CN107799778A - A kind of carbon fiber loaded noble metal catalyst and its preparation method and application - Google Patents
A kind of carbon fiber loaded noble metal catalyst and its preparation method and application Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
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Abstract
The invention discloses a kind of carbon fiber loaded noble metal catalyst and its preparation method and application, the preparation method comprises the following steps：(1) carbonaceous gas and oxygen are passed through into catalyst, 18 32h are reacted at 500 1000 DEG C, carbon fiber is made；(2) stabilizer and reducing agent are added into precious metal solution, 2 20h are reacted at 60 120 DEG C, obtain noble metal colloidal sol；(3) equi-volume impregnating and/or excessive infusion process are used, by impregnated carbon fiber in the noble metal colloidal sol, regulation pH value to 45, heating stirring is simultaneously aided with 5 20h of ultrasonic vibration reaction；(4) carbon fiber after dipping is placed in inert gas and calcined, obtain the carbon fiber loaded noble metal catalyst.The preparation method simple process of the present invention, under each step coordinated, using carbon fiber to be carbon-based, is prepared the excellent carbon fiber loaded noble metal catalyst of catalytic performance.
Description
Technical field
The invention belongs to field of catalyst preparation, be related to a kind of carbon fiber loaded noble metal catalyst and preparation method thereof and
Using.
Background technology
In recent years, carbon fiber because its have specific surface area big, high mechanical strength, conduct electricity very well, chemical stability is good etc.
Excellent physicochemical properties, it has also become study hotspot, and it is applied to electrochemical field as a kind of carbon-based material.
The easy adsorption reaction thing in surface of noble metal, and absorption affinity is moderate, advantageously forms intermediate active compound, not only
Chemical reaction velocity can be accelerated, and be not involved in reacting in itself, there is the characteristic such as high temperature resistant, anti-oxidant, corrosion-resistant, it has also become
Important catalysis material is applied to catalyst field.
Infusion process is to be adsorbed based on metal salt solution or be stored in the capillary of carrier and penetrate into the principle of inner surface, is made
One of common method of standby solid catalyst.Carrier is generally put into metal salt solution by this method, after dipping reaches balance,
Carrier is isolated, removes excessive solution, then catalyst is made through treatment process such as drying, calcining, activation.The letter of infusion process method
It is single, it is cheap, turn into the main method that load type metal catalyst is prepared in industry at present.
CN102658133A discloses a kind of preparation method of activated carbon supported noble metal catalyst, and this method is by activated carbon
Carrier mixes with the nitrate solution containing noble metal or chlorination saline solution, 25-90 DEG C of stirring 2-6h, then in 25-80 DEG C of condition
Lower addition alkaline aqueous solution adjusts reacting liquid pH value to 6-9,25-80 DEG C of insulated and stirred 0.5-4h, obtains slurries, locates after slurries
Reason, obtain the activated carbon supported noble metal catalyst.But this method condition is harsh, the dispersion effect of activated carbon is poor so that
Precious metal catalyst hydraulic performance decline, service life are short.
CN103691428A discloses a kind of preparation method of charcoal supported noble metal catalyst, and this method using infusion process to being obtained
The carrier of the carried noble metal presoma obtained is reduced using atmosphere cold plasma, obtains the catalysis of high-performance carbon supported noble metal
Agent.But this method complex process, cost is higher, and yield is relatively low.
Therefore it provides a kind of preparation method of simple, the lower-cost noble metal catalyst of technique, obtains catalytic performance
Noble metal catalyst good, load capacity is high, it is significant in electrochemical catalysis field.
The content of the invention
In view of the shortcomings of the prior art, the present invention provide a kind of carbon fiber loaded noble metal catalyst and preparation method thereof and
Using methods described technique is simple, cost is relatively low, and the noble metal catalyst of preparation is loaded with high content using carbon fiber as carrier
Noble metal, catalytic activity is up to 99.5%.
