isopropyl alcohol, ice-bath ultrasonic 15-30min dispersion forms the ethylene glycol suspension-turbid liquid of uniform graphene oxide.Again the XC-72 active carbon 5-30mg handled well is added in above-mentioned graphite oxide ethylene glycol solution, after mixing magnetic agitation 20-60min, ice-bath ultrasonic process 10-20min; The H of 1.7-3.4mL, 0.0386mol/L is instilled in scattered mixture
2ptCl
6with 1.33-2.66mL, 0.1mol/L Co (CH
3cOO)
2solution, magnetic agitation 30-60min, the NaOH solution adjust ph adding 0.2mol/L is 8-11, stirs 10-20min.Put into microwave reactor (power 800W), adopt microwave 1-2min, suspend 0.5-2min, then the program microwave reaction of microwave 0.5-2min.Question response system is cooled to room temperature, with acetone and ethanol repeatedly washing and filtering no longer occur thick to the product after filtering, 60 DEG C of dryings, are ground to Powdered.By above-mentioned gained sample, put into tube furnace, under an argon, 300 DEG C of calcination 30min, collect sample and put into drier.
Metal alloy nanoparticles-Graphene that the present invention utilizes microwave ethylene glycol assisted Reduction method to prepare and XC-72 active carbon composite catalyst, simple, efficiency is high, and the Graphene obtained has single layer structure, the even particle size distribution of alloy particle, average grain diameter is about 1.5nm.By with the interaction of XC-72 active carbon and the catalytic activity that can improve nano particle to the electronics modification of metal nanoparticle.The catalyst obtained has excellent hydrogen reduction electrocatalysis characteristic.
Compared with prior art, the present invention has the following advantages: other carbon carriers relatively, the single-layer graphene of perfect structure its there is excellent physical property, as larger specific area, outstanding mechanical property and better electronic conduction ability.Because the sticky coefficient of ethylene glycol is large, when being uniformly dispersed wherein by graphite oxide, required ultrasonic time increases, but also can add energy between oxidized graphite flake layer due to the lengthening of ultrasonic time simultaneously, thus facilitates the reunion of graphite oxide.Based on this point, in ethylene glycol, add appropriate viscosity coefficient little, low-boiling dispersion aids-isopropyl alcohol, effectively improve the extent of exfoliation of graphite oxide.Add active carbon XC-72 and Graphene compound, the extent of exfoliation of Graphene can be improved on the one hand, carrier on the other hand as catalyst more can adsorb duct for noble metal provides, effectively can improve bimetallic catalyst being uniformly distributed on Graphene, effectively improve the utilance of noble metal, greatly improve the efficiency of battery.The Pt-Co double metallic composite material that the present invention obtains has less particle diameter, and the alloy effect of Pt and Co is relatively more complete, and dispersed at graphenic surface, thus improves the electro catalytic activity of catalyst.
Accompanying drawing explanation
Fig. 1 is the Pt of different GO and XC-72 mass ratio
1-Co
1the XRD figure of/rGO-XC-72 alloy catalyst, Pt
1-Co
1/ rGO
1-XC-72
1(a), Pt
1-Co
1/ rGO
2-XC-72
1(b), Pt
1-Co
1/ rGO
4-XC-72
1(c), Pt
1-Co
1/ rGO (d);
Fig. 2 is Pt
1-Co
1/ rGO
4-XC-72
1transmission electron microscope picture;
Fig. 3 is supporting Pt
1-Co
1transmission electron microscope on single-layer graphene and diffraction pattern thereof;
Fig. 4 is the cyclic voltammetry curve figure of each catalyst;
Fig. 5 is the linear scan curve chart of each catalyst.
Embodiment
Below in conjunction with drawings and Examples, technical scheme of the present invention is further described; but do not limit to so; everyly technical solution of the present invention modified or equivalent to replace, and not departing from the spirit and scope of technical solution of the present invention, all should be encompassed in protection scope of the present invention.
