CN100553768C - A kind of loaded and non-supported catalyst and preparation method - Google Patents
A kind of loaded and non-supported catalyst and preparation method Download PDFInfo
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Abstract
一种活性组份粒子形状、晶面取向可控的催化剂的制备方法，步骤为：a)配置活性组分的可溶性金属盐水溶液，该溶液中金属盐的浓度为1.0×10-6～10mol/L，加入碱溶液至pH值为3-9；b)配置保护剂及稳定剂的水溶液，该溶液中的保护剂及或稳定剂的浓度为1.0×10-5～20mol/L，加入碱溶液至pH值为4-9；c)将步骤a与b的两种溶液混合均匀，用还原剂进行还原；d)在步骤c的混合溶液中加入沉降剂，过滤；干燥，得非担载型催化剂。其中步骤d中加入载体后再加入沉降剂，过滤；干燥，得担载型催化剂。本发明工艺流程简单、成本低廉、环境友好、易于批量生产。A method for preparing a catalyst with controllable particle shape and crystal plane orientation of the active component, the steps are: a) preparing an aqueous solution of a soluble metal salt of the active component, and the concentration of the metal salt in the solution is 1.0×10 -6 to 10 mol/ L, add alkaline solution to pH 3-9; b) prepare an aqueous solution of protective agent and stabilizer, the concentration of protective agent and/or stabilizer in the solution is 1.0×10 -5 ~ 20mol/L, add alkaline solution until the pH value is 4-9; c) mix the two solutions in step a and b evenly, and reduce with a reducing agent; d) add a sedimentation agent to the mixed solution in step c, filter; dry to obtain a non-supported catalyst. Wherein, after adding the carrier in step d, adding the precipitating agent, filtering and drying, a supported catalyst is obtained. The invention has the advantages of simple technological process, low cost, environmental friendliness and easy batch production.
Description
Technical field
The present invention relates to a kind of loaded and non-supported metallic catalyst and preparation method.
Background technology
Fuel cell is a kind of electrochemical reaction appts that the chemical energy of fuel and oxidant is directly changed into electric energy.Because simple, the characteristics such as theoretical energy density is high, environmental friendliness of fuel cell structure have broad application prospects at aspects such as electric vehicle electrical source of power, dispersion power station, portable portable power sources.
Catalyst is one of critical material of fuel cell, the Preparation of catalysts method has infusion process, coprecipitation, liquid phase reduction, colloid method, the electrochemistry precipitation method etc. usually, and these methods still can not be controlled the particle size and the high preferred orientation of active constituent metallic at present.The size of active constituent particle and high preferred orientation are most important to the responsive catalytic reaction of structure, and the catalyst decentralization that particle is little is higher usually, and metallic catalyst can provide more surface-active position, catalyst utilization height under the identical carrying capacity; The high preferred orientation of active constituent particle directly influences its catalytic activity.As before showing in the result of study on the single-crystal surface: hydrogen evolution reaction (HER) is different with the kinetic rate of hydroxide reaction (HOR) on different Pt (hkl) crystal face.In acid solution, (under 0.2～0.2V), the active order of Pt monocrystalline electrode is Pt (111)＜Pt (100)＜Pt (110) to lower overpotential, and temperature independent; In alkaline solution, during low temperature (275K), the active order of Pt monocrystalline electrode is identical with the former, and the active order under higher temperature then is: Pt (100)＜Pt (111)≤Pt (110); In KOH solution, the active order of the reduction reaction of oxygen on Pt monocrystalline electrode surface is Pt (100)＜Pt (110)＜Pt (111), and at H
2SO
4In the solution, its active order is: Pt (111)＜＜Pt (100)＜Pt (110); The catalytic activity of methyl alcohol oxidation on Pt (111)/Ru electrode surface is than high about 25 times of present commercial Pt/Ru catalyst.
In addition, present many preparation method experimental period is long, energy consumption is big, cost is high, is unfavorable for large-scale production.Some process adopts poisonous reducing agent or process accessory substance many, and environmental pollution is serious.
American documentation literature 5,641,723 disclose and have a kind ofly prepared metallic catalyst by colloid method, and its process is as follows: adopt NR
4BR
3H is reducing metal salt in the solution of oxolane (THF); the nano level metal colloid that has prepared the various quaternary ammonium salt protection; its particle size distribution range is narrower; it is supported on the various carrier then; distribution of particles is more even, but this method need operate under the anhydrous environment of anaerobic, has used a large amount of toxic organic solvents in the process; accessory substance is many, the process more complicated, and is wayward to the size and the high preferred orientation of active constituent particle.
