CN104174392A - One-step preparation method and application of supported platinum-based multi-metal catalysts - Google Patents
One-step preparation method and application of supported platinum-based multi-metal catalysts Download PDFInfo
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- CN104174392A CN104174392A CN201310202605.4A CN201310202605A CN104174392A CN 104174392 A CN104174392 A CN 104174392A CN 201310202605 A CN201310202605 A CN 201310202605A CN 104174392 A CN104174392 A CN 104174392A
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Abstract
A one-step preparation method and an application of supported platinum-based multi-metal catalysts are provided. The one-step preparation method comprises the specific steps: evenly mixing a carrier with an aqueous solution of a reducing agent, a surfactant, a platinum metal precursor and a non-platinum metal precursor, carrying out a reaction for 0.5-5 hours, and washing for multiple times at a low temperature (less than or equal to 100 DEG C) to enable the surfactant and other by-products in the product to be effectively removed. The platinum-based multi-metal catalysts having different metal loads (10-95 wt%) and different compositions and supported by different carriers are obtained, and the prepared supported platinum-based multi-metal catalysts are nanoparticles evenly dispersed on the surface of the carrier. The supported platinum-based multi-metal catalysts can be prepared through the one-step reaction, the reaction conditions are mild, operations are simple, the reaction is rapid, and synthesis is easy to enlarge. The prepared supported platinum-based multi-metal catalysts can be applied in the fields of petrochemical industry, chemical pharmacy, automobile tail gas purification and fuel cells.
Description
Technical field
The invention belongs to petrochemical industry, chemical pharmacy, purifying vehicle exhaust and fuel cell and use field, be specifically related to an one step preparation method and the application of a kind of loaded platinum Quito metallic catalyst.
Background technology
Platinum based catalyst is being brought into play irreplaceable effect in fields such as petrochemical industry, chemical pharmacy, purifying vehicle exhaust and fuel cells, but platinum reserves are limited, expensive, limited its large-scale application.Platinum based catalyst is supported on to the consumption that can effectively reduce platinum on various carrier materials, improves the utilization ratio of platinum.As in fuel cell field, adopt the earliest non-supported platinum black eelctro-catalyst, in electrode, platinum consumption is up to 10mg/cm
2; For improving platinum utilization ratio, reduce fuel cell cost, people are by adopting loaded Pt/C catalyst can make the consumption of Pt in electrode be reduced to 0.1～0.5mg/cm
2.Pt carrying capacity reduces to reduce the cost of fuel cell, the commercialization process of propellant battery.
Exploitation Pt Quito constituent element catalyst is another effective means that improves Pt utilization ratio.Compare with single constituent element Pt catalyst, Pt Quito constituent element catalyst all shows excellent catalytic activity and selective in various catalytic reactions, is subject in recent years people's extensive concern.If the main active of three-effect catalyst for purifying tail gas of car is the noble metals such as Pt, Rh, Pd.As in fuel cell field, people study discovery, and the metals such as Pd, Ru, Au, Fe, Ni, Cr are introduced catalytic activity and the long-term operation stability that can obviously improve Pt catalyst.The oxygen reduction reaction catalytic activity (Byungkwon Lim, et al., the Science that are significantly improved as Pt-Pd bimetallic eelctro-catalyst tool, 2009,324,1302), Oxidation of Formic Acid catalytic reaction activity, (Zhi-Cheng Zhang, et al., Nanoscale, 2012,4,2633), methanol oxidation catalytic activity (Shaojun Guo, et al., ACS Nano, 2010,4,1,547); PtRu catalyst is openly to report the best methanol oxidation catalyst of catalytic activity (Iwasita, et al, Langmuir, 2000,16,522) at present; The introducing of Au can obviously improve the stability (Zhang J.Science, 2007,315,220) of Pt catalyst in fuel cell.
Pt Quito constituent element metallic particles is dispersed in to carrier surface and forms supported catalyst and not only can reduce the consumption of precious metals pt, improve the utilization ratio of Pt, can improve catalytic performance, become the study hotspot of catalytic field simultaneously.At present about the preparation method of loaded Pt Quito metallic catalyst has bibliographical information.If Hu Linjie etc. is by utilizing the difference of Pt and Pd presoma salt solubility in different solvents, adopt immersion reduction method to obtain the Pt-Pd bimetallic catalyst (CN1245204A) with higher hydrogenation activity and sulfur resistance.Wei Zidong etc. introduce the surface functional groups such as carboxyl, hydroxyl and sulfydryl by chemical oxidation and sulfhydrylation in carbon nano tube surface, then utilize chemical reduction method that palladium-platinum bimetallic catalyst with nucleocapsid structure is loaded on to carbon nano tube surface.Shao Zhi has just waited and has utilized step-by-step reduction legal system for platinum palladium bimetallic catalyst (200910248847.0).Lei Yijie etc. utilize the difference of the reduction potential of different metal presoma, adopt the different reducing agent of reducing power to obtain loaded PtCu catalyst (201110029583.7) by stepwise reaction.Wu Bing etc. carry out pretreatment by carbon carrier in the concentrated sulfuric acid and red fuming nitric acid (RFNA) mixed solution, then adopt the auxiliary formic acid reducing process of microwave to obtain finely dispersed Pt-Co catalyst (201110105441.4).
