CN101219378A - Process for producing direct methanol fuel cell electro-catalyst - Google Patents
Process for producing direct methanol fuel cell electro-catalyst Download PDFInfo
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- CN101219378A CN101219378A CNA2007100328054A CN200710032805A CN101219378A CN 101219378 A CN101219378 A CN 101219378A CN A2007100328054 A CNA2007100328054 A CN A2007100328054A CN 200710032805 A CN200710032805 A CN 200710032805A CN 101219378 A CN101219378 A CN 101219378A
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Abstract
The invention discloses a preparation method of an electrocatalyst of direct methanol fueled battery. A carbon nano tube carrier is purified and activated, and then a solution of platinum or platinum-ruthenium mixture nano particles is prepared; the carbon nano tube and platinum or platinum-ruthenium mixture are mixed in a mass ratio of 1: 0.02 to 1: 0.80: firstly, the carbon nano tube is dispersed with glycol, and added with the platinum or platinum- ruthenium mixture nano particle solution, then treated by 200 to 500W ultrasonic for 1 to 5 hours, thus the electrocatalyst of the direct methanol fueled battery is prepared. The preparation method of the electrocatalyst of the invention does not need surfactant, stabilizer or functional molecule, metal particles do not congregate at normal temperature and are loaded on high density small grain diameter of the carbon nano tubes.
Description
Technical field
The present invention relates to catalyst field, particularly a kind of preparation method of DMFC eelctro-catalyst.
Background technology
(direct methanol fuel cell, DMFC), low price abundant owing to its fuel source, transportation and storage are safer is subjected to extensive attention to DMFC.Yet the poisoning effect of the low catalytic activity of anode catalyst and methanol oxidation intermediate carbonyl compound causes the practical application development speed of DMFC comparatively slow always.The noble metal nano particles such as platinum of employing high dispersive are carried on carbon nano tube surface and are widely studied as the DMFC catalyst.It is little and to be evenly distributed be the content that Many researchers is considered how to design preparation tube wall surface noble metal particle diameter.At present, method for preparing catalyst mainly contains following several: (1) immersion reduction method [Xing Wei, Rongbing, Lu Tianhong.Method of preparing ofnanometer electrocatalyst for proton exchange membrane fuel cell.USAPatent, 2003,6518217], be to prepare the simplest method commonly used of carrier metal catalyst, be maceration extract directly promptly with various slaines, with different reducing agents, different carbonaceous materials are made carrier, even substitute Preparation of Activated Carbon catalyst commonly used with CNT simply.Basic process is, carrier is scattered in the maceration extract that contains various platinum presomas fully dipping, adds various reducing agents reducing metal ion or metal complexs such as sodium borohydride, hydrazine, formaldehyde then; After treating that perhaps the part maceration extract is adsorbed on the carrier carbon material of loose structure, make it reduction, the metal-carrier granular that obtains disperseing at a certain temperature with reducibility gas.This method mainly is to rely on capillarity to make metal salt solution be penetrated in the pore structure of carrier inside prosperity by dipping, active component is fully adsorbed and stable existence, therefore, the performance of the adsorption capacity appreciable impact last catalyst of the active component in the liquid on carrier strengthens its adhesive ability so part Study person adds various stabilizing agents (for example natrium citricum, disodium ethylene diamine tetraacetate, sodium tartrate etc.).When the adding reducing agent reduces, because the influence of diffusional resistance, active component in the bulk solution at first is reduced, because the existence of adsorption equilibrium, along with reaction is carried out, the concentration of active component reduces gradually in the solution, the adsorption equilibrium that active component exists between bulk solution and carrier moves to the solution direction, be adsorbed on the interpore part active component of carrier granular desorption and get back to bulk solution participation reduction reaction, therefore, must cause metallic gathering in the carried catalyst at last, particle diameter is bigger, skewness and load capacity are low etc., influence catalytic performance.If add functional compounds coupling activity component and carriers such as surfactant, perhaps use the gas reduction method, also to carry out at a certain temperature at last, also can cause metallic to be assembled.Platinum compounds such as H commonly used