United States Patent (USP) 3,992,331 have introduced a kind of method for preparing the high dispersive platinum catalyst.This method is prepared into sulfurous acid platinum sodium (Na with chloroplatinic acid earlier
6[Pt (SO
3)
4]), then by ion-exchange, sodium ion in the sulfurous acid platinum sodium is exchanged into hydrogen ion, in air, heat and boil, remove unnecessary sulfite ion, the dry at a certain temperature black colloid that makes platinum, this colloid can be distributed in the water or in other solvent once more, thereby is easy to support on the various carriers.Utilize this method can prepare the platinum catalyst of 1-3nm, avoided in the catalyst trace chlorine the harmful effect of its catalytic activity.But this preparation method is difficult to control the size and the high preferred orientation of active constituent particle, and preparation cost is higher, technological process is complicated.
Document (H.E.Van Dam, J.Catal.131 (1991) 335) has been introduced the method for preparing platinum catalyst with formaldehyde as reducing agent.Detailed process is as follows: chloroplatinic acid aqueous solution is added in the active carbon, slowly stir under the room temperature, flood after 5 days to adsorption equilibrium filtration, hydrothermal treatment consists in 95 ℃ of closed containers, adding formaldehyde reduction at last, to make platiniferous be that 5wt% has the carbon supported catalyst than high degree of dispersion.Because the reducing agent reducing power is stronger, its broad particle distribution of metallic catalyst of this method preparation is difficult to control the size and the high preferred orientation of active constituent particle.In addition, formaldehyde has certain toxicity as reducing agent.
Document (L.S.Sarma, Journal of Power Sources 139 (2005) 44-54) has been introduced a kind of with Nafion polymer used as stabilizers and protective agent, and polyalcohol prepares the method for platinum ruthenium catalyst as reducing agent.The catalyst of this method preparation has better decentralization, particle diameter is at 3-7nm, detailed process is as follows: with the methanol aqueous solution of the mixed solution furnishing different proportion of chloroplatinic acid and ruthenic chloride, the Nafion solution (ratio of Nafion solution and catalyst remained on 1: 3) that adds Vulcan XC-72 and 5wt%, the pH value of regulating mixed solution is 11,70 ℃ were stirred 5 hours down, add carbon carrier, sedimentation, filtration.The platinum ruthenium catalyst productive rate of this method preparation is higher, but the size of catalyst activity component particle and high preferred orientation are difficult to control, and used reducing agent has certain toxicity.
Summary of the invention
The purpose of this invention is to provide a kind of active constituent shape of particle, the controlled Preparation of catalysts method of high preferred orientation.
Catalyst of the present invention can be loaded and non-supported catalyst, and its main preparation process is:
A) the soluble metal saline solution of preparation active component, the concentration that this GOLD FROM PLATING SOLUTION belongs to salt is 1.0 * 10
-6～10mol/L, adding aqueous slkali to pH value is 3-9;
B) prepare protectant aqueous solution, the protectant concentration in this solution is 1.0 * 10
-5～20mol/L, adding aqueous slkali to pH value is 4-9;
C) two kinds of solution with step a and b mix, and reduce with reducing agent;
D) in the mixed solution of step c, add sedimentation agent, filter; Drying gets non-supported catalyst;
Described active component is: I, VIII subgroup and Ti, Cr, Mo, Re, Sn main group metal or its mixture or its alloy or its oxide;
Described protective agent is the polymer or the organic matter that can make the metallic stable existence, as: polyvinylpyrrolidone [Poly (vinyl-pyrrolidone)], polyacrylic acid [Sodium Polyacrylate], polypyrrole [Polypyrrole], polyvinyl alcohol [Poly (vinyl-alcohol)], glucose, citric acid, starch, Nafion polymer, polyalcohol or contain five-membered ring or polynary ring organic matter or its solution of P, S, N atom;
Described reducing agent is: hydrogen, polyalcohol, sodium borohydride, formalin or its mixed solution;
Described sedimentation agent is: nitric acid, sulfuric acid, oxalic acid, acetic acid, carbonic acid and contain organic matter, acetone, butanone and ketone, ether, ethanol, isopropyl alcohol and alcohols, cyclohexane, normal butane and little molecule alkane or its mixture of sulfonate radical.