In sum, although said method all can obtain loaded Pt Quito metallic catalyst, effectively reduce the consumption of noble metal platinum, the utilization rate of raising catalyst, but carbon carrier is surface-functionalized or step-by-step reduction in advance, preparation technology's very complicated, and said method is in the time preparing the higher catalyst of metal carrying capacity (>10wt%), be difficult to realize dispersed at carrier surface of metallic particles.For the problems referred to above, the present invention adopts one-step method can make loaded Pt Quito metallic catalyst, simple to operate, environmental friendliness, consuming time short, be easy to amplify synthetic, Pt Quito metallic catalyst of preparation has good catalytic activity, can be applicable to the fields such as fuel cell, electrochemical sensor, petrochemical industry, chemical pharmacy, purifying vehicle exhaust.
Summary of the invention
The object of the present invention is to provide an one step preparation method and the application of a kind of loaded platinum Quito metallic catalyst, the inventive method is simple to operate, is swift in response, and easily amplifies synthetic.In prepared loaded Pt Quito metallic catalyst, metal nanoparticle is evenly distributed on carrier surface, narrow size distribution, metal load ranges wide (10～95wt%), can be applicable to the fields such as fuel cell, electrochemical sensor, petrochemical industry, chemical pharmacy, purifying vehicle exhaust.
The invention provides an one step preparation method of a kind of loaded platinum Quito metallic catalyst, the method concrete steps are: by even the aqueous solution of carrier and reducing agent, surfactant, platinum presoma and non-platinum precursor, wherein reducing agent and platinum presoma and the molar concentration ratio of non-platinum precursor in the aqueous solution are 20:1-1:1, and surfactant and platinum presoma and the molar concentration ratio of non-platinum precursor in the aqueous solution are 100:1-1:1; React 0.5～5 hour; Repeatedly clean post-drying, obtain loaded platinum Quito metallic catalyst.
One one step preparation method of loaded platinum provided by the invention Quito metallic catalyst, described carrier is carbon black, CNT, carbon fiber, one or more mixtures in the graphene oxide of Graphene, reduction, mesoporous carbon, titanium dioxide, alundum (Al2O3), silica, molecular sieve; The specific area of described carrier is 50～2000m
2/ g.
One one step preparation method of loaded platinum provided by the invention Quito metallic catalyst, described reducing agent is one or more mixtures in the derivative of formaldehyde, formic acid, lithium borohydride, sodium borohydride, potassium borohydride, methyl alcohol, ethanol, polyalcohol, hydrazine hydrate, ethanedioic acid, malic acid, citric acid, glucose, sucrose, ascorbic acid and above-mentioned reducing agent or analog; Reducing agent molar concentration in reaction system is 0.5～5000mmol/L.
One one step preparation method of loaded platinum provided by the invention Quito metallic catalyst, described surfactant is softex kw, OTAC, neopelex, sodium cetanesulfonate, potassium stearate, the oleoyl amino acid sodium that contracts more, sodium dodecyl aminopropionitrile, NaLS, laurate sorbitan ester, oleic acid diethyl amide, dodecyldimethylammonium hydroxide inner salt, myristyl dimethyl methyl ethyl betaine, stearic acid, oleyl amine, oleic acid, one or more mixtures in the derivative of alkyl polyoxyethylene ether compounds and above-mentioned surfactant or analog, the molar concentration of surfactant in reaction system is 0.01～10000mmol/L.