In a first aspect, the present invention provides a kind of preparation method of carbon fiber loaded noble metal catalyst, comprise the following steps：
(1) carbonaceous gas and oxygen are passed through into catalyst, reacts 18-32h at 500-1000 DEG C, carbon fiber is made；
(2) stabilizer and reducing agent are added into precious metal solution, 2-20h is reacted at 60-120 DEG C, obtains noble metal
Colloidal sol；
(3) equi-volume impregnating and/or excessive infusion process are used, by impregnated carbon fiber in the noble metal colloidal sol, is adjusted
Save pH value to 4-5, heating stirring and be simultaneously aided with ultrasonic vibration reaction 5-20h；
(4) carbon fiber after dipping is placed in inert gas and calcined, obtain the carbon fiber loaded noble metal catalyst.
Volume of the invention by adjusting carbonaceous gas, the carbon fiber that tactical rule, particle diameter are small, specific surface area is big is obtained,
By adjusting the mass ratio of carbonaceous gas and precious metal solution, obtaining uniform load has the carbon fiber of noble metal, in each step
Under coordinated, the carbon fiber loaded precious metals yield that is prepared is up to 99.8%, and catalyst catalytic performance is up to 99.5%.
Preferably, step (1) described catalyst includes gama-alumina nickel-loaded, gama-alumina load iron or gamma oxidation
Aluminium loads the combination of any one or at least two in dilval, such as can be gama-alumina nickel-loaded and gamma oxidation
The combination of aluminium load iron, the combination of gama-alumina nickel-loaded and gama-alumina load dilval or gama-alumina load iron
With the combination of gama-alumina load dilval, preferably gama-alumina load dilval.
Preferably, the volume ratio of step (1) carbonaceous gas and the oxygen is (1-5):1, such as can be 1:1、
2:1、3:1、4:1 or 5:1, preferably 3:1.
Preferably, step (1) described carbonaceous gas includes at least two combination in methane, ethene or carbon monoxide,
Such as can be the combination of methane and ethene, the combination of methane and carbon monoxide, ethene and the combination of carbon monoxide or methane,
The combination of the combination of ethene and carbon monoxide, preferably methane, ethene and carbon monoxide；
Preferably, the volume ratio of the methane, ethene and carbon monoxide is (1-3):(1-2):2, such as can be 1:1:
2、2:1:2、3:1:2、1:2:2、2:2:2 or 3:2:2, preferably 2:1:2.
Preferably, the temperature of step (1) described reaction is 500-800 DEG C, for example, can be 500 DEG C, 520 DEG C, 550 DEG C,
580 DEG C, 600 DEG C, 620 DEG C, 650 DEG C, 680 DEG C, 700 DEG C, 720 DEG C, 750 DEG C, 780 DEG C or 800 DEG C, preferably 650 DEG C.
Preferably, the time of step (1) described reaction is 20-30h, for example, can be 20h, 21h, 22h, 23h, 24h,
25h, 26h, 27h, 28h, 29h or 30h, preferably 25h.
Preferably, the particle diameter of step (1) described carbon fiber is 10-50nm, for example, can be 10nm, 12nm, 15nm,
18nm, 20nm, 22nm, 25nm, 28nm, 30nm, 32nm, 35nm, 38nm, 40nm, 42nm, 45nm, 48nm or 50nm.
Preferably, the specific surface area of step (1) described carbon fiber is 200-1000m2/ g, such as can be 200m2/g、
250m2/g、300m2/g、350m2/g、400m2/g、450m2/g、500m2/g、550m2/g、600m2/g、650m2/g、700m2/g、
750m2/g、800m2/g、850m2/g、900m2/g、950m2/ g or 1000m2/g。
Preferably, step (2) described noble metal includes any of platinum, ruthenium, palladium, rhodium, iridium or gold or at least two
Combination, preferably platinum.
Preferably, step (2) described stabilizer includes polyethylene glycol, polyvinyl pyridine, polyvinyl alcohol, positive esters of silicon acis or lemon
In lemon acid sodium any one or at least two combination, preferably polyethylene glycol.