Among the above-mentioned preparation method, in steps d, add add sedimentation agent again behind the carrier after, filter; Drying promptly gets supported catalyst;
Described carrier is: active carbon, carbon black, carbon nanotube, charcoal nanofiber, molecular sieve, aluminium oxide, silica, titanium oxide or its mixture.
Among the preparation method of the present invention, the aqueous solution among step a and the step b is the mixed solution of water and polyalcohol.
Among the preparation method of the present invention, little molecule alkane carbon number is 1～9.
Being shaped as of the catalyst of the present invention preparation is spherical, linear, tetrahedron, hexahedron, polyhedron, bar-shaped or netted.
Among the preparation method of the present invention, protective agent (being also referred to as stabilizing agent) can adopt mist heating removal under ultrasonic method or the high temperature.
Specifically, active constituent shape of particle of the present invention, loaded and the non-supported catalyst that high preferred orientation is controlled, with I, VIII subgroup and Ti, Cr, Mo, Re, Sn main group metal or its mixture, or its alloy, or its oxide is an active component, with the salt or its mixture that contain above-mentioned active constituent is precursor, with active carbon, carbon black, carbon nanotube, the charcoal nanofiber, molecular sieve, aluminium oxide, silica, titanium oxide or its mixture are carrier, with polyvinylpyrrolidone, polyacrylic acid, polypyrrole, polyvinyl alcohol, glucose, citric acid, starch, Nafion polymer or polyhydric alcohol solutions are protective agent, with hydrogen, polyalcohol, sodium borohydride, formalin or its mixed solution are reducing agent; Sedimentation agent is nitric acid, sulfuric acid, oxalic acid, acetic acid, carbonic acid and organic matter, acetone, butanone and ketone, ether, ethanol, isopropyl alcohol and the alcohols that contains sulfonate radical, cyclohexane, normal butane and little molecule alkane or its mixture.
Method provided by the invention prepares loaded and non-supported noble metal catalyst, and technological process is simple, with low cost, environmental friendliness, be easy to produce in batches.The catalyst particle size of preparation is controlled, decentralization is high, the pattern and the high preferred orientation of selecting the superior are controlled to a certain extent, can improve organic molecule oxidation and oxygen reduction reaction speed and dynamic processes such as methyl alcohol, formic acid, ethanol, dimethyl ether, significantly improve catalyst utilization.Method provided by the invention can be widely used in hydrogen-oxygen proton exchange membrane fuel cell (PEMFC), directly alcohol fuel battery (DAFC comprises the fuel cell of the direct charging of organic molecule) and have with the similar electrochemical reaction appts of above-mentioned fuel cell structure, senser element in Preparation of catalysts.
Catalyst activity component decentralization height, the narrow diameter distribution of the present invention's preparation, and can effectively control the active constituent particle size; Can control the high preferred orientation according to qualifications of active constituent particle to a certain extent; Not under the removal situation fully, catalyst has certain hydrophobicity, and is significant with management to the discharge of DMFC negative electrode water at protective agent; The catalyst preparation process flow process is simple, with low cost, environmental friendliness, be easy to produce in batches; Adopt hydrogen, the harmful effect that accessory substance is too much or post processing causes environment in the catalyst preparation process can be avoided or reduce to polyalcohol or other eco-friendly reducing agent.