One one step preparation method of loaded platinum provided by the invention Quito metallic catalyst, described platinum presoma is one or more mixtures in the derivative of chloroplatinic acid, chloroplatinous acid, chloroplatinate, chloroplatinite and above-mentioned platinum presoma or analog; The molar concentration of platinum presoma in reaction system is 1mmol-500mmol/L.。
One one step preparation method of loaded platinum provided by the invention Quito metallic catalyst, one or more mixtures in the derivative that described non-platinum presoma is ruthenium compound, rhodium compound, palladium compound, silver compound, rhenium compound, osmium compound, iridic compound, gold compound, iron compound, cobalt compound, nickel compound, copper compound and above-mentioned non-platinum presoma or analog;
Described ruthenium compound is one or more mixtures in the analog of ruthenium trichloride, ruthenium hydrochloride, ruthenium hydrochloride salt and above-mentioned ruthenium compound or derivative;
Described rhodium compound is one or more mixtures in the analog of rhodium chloride, the acid of chlorine rhodium, chlorine rhodate and above-mentioned rhodium compound or derivative;
Described palladium compound is one or more mixtures in the analog of palladium chloride, tetrachloro-palladium acid, tetrachloro-palladium acid salt and above-mentioned palladium compound or derivative;
Described silver compound is one or more mixtures in analog or the derivative of silver nitrate and above-mentioned silver compound;
Described rhenium compound is one or more mixtures in the analog of rhenium pentachloride, perrhenic acid, perrhenate and above-mentioned rhenium compound or derivative;
Described osmium compound is one or more mixtures in the analog of osmium tetrachloride, chlorine osmic acid, chloro-osmate and above-mentioned osmium compound or derivative;
Described iridic compound is one or more mixtures in the analog of iridic chloride, chloro-iridic acid, chloroiridate and above-mentioned iridic compound or derivative;
Described gold compound is one or more mixtures in the analog of gold trichloride, gold chloride, chloroaurate and above-mentioned gold compound or derivative;
Described iron compound is one or more mixtures in the analog of ferric trichloride, dichloride ferrous iron, ferric sulfate, ferrous sulfate, ferric nitrate, ferrous nitrate and above-mentioned iron compound or derivative;
Described cobalt compound is one or more mixtures in the analog of cobaltous dichloride, cobaltic chloride, cobalt nitrate, cobaltous sulfate and above-mentioned cobalt compound or derivative;
Described nickel compound is one or more mixtures in the analog of nickel chloride, nickelous sulfate, nickel nitrate and above-mentioned nickel compound or derivative;
Described copper compound is one or more mixtures in the analog of copper chloride, stannous chloride, copper sulphate, cuprous sulfate, copper nitrate, cuprous nitrate and above-mentioned copper compound or derivative.
The molar concentration of described non-platinum presoma in reaction system is 1mmol-500mmol/L.
One one step preparation method of loaded platinum provided by the invention Quito metallic catalyst, described cleaning process adopts centrifugal or filter type, and wherein cleaning process solvent used is one or more mixtures in analog or the derivative of water, methyl alcohol, ethanol, monochloro methane, carrene, chloroform, carbon tetrachloride, benzene, toluene, cyclohexane and above-mentioned solvent.
Loaded platinum Quito metallic catalyst prepared by the method for the invention, in this loaded platinum Quito metallic catalyst, metal dead weight capacity is 10%～95%, and wherein the carrying capacity of platinum is 5%～90%, and metal nanoparticle is dispersed at carrier surface.
Loaded platinum Quito metallic catalyst prepared by the method for the invention is applied to petrochemical industry, chemical pharmacy, purifying vehicle exhaust and fuel cell.
Compared with the preparation method of loaded Pt Quito metallic catalyst of existing report, the present invention has the following advantages:
A) the present invention adopts one-step synthesis can make loaded Pt Quito metallic catalyst, and simple to operate, environmental friendliness, consuming time short, is suitable for large-scale production;
B) adopt the noble metal load ranges 10wt%～95wt% of loaded Pt Quito metallic catalyst prepared by described method, and carrier range of choice is wide;
C) metal nanoparticle high degree of dispersion on carrier surface, does not reunite and is scattered;
D) there is good catalytic activity, can be used for the fields such as fuel cell, electrochemical sensor, petrochemical industry, chemical pharmacy, purifying vehicle exhaust.
Brief description of the drawings
Fig. 1 is the Pt that the embodiment of the present invention 1 obtains
3pd
1the transmission electron microscope picture (TEM) of/XC-72R (40wt%) catalyst;
Fig. 2 is the Pt that the embodiment of the present invention 1 obtains
3pd
1/ XC-72R (40wt%) catalyst is at the saturated 0.1M HClO of nitrogen
4cyclic voltammetry curve in the aqueous solution;
Fig. 3 is the Pt that the embodiment of the present invention 1 obtains
3pd
1/ XC-72R (40wt%) catalyst is at the saturated 0.1M HClO of oxygen
4oxygen reduction reaction polarization curve in the aqueous solution, electrode rotary speed is 1600rpm, potential scanning speed is 10mV/s;
Fig. 4 is the Pt that the embodiment of the present invention 2 obtains
1pd
1the transmission electron microscope picture (TEM) of/XC-72R (40wt%) catalyst;
Fig. 5 is the Pt that the embodiment of the present invention 3 obtains
9pd
1the transmission electron microscope picture (TEM) of/XC-72R (40wt.%) catalyst;
Fig. 6 is the Pt that the embodiment of the present invention 4 obtains
3pd
1the transmission electron microscope picture (TEM) of/EC-600J (40wt.%) catalyst;
Fig. 7 is the Pt that the embodiment of the present invention 5 obtains
1pd
1the transmission electron microscope picture (TEM) of/r-GO (80wt.%) catalyst;
Fig. 8 is the Pt that the embodiment of the present invention 6 obtains
1pd
1the transmission electron microscope picture (TEM) of/r-GO (40wt.%) catalyst;
Fig. 9 is the Pt that the embodiment of the present invention 7 obtains
9pd
1the transmission electron microscope picture (TEM) of/r-GO (80wt.%) catalyst;
Figure 10 is the Pt that the embodiment of the present invention 8 obtains
9pd
1the transmission electron microscope picture (TEM) of/r-GO (40wt.%) catalyst;
The Pt that Figure 11 embodiment of the present invention 12 obtains
9pd
3au
1/ G(60) the transmission electron microscope picture (TEM) of catalyst;
The Pt that Figure 12 embodiment of the present invention 15 obtains
9pd
3au
1/ TiO
2the transmission electron microscope picture (TEM) of catalyst.