2PtCl
6And the absorption between the carbon carrier neither a simple electrostatic process, and carbon also can reduce a part of platinum presoma in the time of absorption, and asynchronous reduction also can cause the particle diameter skewness.In addition, because the carbon internal microcellular structure is abundant, the metallic that partial reduction obtains is hidden in it deeply, and the diffusion-restricted of being reacted can not make full use of, and causes the effective active component to reduce, and reduces the utilization rate of platinum.(2) colloid reducing process [Yuan Wang; Jiawen Ren; Kai Deng; Linlin Gui; Youqi Tang.Preparation of Tractable Platinum; Rhodium; andRuthenium Nanoclusters with Small Particle Size in Organic Media.Chem.Mater.2000,12,1622-1627]; commonly used is the reduction of ethylene glycol method at present; the compound that is about to platinum melts in ethylene glycol solution, adds surfactant, regulates the pH value; 130～160 ℃ of reduction under inert gas shielding; because reaction temperature is fast at a high speed, the nucleation and growth of metallic almost carries out synchronously, again because various stabilizing agent (polymer and then; complex; cellulose derivative, even methyl alcohol etc.) coat the metal nanoparticle that has just synthesized, make it to be difficult for assembling; thereby reach homodisperse effect, load on the various carriers by various ways then.Nano platinum particle loads to the carbon nano tube surface design route and is divided three classes: the one, and with the carbon nano tube surface functionalization, allow nano platinum particle be coupled then; The 2nd, seek ideal functionality molecule (quaternary amine for example, alkyl hydrosulfide, triphenylphosphine etc.) modify nano platinum particle, allow its grafting to carbon nano tube surface by ways such as phase transfers, because CNT is very poor in aqueous solution dissolubility, but organic solvent for example toluene certain dissolubility is arranged; The 3rd, be regardless of to go on foot and carry out, with CNT and platinum presoma, surfactant mixes, and nano platinum particle restores promptly and carrier is wrapped in together.But the removal of these functional moleculars, surfactant, stabilizing agent at last also is to carry out at a certain temperature, so metallic is reunited after causing load easily.
Summary of the invention
The objective of the invention is to overcome the shortcoming that exists in the prior art, provide that a kind of good stability, cost are low, the preparation method of the simple DMFC eelctro-catalyst of technology.
Purpose of the present invention is achieved through the following technical solutions:
The preparation method of DMFC eelctro-catalyst comprises the steps: at first carbon nanotube carrier to be carried out purifying and activation processing; Prepare platinum or platinum ruthenium mixture nano-particle solution then; Be 1: 0.02～1: 0.80 proportioning again by the mass ratio of CNT and platinum or platinum ruthenium mixture, adopt the ethylene glycol dispersing Nano carbon tubes earlier, add platinum or platinum ruthenium mixture nano-particle solution then, adopt 200～500W ultrasonic wave to carry out ultrasonic wave again and handled 1～5 hour, prepare the DMFC eelctro-catalyst.
Describedly carbon nanotube carrier is carried out purification process be meant CNT soaked 12～48 hours that filtration washing to filtrate is neutral then in concentrated hydrochloric acid, again 80～100 ℃ dry 1～2 hour down, obtain the carbon nanotube carrier of purifying.
It is described that carbon nanotube carrier is carried out activation processing is to carry out activation processing by the multistep oxidation, promptly CNT is joined in the container, added hot reflux 1～5 hour, centrifugation at 0～100 ℃ with 1～5mmol/L NaOH, be filtered to filtrate for neutral, 80～100 ℃ of dryings are 1～2 hour again; Placing volume ratio then is 3: 1 dense HNO
3(content 65～68%) and dense H
2SO
4In the mixed acid solution of (content 95～98%), added hot reflux 1～5 hour at 60～100 ℃, centrifugation, filtration washing to filtrate is neutral, 80～100 ℃ of dryings 1～2 hour.