Description of drawings
Fig. 1 makes protectant platinum black catalyst (sample 1) transmission electron microscope (TEM) figure for the polyvinylpyrrolidone (PVP) of the present invention's preparation;
Fig. 2 A, 2B make protectant platinum black catalyst (sample 2) transmission electron microscope (TEM) figure for the Sodium Polyacrylate (PAA) of the present invention's preparation;
Fig. 3 makes protective agent for the polyvinylpyrrolidone (PVP) of the present invention's preparation, and the noble metal carrying capacity is 20% Pt-Ru/C catalyst (sample 3) transmission electron microscope (TEM) figure;
Fig. 4 makes protective agent for the polyvinylpyrrolidone (PVP) of the present invention's preparation, and the noble metal carrying capacity is 20% Pt-Ru/C catalyst (sample 4) XRD spectra;
Fig. 5 makes protectant platinum nano-wire catalyst (sample 4) transmission electron microscope (TEM) figure for the polyvinylpyrrolidone (PVP) of the present invention's preparation;
Fig. 6 makes protectant platinum black catalyst (sample 5) transmission electron microscope (TEM) figure for the polyvinylpyrrolidone (PVP) of the present invention's preparation;
Fig. 7 A, 7B make protectant tetrahedron platinum black catalyst (sample 6) transmission electron microscope (TEM) figure and particle diameter distribution map for the polyvinylpyrrolidone (PVP) of the present invention's preparation;
Fig. 8 A, 8B, 8C make protective agent for the polyvinylpyrrolidone (PVP) of the present invention's preparation, and the noble metal carrying capacity is 10% Pt-Ru/C catalyst (sample 7) transmission electron microscope (TEM) figure, particle diameter distribution map and EDX figure;
Fig. 9 makes protective agent for the polyvinylpyrrolidone (PVP) of the present invention preparation, and the noble metal carrying capacity is that 40% carbon carries platinum black catalyst (sample 8) cyclic voltammetry curve;
Figure 10 A, 10B make protective agent for the present invention prepares with starch, and the noble metal carrying capacity is 45% Pt-Ru/C catalyst (sample 9) transmission electron microscope (TEM) figure and DMFC monocell performance curve.
The specific embodiment
In order to further specify the present invention, enumerate following examples, do not limit scope of invention.
The preparation process of sample 1 is as follows: the preparation platinum acid chloride solution: 1 gram chloroplatinic acid is dissolved in the mixed solvent of 50 ml waters and 50 milliliters of ethylene glycol compositions, stirs; Preparation protective agent solution: 1 gram polyvinylpyrrolidone (PVP) is dissolved in the mixed solvent that 50ml water, 50 milliliters of ethylene glycol, 100 ethanol forms, stirs.Above-mentioned two kinds of solution are mixed, after stirring, add 2ml 1mol/L NaOH ethylene glycol solution; be warming up to 130 ℃, stir, kept 2 hours; reduce to room temperature; filter washing, centrifugation; black sedimentation material is collected; drying is 8 hours under 80 ℃, obtains polyvinylpyrrolidone (PVP) and makes protective agent (stabilizing agent), and ethylene glycol is done the platinum catalyst of reducing agent.
The preparation process of sample 2 is as follows: the preparation platinum acid chloride solution: 1 gram chloroplatinic acid is dissolved in the mixed solvent of 50 ml waters, 50 milliliters of ethylene glycol compositions, stirs; Preparation protective agent solution: 500 milligrams of Sodium Polyacrylates (PAA) are dissolved in the mixed solvent that 50ml water, 50 milliliters of ethylene glycol, 100 ethanol forms, stir.Above-mentioned two kinds of solution are mixed, after stirring, add 2ml 1mol/L NaOH ethylene glycol solution; stir, feed hydrogen, kept 10 minutes; continue to stir 6 hours, filter, washing; the mixed solution that adds acetone and ethanol is as sedimentation agent, and black sedimentation material is collected in centrifugation; drying is 8 hours under 80 ℃; obtain Sodium Polyacrylate (PAA) and make protective agent (stabilizing agent), hydrogen and ethanol are reducing agent, and the mixed solution of acetone and ethanol is the platinum catalyst of sedimentation agent.
The preparation process of sample 3 is as follows: the preparation platinum acid chloride solution: 1 gram chloroplatinic acid is dissolved in the mixed solvent of 150 ml waters, 150 milliliters of ethylene glycol compositions, stirs; Preparation ruthenium trichloride solution: 1 gram ruthenium trichloride trihydrate is dissolved in the mixed solvent of 50 ml waters, 50 milliliters of ethylene glycol and 100 milliliters of ethanol compositions, stirs; Configuration protection agent solution: 1 gram polyvinylpyrrolidone (PVP) is dissolved in the mixed solvent that 50ml water, 50 milliliters of ethylene glycol, 100 ethanol forms, stirs.Above-mentioned three kinds of solution are mixed; after stirring; add 8ml 1mol/L NaOH ethylene glycol solution; stir, feed hydrogen, kept 15 minutes; continue to stir 6 hours; add 5 and restrain the XC-72R carbon dust that is dispersed in ethylene glycol, add the 1.5mol/L aqueous hydrochloric acid solution and cook sedimentation agent, stir; filter; black sedimentation material is collected in washing, and 80 ℃ following dry 8 hours; obtain polyvinylpyrrolidone (PVP) and make protective agent (stabilizing agent); hydrogen is reducing agent, and carbon dust is done carrier, and aqueous hydrochloric acid solution is the Pt-Ru/C catalyst of sedimentation agent.