Detailed description of the invention
The following examples will be further described the present invention, but not thereby limiting the invention.
Embodiment 1:Pt
3pd
1/ XC-72R (40wt%)
Be dispersed in the 60mL aqueous solution ultrasonic Vulcan XC-72R carbon dust (60mg), under stirring, add aqueous ascorbic acid (150mM) and the 10mL Brij30 aqueous solution (1mM) of 10mL; After stirring at room temperature 10min, in above-mentioned reaction system, add 11.6mL K
2pdCl
4and K
2ptCl
4mixed aqueous solution, wherein K
2pdCl
4and K
2ptCl
4concentration in this mixed solution is respectively 5mM and 15mM.React after 1 hour, the deionized water of utilizing 2L is repeatedly after suction filtration, washing, is placed in 60 DEG C of vacuum drying ovens dry 10 hours, obtains Pt
3pd
1/ XC-72R (40wt%) catalyst.Fig. 1 is obtained Pt
3pd
1the transmission electron microscope picture (TEM) of/XC-72R (40wt%) catalyst.As seen from Figure 1, Pt-Pd bimetal nano catalyst is grown in carrier surface, there is no obvious particle aggregation and is scattered.Adopt rotating disk electrode (r.d.e) to carry out electro-chemical activity evaluation obtained catalyst, concrete steps are as follows: the Pt that accurately weighs 5mg
3pd
1/ XC-72R (40wt%) catalyst, adds the Nafion (5wt%) of 50 μ L and the mixed solution of 5mL second alcohol and water, and ultrasonic dispersion obtains catalyst slurry, and it is 0.19625cm that the catalyst slurry that pipettes 10 μ L is evenly coated in area
2glass carbon rotating disk electrode (r.d.e) on, dry and obtain working electrode.The method of testing of catalyst electrochemical surface area is to be connected with the HClO of 0.1M of high pure nitrogen
4cyclic voltammetric (CV) curve that records catalyst in the aqueous solution, potential scan window is 0～1200mV(vs.RHE), sweep speed is 50mV/s.Electric quantity integration area by hydrogen adsorption-desorption peak district on CV curve can calculate corresponding electrochemical surface area (ECSA).The method of testing of hydrogen reduction activity is the 0.1MHClO saturated at oxygen
4the speed of sweeping with 10mV/s in the aqueous solution scans 1200mV from 0mV and obtains hydrogen reduction curve.The CV curve of catalyst and polarization curves of oxygen reduction respectively as shown in Figures 2 and 3, calculate the Pt of gained
3pd
1eCSA and the 0.9V(vs.RHE of/XC-72R (40wt%) catalyst) the specific mass activity of oxygen reduction reaction is respectively 33m under polarization potential
2/ g and 160mA/mg
pt+Pd, with commercialization Pt/C(40wt%) and close.
Embodiment 2:Pt
1pd
1/ XC-72R (40wt%)
Be dispersed in the 60mL aqueous solution ultrasonic Vulcan XC-72R carbon dust (60mg), under stirring, add the aqueous ascorbic acid (150mM) of 10mL and the Brij30 aqueous solution (1mM) of 10mL; After stirring at room temperature 10min, to the K that adds 13.2mL in above-mentioned reaction system
2pdCl
4and K
2ptCl
4mixed aqueous solution, wherein K
2pdCl
4and K
2ptCl
4concentration in this mixed solution is respectively 10mM and 10mM.React after 1 hour, the deionized water of utilizing 2L is repeatedly after suction filtration, washing, is placed in 60 DEG C of vacuum drying ovens dry 10 hours, obtains Pt
1pd
1/ XC-72R (40wt%) catalyst.Fig. 4 is obtained Pt
1pd
1the transmission electron microscope picture (TEM) of/XC-72R (40wt%) catalyst.As seen from Figure 4, Pt-Pd bimetal nano catalyst original position is grown in carrier surface, there is no obvious particle aggregation and is scattered.