Described preparation nano platinum particle is meant: the chloroplatinic acid and 1～5 gram NaOH of 0.1～1 gram are dissolved in 50～250mL ethylene glycol solution (pH ≈ 12～14) respectively, and ultrasonic then dispersion mixes; Logical 10～30 minutes deaerations of nitrogen; 130～160 ℃ of oil baths added hot reflux 1～5 hour under blanket of nitrogen then, carried out electromagnetic agitation simultaneously, obtained nano platinum particle at last.
Described preparation platinum ruthenium mixture nano particle is meant: the ruthenium trichloride and 1～5 gram NaOH of 0.1～1 gram are dissolved in 50～250mL ethylene glycol solution (pH ≈ 12～14) respectively, and ultrasonic then dispersion mixes; Logical 10～30 minutes deaerations of nitrogen; 130～160 ℃ of oil baths added hot reflux 1～5 hour under blanket of nitrogen then, carried out electromagnetic agitation simultaneously, obtained ruthenium nano particle; Last again ruthenium nano particle the mixing with the above-mentioned nano platinum particle for preparing obtains platinum ruthenium mixture nano particle.
The present invention adopts ultrasonic wave that CNT and platinum or platinum ruthenium mixture nano particle are evenly mixed by microwave vibrations.Ultrasonic wave is the same with sound wave, it is a kind of vibration wave of density, pressure in the medium is done alternately to change, and as a certain definite point in the liquid is observed, is the center with the static pressure, produce the increase and decrease of pressure, if increase ultrasonic intensity successively, pressure amplitude can produce a kind of power of tearing also along with increase in this regional liquid, and form the cavity of vacuum, and vanished by the extrusion of the compression stress of back again.This vibration under the sound field effect, when acoustic pressure reaches certain value, bubble will increase rapidly, and will be closed suddenly again then.When bubble is closed,, powerful shock wave will be produced because liquid collides mutually.This shock wave makes platinum or platinum ruthenium mixture nano particle spread loads to carbon nano tube surface, make platinum or platinum ruthenium mixture nano particle by with the functional group coupled load of carbon nano tube surface to carbon nano tube surface.
The present invention compared with prior art has following advantage and effect:
(1) preparation method of eelctro-catalyst of the present invention is simple, need not surfactant, stabilizing agent or functional molecular etc., and metallic particles can not be reunited at normal temperatures, and in the load of carbon nano tube surface high density small particle diameter.
(2) the catalyst electro-catalysis methanol oxidation effect that makes is than commercial catalysts (Pt/C (VulcanXC-72,20%, JM) good, just sweeping the oxidation peak quality and exceeding approximately 34% than current density, just sweeping the oxidation peak quality and exceeding 2 times of commercial catalysts than the ratio of current density than current density and the negative oxidation peak quality of sweeping.
Description of drawings
Fig. 1 is the transmission electron microscope picture that the CNT of nano platinum particle (a) and the present invention's preparation carries platinum (Pt/MWCNTs) eelctro-catalyst (b).
Fig. 2 is the infrared spectrogram of CNT preliminary treatment front and rear surfaces group.
The graph of pore diameter distribution that Fig. 3 obtains for CNT preliminary treatment anteroposterior diameter nitrogen adsorption desorption thermoisopleth.
The CNT that Fig. 4 prepares for the present invention carries platinum (Pt/MWCNTs) catalyst and carbon carries platinum (Pt/C, X-ray diffraction JM) (XRD) comparison diagram.
Fig. 5 is the methanol catalytic oxidation comparison diagram of the existing catalyst of catalyst and market of the present invention's preparation.
The specific embodiment
Below in conjunction with embodiment the present invention is done further detailed description, but embodiments of the present invention are not limited thereto.
1 gram chloroplatinic acid and 1 gram NaOH are dissolved in the 50mL ethylene glycol solution respectively, and ultrasonic then dispersion mixes; Logical 15 minutes deaerations of nitrogen, the oil bath of 130 ℃ of degree added hot reflux 3 hours under blanket of nitrogen then, and the magnetic that do not have a power failure therebetween stirs; Treat to stop ventilation after temperature is reduced to room temperature, make 3.76mg/mL platinum colloidal sol.