Table 1 is made protective agent for the polyvinylpyrrolidone (PVP) of embodiment 3 preparation, and the noble metal carrying capacity is the crystal grain distribution statistics table of 20% Pt-Ru/C catalyst (sample 3):
Table 1:
Embodiment 4
The preparation process of sample 4 is as follows: the preparation platinum acid chloride solution: 1 gram chloroplatinic acid is dissolved in the mixed solvent of 50 ml waters, 50 milliliters of ethylene glycol compositions, stirs; Preparation protective agent solution: 1 gram polyvinylpyrrolidone (PVP) is dissolved in the mixed solvent that 50ml water, 50 milliliters of ethylene glycol, 100 ethanol forms, stirs; Preparation ferric chloride solution: 200 milligrams of iron chloride are dissolved in the mixed solvent of 200 water, 50 milliliters of ethylene glycol compositions, stir; Above-mentioned preceding two kinds of solution are mixed, after stirring, add 6ml 1mol/L NaOH ethylene glycol solution, be warming up to 140 ℃, stir, kept 1 hour, add the ferric chloride solution of preparation again, continue to stir 2 hours.Add the 1.5mol/L aqueous hydrochloric acid solution and cook sedimentation agent; stir; filter; black sedimentation material is collected in washing, and 80 ℃ following dry 12 hours; obtain polyvinylpyrrolidone (PVP) and make protective agent (stabilizing agent); ethylene glycol is reducing agent, and molysite is a guiding agent, and aqueous hydrochloric acid solution is the platinum nano-wire catalyst of sedimentation agent.
The preparation process of sample 5 is as follows: the preparation platinum acid chloride solution: 1 gram chloroplatinic acid is dissolved in the mixed solvent of 50 ml waters, 50 milliliters of ethylene glycol compositions, stirs; Configuration protection agent solution: 1 gram polyvinylpyrrolidone (PVP) is dissolved in the mixed solvent that 50ml water, 50 milliliters of ethylene glycol, 100 ethanol forms, stirs.Above-mentioned two kinds of solution are mixed, after stirring, add 20ml 1mol/L NaOH ethylene glycol solution; stir, feed hydrogen, kept 10 minutes; continue to stir 6 hours, filter, washing; add n-hexane and acetone mixed liquor and cook sedimentation agent, black sedimentation material is collected in centrifugation; drying is 8 hours under 80 ℃; obtain polyvinylpyrrolidone (PVP) and make protective agent (stabilizing agent), hydrogen is reducing agent, and the mixed solution of n-hexane and acetone is the platinum catalyst of sedimentation agent.
The preparation process of sample 6 is as follows: the preparation platinum acid chloride solution: 1 gram chloroplatinic acid is dissolved in the mixed solvent of 100 ml waters, 100 milliliters of ethylene glycol compositions, stirs; Preparation liquor argenti nitratis ophthalmicus: 200 milligrams of silver nitrate powder dissolutions in 100 milliliters of ethylene glycol solvents, are stirred; Preparation protective agent solution: 500 milligrams of polyvinylpyrrolidones (PVP) are dissolved in the mixed solvent of 50ml water, 50 milliliters of ethylene glycol compositions, stir; Above-mentioned three kinds of solution are mixed, after stirring, put into the microwave reaction stove; heated 2 minutes, and took out, stir; reduce to room temperature, filter, washing; black sedimentation material is collected in centrifugation, and 80 ℃ following dry 12 hours; obtain polyvinylpyrrolidone (PVP) and make protective agent (stabilizing agent); ethylene glycol is reducing agent, and silver nitrate is a guiding agent, and the mixed liquor of n-hexane, acetone and ethanol is the tetrahedron platinum catalyst of sedimentation agent.