Embodiment 3:Pt
9pd
1/ XC-72R (40wt%)
Be dispersed in the 60mL aqueous solution ultrasonic Vulcan XC-72R carbon dust (60mg), under stirring, add the aqueous ascorbic acid (150mM) of 10mL and the Brij30 aqueous solution (1mM) of 10mL; After stirring at room temperature 10min, to the K that adds 10.64mL in above-mentioned reaction system
2pdCl
4and K
2ptCl
4mixed aqueous solution, wherein K
2pdCl
4and K
2ptCl
4concentration in this mixed solution is respectively 2mM and 18mM.React after 1 hour, the deionized water of utilizing 2L is repeatedly after suction filtration, washing, is placed in 60 DEG C of vacuum drying ovens dry 10 hours, obtains Pt
9pd
1/ XC-72R (40wt%) catalyst.Fig. 5 is obtained Pt
9pd
1the transmission electron microscope picture (TEM) of/XC-72R (40wt%) catalyst.As seen from Figure 5, Pt-Pd bimetal nano catalyst original position is grown in carrier surface, there is no obvious particle aggregation and is scattered.
Embodiment 4:Pt
3pd
1/ EC-600J (40wt%)
Be dispersed in the 60mL aqueous solution ultrasonic EC-600J carbon dust (60mg), under stirring, add the aqueous ascorbic acid (150mM) of 10mL and the Brij30 aqueous solution (1mM) of 10mL; After stirring at room temperature 10min, to the K that adds 11.6mL in above-mentioned reaction system
2pdCl
4and K
2ptCl
4mixed aqueous solution, wherein K
2pdCl
4and K
2ptCl
4concentration in this mixed solution is respectively 5mM and 15mM.React after 1 hour, the deionized water of utilizing 2L is repeatedly after suction filtration, washing, is placed in 60 DEG C of vacuum drying ovens dry 10 hours, obtains Pt
3pd
1/ EC-600J (40wt%) catalyst.Fig. 6 is obtained Pt
3pd
1the transmission electron microscope picture (TEM) of/EC-600J (40wt%) catalyst.As seen from Figure 6, Pt-Pd bimetal nano catalyst original position is grown in carrier surface, there is no obvious particle aggregation and is scattered.
Embodiment 5:Pt
1pd
1/ rGO (80wt%)
By (60mg) ultrasonic being dispersed in the 60mL aqueous solution of graphene oxide (r-GO) of reduction, under stirring, add the aqueous ascorbic acid (150mM) of 10mL and the Brij30 aqueous solution (1mM) of 10mL; After stirring at room temperature 10min, to the K that adds 79.2mL in above-mentioned reaction system
2pdCl
4and K
2ptCl
4mixed aqueous solution, wherein K
2pdCl
4and K
2ptCl
4concentration in this mixed solution is respectively 10mM and 10mM.React after 1 hour, the deionized water of utilizing 2L is repeatedly after suction filtration, washing, is placed in 60 DEG C of vacuum drying ovens dry 10 hours, obtains Pt
1pd
1/ rGO (80wt%) catalyst.Fig. 7 is obtained Pt
1pd
1the transmission electron microscope picture (TEM) of/rGO (80wt%) catalyst.As seen from Figure 7, Pt-Pd bimetal nano catalyst original position is grown in carrier surface, there is no obvious particle aggregation and is scattered.
Embodiment 6:Pt
1pd
1/ rGO (40wt%)
By (60mg) ultrasonic being dispersed in the 60mL aqueous solution of graphene oxide (r-GO) of reduction, under stirring, add the aqueous ascorbic acid (150mM) of 10mL and the Brij30 aqueous solution (1mM) of 10mL; After stirring at room temperature 10min, to the K that adds 11.6mL in above-mentioned reaction system
2pdCl
4and K
2ptCl
4mixed aqueous solution, wherein K
2pdCl
4and K
2ptCl
4concentration in this mixed solution is respectively 10mM and 10mM.React after 1 hour, the deionized water of utilizing 2L is repeatedly after suction filtration, washing, is placed in 60 DEG C of vacuum drying ovens dry 10 hours, obtains Pt
1pd
1/ rGO (40wt%) catalyst.Fig. 8 is obtained Pt
1pd
1the transmission electron microscope picture (TEM) of/rGO (40wt%) catalyst.As seen from Figure 8, Pt-Pd bimetal nano catalyst original position is grown in carrier surface, there is no obvious particle aggregation and is scattered.