CNT was soaked in concentrated hydrochloric acid 24 hours, and filtration washing to filtrate is neutral then, descends dry 2 hours at 100 ℃ again, obtains the carbon nanotube carrier of purifying.CNT is joined in the round-bottomed flask, NaOH (3mmol/L) added hot reflux 1 hour for 70 ℃ again, and centrifugation is filtered to filtrate for neutral, 100 ℃ of dryings 2 hours; Placing volume ratio then is 3: 1 dense HNO
3With dense H
2SO
4Mixed acid solution in, 70 ℃ added hot reflux 5 hours, centrifugation, filtration washing to filtrate is neutral, 100 ℃ of dryings 2 hours.
Weighing 100mg is scattered in a small amount of ethylene glycol solution through the CNT of above-mentioned purifying and activation processing is ultrasonic.Dropwise add the above-mentioned platinum colloidal sol 6mL for preparing, the ultrasonic dispersion of 250W 5 hours, centrifugation is repeatedly washed with absolute ethyl alcohol and distilled water, and 100 ℃ of dryings obtain load capacity and are about 18.4% Pt/MWCNTs catalyst.
Embodiment 2:
0.4 gram ruthenium trichloride and 1 gram NaOH are dissolved in the 50mL ethylene glycol solution respectively, and ultrasonic then dispersion mixes; Logical 15 minutes deaerations of nitrogen; 130 ℃ of oil baths added hot reflux 3 hours under blanket of nitrogen then, and the magnetic that do not have a power failure therebetween stirs; Treat to stop ventilation after temperature is reduced to room temperature, make 0.39mg/mL ruthenium colloidal sol.
CNT was soaked in concentrated hydrochloric acid 24 hours, and filtration washing to filtrate is neutral then, descends dry 2 hours at 100 ℃ again, obtains the carbon nanotube carrier of purifying.CNT is joined in the round-bottomed flask, NaOH (3mmol/L) added hot reflux 1 hour for 70 ℃ again, and centrifugation is filtered to filtrate for neutral, 100 ℃ of dryings 2 hours; Placing volume ratio then is 3: 1 dense HNO
3With dense H
2SO
4Mixed acid solution in, 70 ℃ added hot reflux 5 hours, centrifugation, filtration washing to filtrate is neutral, 100 ℃ of dryings 2 hours.Weighing 100mg is through the CNT of above-mentioned processing, pipetting the ruthenium colloidal sol that platinum colloidal sol that 10mL embodiment 1 prepares and 10mL present embodiment prepare mixes, dropwise add, the ultrasonic dispersion of 250W 5 hours, centrifugation, repeatedly wash with absolute ethyl alcohol and secondary water, 100 ℃ of dryings obtain load capacity and are about 20.2% PtRu/MWCNTs catalyst (the PtRu mass ratio is about 10: 1).
Embodiment 3:
Present embodiment except that following characteristics with embodiment 1: 130 ℃ of oil baths added hot reflux 3 hours under blanket of nitrogen.
Embodiment 4:
Present embodiment except that following characteristics with embodiment 1: 130 ℃ of oil baths added hot reflux 1 hour under blanket of nitrogen.
Embodiment 5:
Present embodiment except that following characteristics with embodiment 1: 145 ℃ of oil baths added hot reflux 5 hours under blanket of nitrogen.
Embodiment 6:
Present embodiment except that following characteristics with embodiment 1: 160 ℃ of oil baths added hot reflux 5 hours under blanket of nitrogen.