Preferably, step (2) described reducing agent includes hydrogen, acetaldehyde, carbon monoxide, polyethylene glycol or polyvinylpyrrolidine
In alkanone any one or at least two combination, preferably acetaldehyde.
Preferably, the temperature of step (2) described reaction is 80-110 DEG C, for example, can be 80 DEG C, 81 DEG C, 82 DEG C, 83 DEG C,
84℃、85℃、86℃、87℃、88℃、89℃、90℃、91℃、92℃、93℃、94℃、95℃、96℃、97℃、98℃、99
DEG C, 100 DEG C, 101 DEG C, 102 DEG C, 103 DEG C, 104 DEG C, 105 DEG C, 106 DEG C, 107 DEG C, 108 DEG C, 109 DEG C or 110 DEG C, be preferably
100℃。
Preferably, the time of step (2) described reaction is 5-15h, for example, can be 5h, 6h, 7h, 8h, 9h, 10h, 11h,
12h, 13h, 14h or 15h, preferably 8h.
Preferably, the mass ratio of step (3) carbon fiber and the noble metal colloidal sol is 10:(1-5), such as can be
10:1、10:2、10:3、10:4 or 10:5, preferably 10:(3-4).
Preferably, the temperature of step (3) described heating is 40-80 DEG C, for example, can be 40 DEG C, 42 DEG C, 45 DEG C, 48 DEG C,
50 DEG C, 52 DEG C, 55 DEG C, 58 DEG C, 60 DEG C, 62 DEG C, 65 DEG C, 68 DEG C, 70 DEG C, 72 DEG C, 75 DEG C, 78 DEG C or 80 DEG C, preferably 60 DEG C.
Preferably, the time of step (3) described reaction is 8-15h, for example, can be 8h, 9h, 10h, 11h, 12h, 13h,
14h or 15h, preferably 10h.
Preferably, step (4) described inert gas includes any one in nitrogen, helium or argon gas or at least two
Combination, such as can be the combination of nitrogen and helium, the combination of nitrogen and argon gas, helium and the combination of argon gas or nitrogen, helium
With the combination of argon gas, preferably argon gas.
Preferably, the temperature of step (4) described calcining is 200-400 DEG C, for example, can be 200 DEG C, 210 DEG C, 220 DEG C,
230℃、240℃、250℃、260℃、270℃、280℃、290℃、300℃、310℃、320℃、330℃、340℃、350
DEG C, 360 DEG C, 370 DEG C, 380 DEG C, preferably 390 DEG C or 400 DEG C, 300 DEG C.
Preferably, step (4) calcining time be 3-5h, such as can be 3h, 3.1h, 3.2h, 3.3h, 3.4h, 3.5h,
3.6h, 3.7h, 3.8h, 3.9h, 4h, 4.1h, 4.2h, 4.3h, 4.4h, 4.5h, 4.6h, 4.7h, 4.8h, 4.9h or 5h, preferably
For 4h.
Preferably, the step of purifying and activated carbon fiber are also included after the step (1).
Preferably, the purifying specifically includes with activated carbon fiber：
(1 ') is dried after carbon fiber is washed into 3-5h in NaOH solution；
(2 ') are dried after carbon fiber is washed into 5-6h in HCl solution；
Carbon fiber is carried out oxidation processes by (3 ') in atmosphere, is then stripped using ethanol, the carbon of obtained activation
Fiber.
Preferably, the concentration of the NaOH solution described in step (1 ') is 3-6M, for example, can be 3M, 3.1M, 3.2M,
3.3M、3.4M、3.5M、3.6M、3.7M、3.8M、3.9M、4M、4.1M、4.2M、4.3M、4.4M、4.5M、4.6M、4.7M、
4.8M, 4.9M, 5M, 5.1M, 5.2M, 5.3M, 5.4M, 5.5M, 5.6M, 5.7M, 5.8M, 5.9M or 6M, preferably 5M.