The preparation process of sample 7 is as follows: the preparation platinum acid chloride solution: 1 gram chloroplatinic acid is dissolved in the mixed solvent of 100 ml waters, 100 milliliters of ethylene glycol compositions, stirs; Preparation ruthenium trichloride solution: 1 gram ruthenium trichloride trihydrate is dissolved in the mixed solvent of 100 ml waters, 100 milliliters of ethylene glycol compositions, stirs; Preparation protective agent solution: 1 gram polyvinylpyrrolidone (PVP) is dissolved in the mixed solvent of 100ml water, 100 milliliters of ethylene glycol compositions, stirs.Above-mentioned three kinds of solution are mixed; after stirring; add 12ml 1mol/L NaOH ethylene glycol solution; stir, be warming up to 140 ℃, kept 3 hours; stir; add 5.2 and restrain the BP-2000 carbon dust that is dispersed in the ethylene glycol, add aqueous solution of nitric acid and cook sedimentation agent, stir; filter; black sedimentation material is collected in washing, and 80 ℃ following dry 12 hours; obtain polyvinylpyrrolidone (PVP) and make protective agent and stabilizing agent; ethylene glycol is reducing agent, and aqueous solution of nitric acid is a sedimentation agent, and the BP-2000 powdered carbon is the platinum ruthenium catalyst of carrier.
The preparation process of sample 8 is as follows: preparation potassium chloroplatinate solution: 1 gram potassium chloroplatinate is dissolved in the mixed solvent of 150 ml waters, 150 milliliters of ethylene glycol compositions, stirs; Preparation protective agent solution: 1 gram polyvinylpyrrolidone (PVP) is dissolved in the mixed solvent of 50ml water, 50 milliliters of ethylene glycol compositions, stirs.Above-mentioned two kinds of solution are mixed; after stirring; add 3ml1mol/L NaOH ethylene glycol solution; logical argon gas 2 minutes; logical again hydrogen 10 minutes; stir; add 2 grams and be dispersed in ethylene glycol solution Vulcan XC-72 carbon dust, the mixed solution that adds cyclohexane and ethanol is a sedimentation agent, filters; washing; black sedimentation material is collected, and 80 ℃ were descended dry 6 hours, and obtained polyvinylpyrrolidone (PVP) and make protective agent (stabilizing agent); hydrogen is reducing agent, and the mixed solution of cyclohexane and ethanol is the carbon supported platinum catalyst of sedimentation agent.
Embodiment 9
The preparation process of sample 9 is as follows: the preparation platinum acid chloride solution: 1 gram chloroplatinic acid is dissolved in the mixed solvent of 100 ml waters, 100 milliliters of ethylene glycol compositions, stirs; Preparation ruthenium trichloride solution: 1 gram ruthenium trichloride trihydrate is dissolved in the mixed solvent of 50 ml waters, 50 milliliters of ethylene glycol and 50 milliliters of ethanol compositions, stirs; Preparation protective agent solution: 1 gram starch dissolution in the mixed solvent of 50ml water, 50 milliliters of ethylene glycol compositions, is stirred.Above-mentioned three kinds of solution are mixed; after stirring; add 12ml 1mol/L NaOH ethylene glycol solution; stir; be warming up to 140 ℃, kept 3 hours, continue to stir; add 4 and restrain the XC-72R carbon that is dispersed in ethylene glycol; the mixed liquor that adds aqueous acetic acid and aqueous hydrochloric acid solution is a sedimentation agent, stirs, and filters; washing; black sedimentation material is collected, and 80 ℃ were descended dry 8 hours, and obtained starch and make protective agent (stabilizing agent); ethylene glycol is reducing agent, and the mixed liquor of aqueous acetic acid and aqueous hydrochloric acid solution is the Pt-Ru/C catalyst of sedimentation agent.
Embodiment 10
Preparation platinum acid chloride solution: 1 gram chloroplatinic acid is dissolved in the mixed solvent of 150 ml waters, 150 milliliters of ethylene glycol compositions, stirs; The aqueous solution of preparation palladium bichloride: 1 gram palladium bichloride trihydrate is dissolved in the mixed solvent of 50 ml waters, 50 milliliters of ethylene glycol and 100 milliliters of ethanol compositions, stirs; Configuration protection agent solution: 1 gram polyvinyl alcohol (PVA) is dissolved in the mixed solvent that 50ml water, 50 milliliters of ethylene glycol, 100 ethanol forms, stirs.Above-mentioned three kinds of solution are mixed; after stirring; add 4ml 1mol/L NaOH ethylene glycol solution; stir, feed hydrogen, kept 15 minutes; continue to stir 6 hours; add 5 grams and be dispersed in the CNT of ethylene glycol and the mixed-powder of nanofiber, add aqueous hydrochloric acid solution and cook sedimentation agent, stir; filter; black sedimentation material is collected in washing, and 80 ℃ following dry 8 hours; obtain polyvinyl alcohol (PVA) and make protective agent (stabilizing agent); hydrogen is reducing agent, and CNT is done carrier, and aqueous hydrochloric acid solution is that the carbon of sedimentation agent carries the platinum palladium catalyst.