Embodiment 7:
Present embodiment except that following characteristics with embodiment 2: weighing 100mg crosses the CNT of above-mentioned processing, pipetting the platinum colloidal sol of 10mL embodiment 1 preparation and the ruthenium colloidal sol of 20mL embodiment 2 preparations mixes, dropwise add, ultrasonic dispersion 5 hours, centrifugation, repeatedly wash with absolute ethyl alcohol and secondary water, 100 ℃ of dryings obtain load capacity and are about 22.1% PtRu/MWCNTs catalyst (the PtRu mass ratio is about 5: 1).
Embodiment 8:
Present embodiment except that following characteristics with embodiment 2: pipette the platinum colloidal sol of 10mL (3.76mg/mL) embodiment 1 preparation and 30mL (0.39mg/mL) the ruthenium colloidal sol of embodiment 2 preparations and mix, dropwise add, ultrasonic dispersion 5 hours, centrifugation, repeatedly wash with absolute ethyl alcohol and secondary water, 100 ℃ of dryings obtain load capacity and are about 24.3% PtRu/MWCNTs catalyst (the PtRu mass ratio is about 3: 1).
Embodiment 9:
Present embodiment except that following characteristics with embodiment 2: pipette the platinum colloidal sol of 10mL (3.76mg/mL) embodiment 1 preparation and the ruthenium colloidal sol of 40mL (0.39mg/mL) embodiment 2 preparations and mix, dropwise add, ultrasonic dispersion 5 hours, centrifugation, repeatedly wash with absolute ethyl alcohol and secondary water, 100 ℃ of dryings obtain load capacity and are about 26.2% PtRu/MWCNTs catalyst (the PtRu mass ratio is about 2.5: 1).
Embodiment 10:
Present embodiment except that following characteristics with embodiment 2: pipette the platinum colloidal sol of 10mL (3.76mg/mL) embodiment 1 preparation and the ruthenium colloidal sol of 50mL (0.39mg/mL) embodiment 2 preparations and mix, dropwise add, ultrasonic dispersion 5 hours, centrifugation, repeatedly wash with absolute ethyl alcohol and secondary water, 100 ℃ of dryings obtain load capacity and are about 27.2% PtRu/MWCNTs catalyst (the PtRu mass ratio is about 2: 1).
Embodiment 11:
Present embodiment except that following characteristics with embodiment 2: pipette the platinum colloidal sol of 10mL (3.76mg/mL) embodiment 1 preparation and the ruthenium colloidal sol of 100mL (0.39mg/mL) embodiment 2 preparations and mix, dropwise add, ultrasonic dispersion 5 hours, centrifugation, repeatedly wash with absolute ethyl alcohol and secondary water, 100 ℃ of dryings obtain load capacity and are about 28.3% PtRu/MWCNTs catalyst (the PtRu mass ratio is about 1: 1).
Test case
Eelctro-catalyst to the present invention's preparation carries out the physical and chemical performance analysis.
As seen from Figure 1, the nano platinum particle particle is about 3nm, is dispersed in carbon nano tube surface, and granular size does not have significant change before and after the load.
As seen from Figure 2, CNT has had abundant hydroxyl, carboxyl etc. to contain the oxygen functional group through the preliminary treatment rear surface, and these groups help the deposition of nanometer platinum particles in carbon nano tube surface, particularly Pt has the crystal plane orientation of (111) on the CNTs that handled, and these factors are all influential to its electro catalytic activity.
Fig. 3 as seen, specific surface area of carbon nanotube increases after preliminary treatment, helps the dispersion of platinum.
Fig. 4 is the XRD figure spectrum of Pt/MWCNTs, has the broadening peak of platinum among the figure, and the particle diameter that Pt be described is a nanoscale, and the strongest peak [111] are 39.8 ° in the 2 θ angles of diffraction and locate, and next is respectively in 46.2 ° [200], 67.4 ° [220] and 81.3 ° [311].The MWCNTs carrier of hydroxyl and carboxyl is with its excellent surface characteristic, makes that the dispersion of Pt particle on its surface presents efficiently, the nanoscale particle of homogeneous.Grain size is pressed the Scherrer equation with the half-peak breadth of [220] crystal face diffraction maximum and is calculated, and draws the platinum grain that is deposited on the CNTs and directly is 2.8nm, the basically identical of 3nm as a result that draws with TEM (Fig. 2).