Preferably, the time of step (the 1 ') washing is 3-5h, for example, can be 3h, 3.1h, 3.2h, 3.3h, 3.4h,
3.5h, 3.6h, 3.7h, 3.8h, 3.9h, 4h, 4.1h, 4.2h, 4.3h, 4.4h, 4.5h, 4.6h, 4.7h, 4.8h, 4.9h or 5h,
Preferably 4h.
Preferably, the temperature of step (the 1 ') washing is 90-120 DEG C, for example, can be 90 DEG C, 92 DEG C, 95 DEG C, 98
DEG C, 100 DEG C, 102 DEG C, 105 DEG C, 108 DEG C, 110 DEG C, 112 DEG C, 115 DEG C, preferably 118 DEG C or 120 DEG C, 100 DEG C.
Preferably, the concentration of step (the 2 ') HCl solution is 3-6M, for example, can be 3M, 3.2M, 3.5M, 3.8M,
4M, 4.2M, 4.5M, 4.8M, 5M, 5.2M, 5.5M, 5.8M or 6M, preferably 5M.
Preferably, the time of step (the 2 ') washing is 5-6h, for example, can be 5h, 5.1h, 5.2h, 5.3h, 5.4h,
5.5h, 5.6h, 5.7h, 5.8h, 5.9h or 6h, preferably 5.5h.
Preferably, the temperature of step (the 2 ') washing is 80-100 DEG C, for example, can be 80 DEG C, 81 DEG C, 82 DEG C, 83
℃、84℃、85℃、86℃、87℃、88℃、89℃、90℃、91℃、92℃、93℃、94℃、95℃、96℃、97℃、98
DEG C, 99 DEG C or 100 DEG C, preferably 85 DEG C.
Preferably, the temperature of step (the 3 ') oxidation processes is 100-220 DEG C, for example, can be 100 DEG C, 110 DEG C,
120 DEG C, 130 DEG C, 140 DEG C, 150 DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 190 DEG C, 200 DEG C, 210 DEG C or 220 DEG C, preferably 180
℃。
Preferably, the time of step (the 3 ') oxidation processes is 3-5h, for example, can be 3h, 3.1h, 3.2h, 3.3h,
3.4h、3.5h、3.6h、3.7h、3.8h、3.9h、4h、4.1h、4.2h、4.3h、4.4h、4.5h、4.6h、4.7h、4.8h、4.9h
Or 5h, preferably 4h.
Preferably, the time of step (the 3 ') extracting is 5-10h, for example, can be 5h, 5.2h, 5.5h, 5.8h, 6h,
6.2h, 6.5h, 6.8h, 7h, 7.2h, 7.5h, 7.8h, 8h, 8.2h, 8.5h, 8.8h, 9h, 9.2h, 9.5h, 9.8h or 10h, it is excellent
Elect 8h as.
As optimal technical scheme, the invention provides a kind of preparation method of carbon fiber loaded noble metal catalyst, bag
Include following steps：
(1) it is (1-5) according to volume ratio into gamma-alumina catalyst:1 is passed through carbonaceous gas and oxygen, in 500-
18-32h is reacted at 1000 DEG C, obtained particle diameter is 10-50nm, specific surface area 200-1000m2/ g carbon fiber；
(2) at 90-120 DEG C, carbon fiber is washed into 3-5h in the NaOH solution that concentration is 3-6M, is then cooled to 80-
100 DEG C, carbon fiber is washed into 5-6h in the HCl solution that concentration is 3-6M, after drying, by carbon fiber oxidation processes in atmosphere
3-5h, then using ethanolic extraction 5-10h, the carbon fiber of obtained activation；
(3) stabilizer and reducing agent are added into precious metal solution, 2-20h is reacted at 60-120 DEG C, obtains noble metal
Colloidal sol；
(4) equi-volume impregnating and/or excessive infusion process are used, by the impregnated carbon fiber of activation in the noble metal colloidal sol
In, the mass ratio of carbon fiber and noble metal colloidal sol is 10:(1-5), regulation pH value is to 4-5, heating stirring at 40-80 DEG C, and auxiliary
5-20h is reacted with ultrasonic vibration；
(5) carbon fiber after dipping is placed in inert gas, 3-5h is calcined at 200-400 DEG C, it is fine to obtain the carbon
Tie up supported precious metal catalyst.