Embodiment 7:Pt
9pd
1/ rGO (80wt%)
By (60mg) ultrasonic being dispersed in the 60mL aqueous solution of graphene oxide (r-GO) of reduction, under stirring, add the aqueous ascorbic acid (150mM) of 10mL and the Brij30 aqueous solution (1mM) of 10mL; After stirring at room temperature 10min, to the K that adds 63.8mL in above-mentioned reaction system
2pdCl
4and K
2ptCl
4mixed aqueous solution, wherein K
2pdCl
4and K
2ptCl
4concentration in this mixed solution is respectively 2mM and 18mM.React after 1 hour, the deionized water of utilizing 2L is repeatedly after suction filtration, washing, is placed in 60 DEG C of vacuum drying ovens dry 10 hours, obtains Pt
9pd
1/ rGO (80wt%) catalyst.Fig. 9 is obtained Pt
9pd
1the transmission electron microscope picture (TEM) of/rGO (80wt%) catalyst.As seen from Figure 9, Pt-Pd bimetal nano catalyst original position is grown in carrier surface, there is no obvious particle aggregation and is scattered.
Embodiment 8:Pt
9pd
1/ rGO (40wt%)
By (60mg) ultrasonic being dispersed in the 60mL aqueous solution of graphene oxide (r-GO) of reduction, under stirring, add the aqueous ascorbic acid (150mM) of 10mL and the Brij30 aqueous solution (1mM) of 10mL; After stirring at room temperature 10min, to the K that adds 10.6mL in above-mentioned reaction system
2pdCl
4and K
2ptCl
4mixed aqueous solution, wherein K
2pdCl
4and K
2ptCl
4concentration in this mixed solution is respectively 2mM and 18mM.React after 1 hour, the deionized water of utilizing 2L is repeatedly after suction filtration, washing, is placed in 60 DEG C of vacuum drying ovens dry 10 hours, obtains Pt
9pd
1/ rGO (40wt%) catalyst.Figure 10 is obtained Pt
9pd
1the transmission electron microscope picture (TEM) of/rGO (40wt%) catalyst.As seen from Figure 10, Pt-Pd bimetal nano catalyst original position is grown in carrier surface, there is no obvious particle aggregation and is scattered.
Embodiment 9:Pt
3pd
1/ MWCNT (40wt%)
By multi-walled carbon nano-tubes MWCNT(60mg) ultrasonic being dispersed in the 60mL aqueous solution, under stirring, add the aqueous ascorbic acid (150mM) of 10mL and the Brij30 aqueous solution (1mM) of 10mL; After stirring at room temperature 10min, to the K that adds 11.6mL in above-mentioned reaction system
2pdCl
4and K
2ptCl
4mixed aqueous solution, wherein K
2pdCl
4and K
2ptCl
4concentration in this mixed solution is respectively 5mM and 15mM.React after 1 hour, the deionized water of utilizing 2L is repeatedly after suction filtration, washing, is placed in 60 DEG C of vacuum drying ovens dry 10 hours, obtains Pt
3pd
1/ MWCNT (40wt%) catalyst.
Embodiment 10:Pt
3pd
1/ XC-72R (40wt%)
Be dispersed in the 60mL aqueous solution ultrasonic Vulcan XC-72R carbon dust (60mg), under stirring, add the NaBH of 10mL
4the Brij30 aqueous solution (1mM) of the aqueous solution (150mM) and 10mL; After stirring at room temperature 10min, to the K that adds 11.6mL in above-mentioned reaction system
2pdCl
4and K
2ptCl
4mixed aqueous solution, wherein K
2pdCl
4and K
2ptCl
4concentration in this mixed solution is respectively 5mM and 15mM.React after 1 hour, the deionized water of utilizing 2L is repeatedly after suction filtration, washing, is placed in 60 DEG C of vacuum drying ovens dry 10 hours, obtains Pt
3pd
1/ XC-72R (40wt%) catalyst.
Embodiment 11:Pt
3pd
1/ XC-72R (40wt%)
Be dispersed in the 60mL aqueous solution ultrasonic Vulcan XC-72R carbon dust (60mg), under stirring, add the NaBH of 10mL
4the softex kw aqueous solution (1mM) of the aqueous solution (150mM) and 10mL; After stirring at room temperature 10min, to the K that adds 11.6mL in above-mentioned reaction system
2pdCl
4and K
2ptCl
4mixed aqueous solution, wherein K
2pdCl
4and K
2ptCl
4concentration in this mixed solution is respectively 5mM and 15mM.React after 1 hour, the deionized water of utilizing 2L is repeatedly after suction filtration, washing, is placed in 60 DEG C of vacuum drying ovens dry 10 hours, obtains Pt
3pd
1/ XC-72R (40wt%) catalyst.