Embodiment 1
(1) take natural flake graphite as raw material, be oxidized by Hummers method and obtain graphite oxide, concrete steps are as follows:
Potassium peroxydisulfate and each 2.5g of phosphorus pentoxide are joined in 25mL concentrated sulfuric acid flask, at oil bath 40-180 DEG C, stirring and refluxing is after it dissolves, slowly add 1.0-5g graphite powder, stirring reaction heating 2-10h, carry out preliminary treatment to natural flake graphite, filtered water obtains the graphite processed after being washed till neutrality; By the graphite processed, put into the 50-200g concentrated sulfuric acid and stir at ice bath, slowly add 8-30gKMnO
4after in ice bath, stir 1-10h; Proceed in the oil bath pan of 35 ± 3 DEG C, stir 20-120min, then 100-300mL distilled water is slowly added drop-wise in said mixture; Thing to be mixed is cool to room temperature, takes out and puts into 2-5L large beaker, add 500-1500mL distilled water and 5-60mLH
2o
2, continuing to be stirred to does not have bubble to produce, and mixed liquor becomes golden yellow from atropurpureus; Leave standstill 5-48h, abandoning supernatant, mixture volume ratio is HCl and the water centrifuge washing repeatedly of 0.1-2:10, obtains the colloid substance of brown; Colloid substance vacuumize at 30-80 DEG C, grinding obtains dark brown solid, i.e. graphite oxide.
(2) first preliminary treatment is carried out to XC-72, namely dry after acidification 12h in 120 DEG C of red fuming nitric acid (RFNA)s; Then by XC-72 good for acidifying at H
2o
2middle ice-bath ultrasonic 30min, washing filtering, vacuumize 4h.
(3) take 40mg graphite oxide powder, add in the mixed solution of 60mL ethylene glycol and 10mL isopropyl alcohol, ice-bath ultrasonic 15min dispersion forms the ethylene glycol suspension-turbid liquid of uniform graphene oxide.The XC-72 active carbon 10mg that reprocessing is good adds in above-mentioned graphite oxide ethylene glycol solution, after mixing magnetic agitation 30min, and ice-bath ultrasonic process 20min.
(4) in scattered mixture, instill the H of 1.7mL, 0.0386mol/L
2ptCl
6with 1.33mL, 0.1mol/L Co (CH
3cOO)
2solution, magnetic agitation 60min, adds the NaOH solution adjust ph (pH value is 8-11) of 0.2mol/L, stirs 10min.Put into microwave reactor (power 800W), adopt microwave 2min, suspend 1min, then the program microwave reaction of microwave 1min.Question response system is cooled to room temperature, with acetone and ethanol repeatedly washing and filtering no longer occur thick to the product after filtering, 60 DEG C of dryings, are ground to Powdered.By above-mentioned gained sample, put into tube furnace, under an argon, 300 DEG C of calcination 30min, collect sample and put into drier.
Embodiment 2
As different from Example 1, control GO and XC-72 mass ratio are 2:1 and 1:1 to the present embodiment, obtain Pt respectively
1-Co
1/ rGO
2-XC-72
1and Pt
1-Co
1/ rGO
1-XC-72
1catalyst.
Embodiment 3
In order to contrast the impact added catalyst performance of active carbon XC-72, spy is one group of contrast experiment.Preparation is simple by graphene-supported catalyst under the same reaction conditions.
(1) step (1) of the preparation reference embodiment 1 of graphite oxide;
(2) take 60mg graphite oxide powder, add in the mixed solution of 60mL ethylene glycol and 10mL isopropyl alcohol, ice-bath ultrasonic 35min dispersion forms the ethylene glycol suspension-turbid liquid of uniform graphene oxide.
(3) step (4) with reference to embodiment 1 utilizes microwave radiation technology ethylene glycol method to obtain Pt
1-Co
1/ rGO catalyst.
By the dry catalyst pulverize obtained, carry out XRD sign.Fig. 1 is Pt and Co atom mass rate when being 1:1, obtains catalyst Pt with the active carbon XC-72 of different quality ratio (being respectively 1:1 (a), 2:1 (b), 4:1 (c) and 1:0 (d)) and graphite oxide
1-Co
1the XRD figure of/GO-XC-72.As shown in Figure 1,2 θ values are 39.8 °, and three peaks of 46.5 ° and 67.8 ° belong to the characteristic diffraction peak of the face-centered cube (fcc) of Pt (JCPDS-ICDD, Card No:04-802).Correspond respectively to (111) of Pt, (200) and (220) crystallographic plane diffraction peak.Prove that all alloy catalysts are all main to exist with single-phase disordered structure.Contrast the data (JCPDS-ICDD) of the diffraction maximum powder diffraction association of mutually isomorphous large volume Pt), the diffraction maximum of Pt-Co alloy offsets to wide-angle.The structure that the skew of Pt (111) diffraction maximum discloses alloy has been incorporated in the middle of the Pt structure of face-centred cubic structure by Co.Because XRD is to mass-sensitive, even very small amount of macroparticle also will make peak shape narrow in sample.Therefore, the broadening of several characteristic peaks of Pt in Fig. 1, shows that prepared several Pt-Co alloy catalysts exist with quite little particle diameter and a kind of ordered form.