Second aspect, it is prepared the invention provides a kind of preparation method as described in relation to the first aspect carbon fiber loaded
Noble metal catalyst.
The third aspect, it is used to make the invention provides a kind of carbon fiber loaded noble metal catalyst as described in second aspect
Standby fuel cell.
Compared with prior art, the present invention has the advantages that：
(1) method of the invention is existed using the mixed gas of methane, ethene and carbon monoxide as carbonaceous gas with oxygen
In rational proportion, the carbon fiber of preparation is regularly arranged into tubulose, and the minimum 12nm of particle diameter, specific surface area is up to
980m2/ g so that noble metal may be uniformly dispersed in the capillary and inner surface of carbon fiber；
(2) using the carbon fiber of the present invention as carbon-based supports, the carbon fiber loaded noble metal catalyst yield of preparation is up to
99.8%, catalytic performance is preferably up to 99.5%；
(3) method technique of the invention is simple, each step Synergistic, and the catalyst production of preparation is high, and performance is excellent, surely
It is fixed reliable.
Embodiment
For the present invention technological means and its effect taken is expanded on further, the present invention is made with reference to embodiments into
Illustrate to one step.It is understood that embodiment described herein is used only for explaining the present invention, rather than to this hair
Bright restriction.
In the examples where no specific technique or condition is specified, according to the technology or condition described by document in the art,
Or carried out according to product description.Agents useful for same or the unreceipted production firm person of instrument, be can be by regular channel commercially available from
The conventional products of acquisition.
The preparation of 1 carbon fiber loaded platinum catalyst of embodiment
(1) it is 6 according to volume ratio into gama-alumina load dilval:3:6:5 are passed through methane, ethene, carbon monoxide
And oxygen, 25h is reacted at 650 DEG C, carbon fiber is made；
At (2) 100 DEG C, carbon fiber is washed into 4h in the NaOH solution that concentration is 5M, is then cooled to 85 DEG C, carbon is fine
Tie up and wash 5.5h in the HCl solution that concentration is 5M, after drying, by the carbon fiber oxidation processes 4h at 180 DEG C in atmosphere, so
Ethanolic extraction 8h, the carbon fiber of obtained activation are used afterwards；
(3) polyethylene glycol and acetaldehyde are added into platinum salt solution, 8h is reacted at 100 DEG C, obtains the colloidal sol of platinum；
(4) by the impregnated carbon fiber of activation in the colloidal sol of the platinum, the mass ratio of the colloidal sol of carbon fiber and platinum is 10:3,
PH value is adjusted to 4-5, heating stirring at 60 DEG C, and it is aided with ultrasonic vibration reaction 10h；
(5) carbon fiber after dipping is placed in argon gas, 4h is calcined at 300 DEG C, obtained the carbon fiber loaded platinum and urge
Agent.
The preparation of 2 carbon fiber loaded ruthenium catalyst of embodiment
(1) it is 1 according to volume ratio into gama-alumina load dilval:1:2:1 is passed through methane, ethene, carbon monoxide
And oxygen, 20h is reacted at 600 DEG C, carbon fiber is made；
At (2) 95 DEG C, carbon fiber is washed into 3.5h in the NaOH solution that concentration is 4M, 82 DEG C are then cooled to, by carbon
Fiber washs 5.5h in the HCl solution that concentration is 4M, after drying, by carbon fiber oxidation processes at 150 DEG C in atmosphere
3.5h, then using ethanolic extraction 9h, the carbon fiber of obtained activation；
(3) polyvinyl pyridine and hydrogen are added into ruthenium salting liquid, 15h is reacted at 80 DEG C, obtains the colloidal sol of ruthenium；
(4) by the impregnated carbon fiber of activation in the colloidal sol of the ruthenium, the mass ratio of the colloidal sol of carbon fiber and ruthenium is 10:4,
PH value is adjusted to 4-5, heating stirring at 50 DEG C, and it is aided with ultrasonic vibration reaction 8h；
(5) carbon fiber after dipping is placed in argon gas, 4.5h is calcined at 350 DEG C, obtain the carbon fiber loaded ruthenium
Catalyst.