Pt/MWCNTs is shown Fig. 5 and Pt/C (JM) is that catalyst is at 0.1CH
3OH+0.5H
2SO
4Catalytic oxidation figure in the solution.As can be seen, when preparing Pt/MWCNTs and make catalyst with the present invention, current density is higher, good catalytic activity.
Claims (5)
1. the preparation method of a DMFC eelctro-catalyst is characterized in that comprising the steps: at first carbon nanotube carrier being carried out purifying and activation processing; Prepare platinum or platinum ruthenium mixture nano-particle solution then; Be 1: 0.02～1: 0.80 proportioning again by the mass ratio of CNT and platinum or platinum ruthenium mixture, adopt the ethylene glycol dispersing Nano carbon tubes earlier, add platinum or platinum ruthenium mixture nano-particle solution then, adopt 200～500W ultrasonic wave to carry out ultrasonic wave again and handled 1～5 hour, prepare the DMFC eelctro-catalyst.
2. the preparation method of according to claim a kind of DMFC eelctro-catalyst, it is characterized in that: describedly carbon nanotube carrier is carried out purification process be meant CNT was soaked in concentrated hydrochloric acid 12～48 hours, filtration washing to filtrate is neutral then, descended dry 1～2 hour at 80～100 ℃ again, obtain the carbon nanotube carrier of purifying.
3. the preparation method of according to claim a kind of DMFC eelctro-catalyst, it is characterized in that: described carbon nanotube carrier is carried out activation processing is to carry out activation processing by the multistep oxidation, promptly CNT is joined in the container, added hot reflux 1～5 hour with 1～5mmol/L NaOH at 0～100 ℃, centrifugation, be filtered to filtrate for neutral, 80～100 ℃ of dryings are 1～2 hour again; Placing volume ratio then is 3: 1 dense HNO
3With dense H
2SO
4Mixed acid solution in, added hot reflux 1～5 hour at 60～100 ℃, centrifugation, filtration washing to filtrate is neutral, 80～100 ℃ of dryings 1～2 hour.
4. the preparation method of according to claim a kind of DMFC eelctro-catalyst, it is characterized in that: described preparation nano platinum particle is meant the chloroplatinic acid of 0.1～1 gram and 1～5 gram NaOH is dissolved in 50～250mL ethylene glycol solution respectively that ultrasonic then dispersion mixes; Logical 10～30 minutes deaerations of nitrogen; 130～160 ℃ of oil baths added hot reflux 1～5 hour under blanket of nitrogen then, carried out electromagnetic agitation simultaneously, obtained nano platinum particle at last.
5. the preparation method of according to claim a kind of DMFC eelctro-catalyst, it is characterized in that: described preparation platinum ruthenium mixture nano particle is meant the ruthenium trichloride of 0.1～1 gram and 1～5 gram NaOH is dissolved in 50～250mL ethylene glycol solution respectively that ultrasonic then dispersion mixes; Logical 10～30 minutes deaerations of nitrogen; 130～160 ℃ of oil baths added hot reflux 1～5 hour under blanket of nitrogen then, carried out electromagnetic agitation simultaneously, obtained ruthenium nano particle; Last again ruthenium nano particle the mixing with the above-mentioned nano platinum particle for preparing obtains platinum ruthenium mixture nano particle.
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| CN112186198A (en) * | 2020-09-17 | 2021-01-05 | 北京航空航天大学 | Direct methanol fuel cell with anode using carbon nanotube paper as diffusion layer |
| CN113629249A (en) * | 2021-06-10 | 2021-11-09 | 中国科学院金属研究所 | Preparation method of MXene-based supported platinum catalyst applied to lithium-sulfur battery anode |
| CN113871645A (en) * | 2021-09-29 | 2021-12-31 | 北京化工大学 | Preparation method of uniformly-loaded carbon nanotube platinum-loaded electrocatalyst |
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