Obtained catalyst Pt
1-Co
1/ rGO
4-XC-72
1transmission electron microscope and high resolution TEM photo see Fig. 2, as can be seen from Figure, active carbon XC-72 is adsorbed on Graphene, Pt
1-Co
1particle diameter is 1 ~ 3nm, and load is at active carbon XC-72 and graphenic surface equably.High resolution TEM demonstrates the Pt that the method obtains
1-Co
1nano particle is face-centerd cubic structure, and this and XRD data match.Can learn from the high power transmission electron microscope picture of Fig. 3, the Graphene of load has the feature diffractional lattice of single-layer graphene, illustrates that the Graphene in catalyst exists with single layer structure form.
Take in the middle of 2mg catalyst is dispersed in 2mL redistilled water and absolute ethyl alcohol mixes with 1:1 solution, sonic oscillation 15min, then gets 4 μ L with pipettor, drips to (0.071cm on polished glass-carbon electrode carefully
2), after natural air drying in its air, then dry with 4 μ L0.5wt.%Nafion ethanolic solution coated electrode surfaces.Adopt three-electrode system, at the H of the saturated 0.5mol/L of nitrogen
2sO
4in be 0.5V/s with sweep speed, sweep limits carries out cyclic voltammetry scan for-0.2 to 1.0V.And carry out linear scan test to work electrode, test condition is: electrode potential scope 0.8-0V; Sweep speed 0.0005V/s; Quiescent time is 5s; Reference electrode is Ag/AgCl electrode; Electrolyte is the H of 0.5mol/L
2sO
4; Be pure platinum electrode to electrode.In electro-chemical test forward direction electrolyte, logical oxygen 30min, keeps oxygen saturation in test process.All tests are all carried out at 25 DEG C.
The cyclic voltammetric (Fig. 4) that comprehensive each work electrode obtains and the data that linear scan curve chart (Fig. 5) obtains as shown in table 1, when GO and XC-72 mass ratio is 2:1, catalyst has maximum electrochemically active specific surface area (179.4 m
2g
-1) and half wave potential (0.56V), mean that its catalyst activity is the highest.And when the amount of GO increases, the activity of catalyst reduces on the contrary.This is XC-72 owing to adulterating in catalyst when measuring very little, and the quantity in Catalyst Adsorption site can be provided to reduce, and corresponding electrochemically active specific surface area also reduces, and electron transfer rate is corresponding reduction also, thus causes the reduction of catalytic activity.But relative to preparing Pt under the same conditions
1-Co
1adding of/rGO, active carbon XC-72 makes the electrochemically active specific surface area of catalyst and hydrogen reduction half wave potential all be improved.