Embodiment 11
Preparation platinum acid chloride solution: 1 gram chloroplatinic acid is dissolved in the mixed solvent of 150 ml waters, 150 milliliters of ethylene glycol compositions, stirs; Preparation tin chloride solution: 1 gram stannic chloride hydrate is dissolved in the mixed solvent of 50 ml waters, 50 milliliters of ethylene glycol and 100 milliliters of ethanol compositions, stirs; Configuration protection agent solution: 1mL Nafion solution is dissolved in the mixed solvent of 10ml water, 10 milliliters of ethanol compositions, stirs.Above-mentioned three kinds of solution are mixed, after stirring, feed hydrogen; kept 15 minutes, and continued to stir 6 hours, add the carbon dust that 5 grams are dispersed in ethylene glycol; add aqueous hydrochloric acid solution and cook sedimentation agent, stir, filter; black sedimentation material is collected in washing, and 80 ℃ following dry 8 hours; obtain Nafion solution and make protective agent (stabilizing agent); hydrogen is reducing agent, and carbon dust is done carrier, and aqueous hydrochloric acid solution is that the carbon of sedimentation agent carries platinum-tin catalyst.
Embodiment 12
Preparation platinum acid chloride solution: 1 gram chloroplatinic acid is dissolved in the mixed solvent of 150 ml waters, 150 milliliters of ethylene glycol compositions, stirs; Preparation liquor ferri trichloridi: 1 gram ferric trichloride is dissolved in the mixed solvent of 50 ml waters, 50 milliliters of ethylene glycol and 50 milliliters of ethanol compositions, stirs; Configuration protection agent solution: 1 gram starch (starch) is dissolved in the mixed solvent of 50ml water, 100 ethanol composition, stirs.Above-mentioned three kinds of solution are mixed; after stirring; add the 4ml 1mol/LNaOH aqueous solution; stir; add formalin, continue to stir 6 hours, add SBA-15 and 1 gram carbon nanohorn that 0.5 gram is dispersed in ethylene glycol; add aqueous hydrochloric acid solution and cook sedimentation agent; stir, filter, washing; black sedimentation material is collected; drying is 8 hours under 80 ℃, obtains starch (starch) and makes protective agent (stabilizing agent), and formaldehyde is reducing agent; SBA-15 and carbon nanohorn are done carrier, and aqueous hydrochloric acid solution is that the carbon that the SBA-15 of sedimentation agent modifies carries the platinum iron catalyst.
Embodiment 13
Preparation platinum acid chloride solution: 1 gram chloroplatinic acid is dissolved in the mixed solvent of 150 ml waters, 150 milliliters of ethylene glycol compositions, stirs; Preparation chlorauric acid solution: 1 gram gold chloride is dissolved in the mixed solvent of 50 ml waters, 50 milliliters of ethylene glycol and 100 milliliters of ethanol compositions, stirs; Configuration protection agent solution: 1 gram natrium citricum is dissolved in the mixed solvent that 50ml water, 50 milliliters of ethylene glycol, 100 ethanol forms, stirs.Above-mentioned three kinds of solution are mixed; after stirring; add the 6ml 1mol/L NaOH aqueous solution; stir, slowly drip the ethylene glycol solution of sodium borohydride, drip the back and continue to stir 3 hours; add 4 and restrain the carbon dust that is dispersed in ethylene glycol; continue to stir 12 hours, add aqueous hydrochloric acid solution and cook sedimentation agent, stir; filter; black sedimentation material is collected in washing, and 80 ℃ following dry 8 hours; obtain natrium citricum and make protective agent (stabilizing agent); sodium borohydride is a reducing agent, and carbon dust is done carrier, and aqueous hydrochloric acid solution is that the carbon of sedimentation agent carries platinum catalyst.
The particle diameter distribution statistics of each sample of the present invention's preparation sees Table 2.
Table 2: sample particle diameter distribution abridged table
Claims (5)
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