Embodiment 12:Pt
9pd
3au
1/ G (40wt%)
By Graphene G(60mg) ultrasonic being dispersed in the 60mL aqueous solution, under stirring, add the aqueous ascorbic acid (150mM) of 10mL and the Brij30 aqueous solution (1mM) of 10mL; After stirring at room temperature 10min, to the K that adds 11.3mL in above-mentioned reaction system
2pdCl
4, K
2ptCl
4and NaAuCl
4mixed aqueous solution, wherein K
2pdCl
4, K
2ptCl
4and NaAuCl
4concentration in this mixed solution is respectively 4.5mM, 14mM and 1.5mM.React after 3 hours, the deionized water of utilizing 2L is repeatedly after suction filtration, washing, is placed in 60 DEG C of vacuum drying ovens dry 10 hours, obtains Pt
9pd
3au
1/ G (40wt%) catalyst.Figure 11 is obtained Pt
9pd
3au
1the transmission electron microscope picture (TEM) of/G (40wt%) catalyst.As seen from Figure 11, Pt-Pd-Au tri-metal nano catalyst original position is grown in carrier surface, there is no obvious particle aggregation and is scattered.
Embodiment 13:Pt
9pd
3ir
1/ G (40wt%)
By Graphene G(60mg) ultrasonic being dispersed in the 60mL aqueous solution, under stirring, add the aqueous ascorbic acid (150mM) of 10mL and the Brij30 aqueous solution (1mM) of 10mL; After stirring at room temperature 10min, to the K that adds 11.3mL in above-mentioned reaction system
2pdCl
4, K
2ptCl
4and NaIrCl
4mixed aqueous solution, wherein H
2pdCl
4, K
2ptCl
4and HAuCl
4concentration in this mixed solution is respectively 4.5mM, 14mM and 1.5mM.React after 3 hours, the deionized water of utilizing 2L is repeatedly after suction filtration, washing, is placed in 60 DEG C of vacuum drying ovens dry 10 hours, obtains Pt
9pd
3ir
1/ G (40wt%) catalyst.
Embodiment 14:Pt
1pd
1/ TiO
2(40wt%)
By TiO
2(60mg) ultrasonic being dispersed in the 60mL aqueous solution, adds the aqueous ascorbic acid (150mM) of 10mL and the Brij30 aqueous solution (1mM) of 10mL under stirring; After stirring at room temperature 10min, in above-mentioned reaction system, add 13.2mL H
2pdCl
4and H
2ptCl
6mixed solution, wherein K
2pdCl
4and K
2ptCl
4concentration in this mixed solution is respectively 10mM and 10mM.React after 1 hour, the deionized water of utilizing 2L is repeatedly after suction filtration, washing, is placed in 60 DEG C of vacuum drying ovens dry 10 hours, obtains Pt
1pd
1/ TiO
2(40wt%) catalyst.
Embodiment 15:Pt
9pd
3au
1/ TiO
2(40wt%)
By TiO
2(60mg) ultrasonic being dispersed in the 60mL aqueous solution, adds the aqueous ascorbic acid (150mM) of 10mL and the Brij30 aqueous solution (1mM) of 10mL under stirring; After stirring at room temperature 10min, to the K that adds 11.3mL in above-mentioned reaction system
2pdCl
4, K
2ptCl
4and NaAuCl
4mixed aqueous solution, wherein K
2pdCl
4, K
2ptCl
4and NaAuCl
4concentration in this mixed solution is respectively 4.5mM, 14mM and 1.5mM.React after 3 hours, the deionized water of utilizing 2L is repeatedly after suction filtration, washing, is placed in 60 DEG C of vacuum drying ovens dry 10 hours, obtains Pt
9pd
3au
1/ TiO
2(40wt%) catalyst.Figure 12 is obtained Pt
9pd
3au
1/ TiO
2(40wt%) the transmission electron microscope picture (TEM) of catalyst.As seen from Figure 12, Pt-Pd-Au tri-metal nano catalyst original position is grown in carrier surface, there is no obvious particle aggregation and is scattered.
Claims (9)
1. an one step preparation method of loaded platinum Quito metallic catalyst, it is characterized in that: the method concrete steps are: by even the aqueous solution of carrier and reducing agent, surfactant, platinum presoma and non-platinum precursor, react 0.5～5 hour; Repeatedly clean post-drying, obtain loaded platinum Quito metallic catalyst;
Described reducing agent and platinum presoma and the molar concentration ratio of non-platinum precursor in the aqueous solution are 20:1-1:1;
Described surfactant and platinum presoma and the molar concentration ratio of non-platinum precursor in the aqueous solution are 100:1-1:1.
2. according to an one step preparation method of loaded platinum Quito metallic catalyst described in claim 1, it is characterized in that: described carrier is carbon black, CNT, carbon fiber one or more mixtures in the graphene oxide of Graphene, reduction, mesoporous carbon, titanium dioxide, alundum (Al2O3), silica, molecular sieve; The specific area of described carrier is 50～2000m
2/ g.