Claims (8)
1. a fuel cell preparation method for Pt-Co/C-single-layer graphene, is characterized in that described method step is as follows:
(1) preparation of graphite oxide: take natural flake graphite as raw material, adopts Hummers method to be oxidized and obtains graphite oxide;
(2) preliminary treatment of active carbon XC-72: adopt red fuming nitric acid (RFNA) acidifying and H
2o
2the processing method combined carries out preliminary treatment to active carbon XC-72, and step is as follows: acidification 10-24h after washing is to neutral in 80-120 DEG C of red fuming nitric acid (RFNA) to take 100-200mgXC-72, and 40-60 DEG C of vacuumize, obtains the XC-72 of acidifying; Then by XC-72 good for acidifying at H
2o
2middle ice-bath ultrasonic 20-40min, washing filtering, vacuumize 4-12h;
(3) preparation of rGO-XC-72 composite carrier load Pt-Co alloy nano particle: take 20-50mg graphite oxide powder, add in the mixed solution of 50-100mL ethylene glycol and 10-30mL isopropyl alcohol, ice-bath ultrasonic 15-30min dispersion forms the ethylene glycol suspension-turbid liquid of uniform graphene oxide; Again the XC-72 active carbon 5-30mg handled well is added in above-mentioned graphite oxide ethylene glycol solution, after mixing magnetic agitation 20-60min, ice-bath ultrasonic process 10-20min; The H of 1.7-3.4mL, 0.0386mol/L is instilled in scattered mixture
2ptCl
6with 1.33-2.66mL, 0.1mol/L Co (CH
3cOO)
2solution, magnetic agitation 30-60min, the NaOH solution adjust ph adding 0.2mol/L is 8-11, stirs 10-20min; Put into microwave reactor, adopt microwave 1-2min, suspend 0.5-2min, then the program microwave reaction of microwave 0.5-2min, question response system is cooled to room temperature, with acetone and ethanol repeatedly washing and filtering no longer occur thick to the product after filtering; Then drying, grinding, calcination, obtain fuel cell Pt-Co/C-single-layer graphene.
2. the preparation method of fuel cell Pt-Co/C-single-layer graphene according to claim 1, is characterized in that, in described step (1), the concrete preparation method of graphite oxide is as follows:
Potassium peroxydisulfate and each 2.5g of phosphorus pentoxide are joined in 25mL concentrated sulfuric acid flask, at oil bath 40-180 DEG C, stirring and refluxing is after it dissolves, slowly add 1.0-5g natural flake graphite powder, stirring reaction heating 2-10h, carry out preliminary treatment to natural flake graphite, filtered water obtains the graphite processed after being washed till neutrality; The graphite processed is put into the 50-200g concentrated sulfuric acid stir at ice bath, slowly add 8-30g KMnO
4after in ice bath, stir 1-10h; Proceed in the oil bath pan of 35 ± 3 DEG C, stir 20-120min, then 100-300mL distilled water is slowly added drop-wise in said mixture; Thing to be mixed is cool to room temperature, takes out and puts into 2-5L large beaker, add 500-1500mL distilled water and 5-60mLH
2o
2, continuing to be stirred to does not have bubble to produce, and mixed liquor becomes golden yellow from atropurpureus; Leave standstill 5-48h, abandoning supernatant, mixture volume ratio is HCl and the water centrifuge washing repeatedly of 0.1-2:10, obtains the colloid substance of brown; Colloid substance vacuumize at 30-80 DEG C, grinding obtains dark brown solid, i.e. graphite oxide.
3. the preparation method of fuel cell Pt-Co/C-single-layer graphene according to claim 1, is characterized in that in described step (3), and the power of microwave reactor is 800W.
4. the preparation method of fuel cell Pt-Co/C-single-layer graphene according to claim 1, is characterized in that, in described step (3), filtration product, 60 DEG C of dryings, is ground to Powdered; Then tube furnace is put into, under an argon, 300 DEG C of calcination 30min.
5. the preparation method of fuel cell Pt-Co/C-single-layer graphene according to claim 1, is characterized in that in described step (3), and the atom mass rate of Pt and Co is 1:1.
6. the preparation method of fuel cell Pt-Co/C-single-layer graphene according to claim 1, is characterized in that in described step (3), GO and XC-72 mass ratio is 4:1.
7. the preparation method of fuel cell Pt-Co/C-single-layer graphene according to claim 1, is characterized in that in described step (3), GO and XC-72 mass ratio is 2:1.
8. the preparation method of fuel cell Pt-Co/C-single-layer graphene according to claim 1, is characterized in that in described step (3), GO and XC-72 mass ratio is 1:1.
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| US20220241756A1 (en) * | 2019-06-14 | 2022-08-04 | University Of Maryland, College Park | Systems and methods for high temperature synthesis of single atom dispersions and multi-atom dispersions |
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| CN111987327B (en) * | 2020-08-26 | 2022-07-08 | 福州大学 | Pt/Co nanoparticle-loaded nitrogen-doped graphene and preparation method thereof |
| CN115337936A (en) * | 2022-10-18 | 2022-11-15 | 无锡威孚环保催化剂有限公司 | Preparation of PtCo/C catalyst and method for catalyzing selective hydrogenation of alpha, beta-unsaturated aldehyde by using PtCo/C catalyst |
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