3. according to an one step preparation method of loaded platinum Quito metallic catalyst described in claim 1, it is characterized in that: described reducing agent is one or more mixtures in the derivative of formaldehyde, formic acid, lithium borohydride, sodium borohydride, potassium borohydride, methyl alcohol, ethanol, polyalcohol, hydrazine hydrate, ethanedioic acid, malic acid, citric acid, glucose, sucrose, ascorbic acid and above-mentioned reducing agent or analog; Reducing agent molar concentration in reaction system is 0.5～5000mmol/L.
4. according to an one step preparation method of loaded platinum Quito metallic catalyst described in claim 1, it is characterized in that: described surfactant is softex kw, OTAC, neopelex, sodium cetanesulfonate, potassium stearate, the oleoyl amino acid sodium that contracts more, sodium dodecyl aminopropionitrile, NaLS, laurate sorbitan ester, oleic acid diethyl amide, dodecyldimethylammonium hydroxide inner salt, myristyl dimethyl methyl ethyl betaine, stearic acid, oleyl amine, oleic acid, one or more mixtures in the derivative of alkyl polyoxyethylene ether compounds and above-mentioned surfactant or analog, the molar concentration of surfactant in reaction system is 0.01～10000mmol/L.
5. according to an one step preparation method of loaded platinum Quito metallic catalyst described in claim 1, it is characterized in that: described platinum presoma is one or more mixtures in the derivative of chloroplatinic acid, chloroplatinous acid, chloroplatinate, chloroplatinite and above-mentioned platinum presoma or analog; The molar concentration of platinum presoma in reaction system is 1mmol-500mmol/L.
6. according to an one step preparation method of loaded platinum Quito metallic catalyst described in claim 1, it is characterized in that: one or more mixtures in the derivative that described non-platinum presoma is ruthenium compound, rhodium compound, palladium compound, silver compound, rhenium compound, osmium compound, iridic compound, gold compound, iron compound, cobalt compound, nickel compound, copper compound and above-mentioned non-platinum presoma or analog;
Described ruthenium compound is one or more mixtures in the analog of ruthenium trichloride, ruthenium hydrochloride, ruthenium hydrochloride salt and above-mentioned ruthenium compound or derivative;
Described rhodium compound is one or more mixtures in the analog of rhodium chloride, the acid of chlorine rhodium, chlorine rhodate and above-mentioned rhodium compound or derivative;
Described palladium compound is one or more mixtures in the analog of palladium chloride, tetrachloro-palladium acid, tetrachloro-palladium acid salt and above-mentioned palladium compound or derivative;
Described silver compound is one or more mixtures in analog or the derivative of silver nitrate and above-mentioned silver compound;
Described rhenium compound is one or more mixtures in the analog of rhenium pentachloride, perrhenic acid, perrhenate and above-mentioned rhenium compound or derivative;
Described osmium compound is one or more mixtures in the analog of osmium tetrachloride, chlorine osmic acid, chloro-osmate and above-mentioned osmium compound or derivative;
Described iridic compound is one or more mixtures in the analog of iridic chloride, chloro-iridic acid, chloroiridate and above-mentioned iridic compound or derivative;
Described gold compound is one or more mixtures in the analog of gold trichloride, gold chloride, chloroaurate and above-mentioned gold compound or derivative;
Described iron compound is one or more mixtures in the analog of ferric trichloride, dichloride ferrous iron, ferric sulfate, ferrous sulfate, ferric nitrate, ferrous nitrate and above-mentioned iron compound or derivative;
Described cobalt compound is one or more mixtures in the analog of cobaltous dichloride, cobaltic chloride, cobalt nitrate, cobaltous sulfate and above-mentioned cobalt compound or derivative;
Described nickel compound is one or more mixtures in the analog of nickel chloride, nickelous sulfate, nickel nitrate and above-mentioned nickel compound or derivative;
Described copper compound is one or more mixtures in the analog of copper chloride, stannous chloride, copper sulphate, cuprous sulfate, copper nitrate, cuprous nitrate and above-mentioned copper compound or derivative;
The molar concentration of described non-platinum presoma in reaction system is 1mmol-500mmol/L.
7. according to an one step preparation method of loaded platinum Quito metallic catalyst described in claim 1, it is characterized in that: described cleaning process adopts centrifugal or filter type, wherein cleaning process solvent used is one or more mixtures in analog or the derivative of water, methyl alcohol, ethanol, monochloro methane, carrene, chloroform, carbon tetrachloride, benzene, toluene, cyclohexane and above-mentioned solvent.
8. loaded platinum Quito metallic catalyst that described in claim 1 prepared by method, it is characterized in that: in this loaded platinum Quito metallic catalyst, metal dead weight capacity is 10%～95%, wherein the carrying capacity of platinum is 5%～90%, and metal nanoparticle is dispersed at carrier surface.
9. loaded platinum Quito metallic catalyst that described in claim 1 prepared by method is applied to petrochemical industry, chemical pharmacy, purifying vehicle exhaust and fuel cell.
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