The preparation of 3 carbon fiber loaded palladium catalyst of embodiment
(1) it is 2 according to volume ratio into gama-alumina load dilval:4:4:5 are passed through methane, ethene, carbon monoxide
And oxygen, 30h is reacted at 800 DEG C, carbon fiber is made；
At (2) 110 DEG C, carbon fiber is washed into 4.5h in the NaOH solution that concentration is 5.5M, is then cooled to 90 DEG C, will
Carbon fiber washs 5.5h in the HCl solution that concentration is 5.5M, after drying, by carbon fiber in atmosphere at 200 DEG C at oxidation
Manage 4.5h, then using ethanolic extraction 6h, the carbon fiber of obtained activation；
(3) polyvinyl alcohol and carbon monoxide are added into palladium salt solution, 5h is reacted at 110 DEG C, obtains the colloidal sol of palladium；
(4) by the impregnated carbon fiber of activation in the colloidal sol of the palladium, the mass ratio of the colloidal sol of carbon fiber and palladium is 10:2,
PH value is adjusted to 4-5, heating stirring at 70 DEG C, and it is aided with ultrasonic vibration reaction 15h；
(5) carbon fiber after dipping is placed in argon gas, 3.5h is calcined at 250 DEG C, obtain the carbon fiber loaded palladium
Catalyst.
The preparation of 4 carbon fiber loaded rhodium catalyst of embodiment
(1) it is 15 according to volume ratio into gama-alumina nickel-loaded:5:10:6 are passed through methane, ethene, carbon monoxide and oxygen
Gas, 18h is reacted at 500 DEG C, carbon fiber is made；
At (2) 90 DEG C, carbon fiber is washed into 3h in the NaOH solution that concentration is 3M, is then cooled to 80 DEG C, carbon is fine
Tie up and wash 5h in the HCl solution that concentration is 3M, after drying, by the carbon fiber oxidation processes 3h at 100 DEG C in atmosphere, then
Using ethanolic extraction 10h, the carbon fiber of obtained activation；
(3) positive esters of silicon acis and polyethylene glycol are added into rhodium salting liquid, reacts 20h at 60 DEG C, obtains the colloidal sol of rhodium；
(4) by the impregnated carbon fiber of activation in the colloidal sol of the rhodium, the mass ratio of the colloidal sol of carbon fiber and rhodium is 10:1,
PH value is adjusted to 4-5, heating stirring at 40 DEG C, and it is aided with ultrasonic vibration reaction 5h；
(5) carbon fiber after dipping is placed in nitrogen, 5h is calcined at 400 DEG C, obtained the carbon fiber loaded rhodium and urge
Agent.
The preparation of 5 carbon fiber loaded Au catalyst of embodiment
(1) it is 3 according to volume ratio into gama-alumina load iron:2:2:7 are passed through methane, ethene, carbon monoxide and oxygen
Gas, 32h is reacted at 1000 DEG C, carbon fiber is made；
At (2) 120 DEG C, carbon fiber is washed into 5h in the NaOH solution that concentration is 6M, 100 DEG C are then cooled to, by carbon
Fiber washs 6h in the HCl solution that concentration is 6M, after drying, by the carbon fiber oxidation processes 5h at 220 DEG C in atmosphere, so
Ethanolic extraction 5h, the carbon fiber of obtained activation are used afterwards；
(3) sodium citrate and PVP are added into gold salt solution, 2h is reacted at 120 DEG C, obtains gold
Colloidal sol；
(4) by the impregnated carbon fiber of activation in the golden colloidal sol, the mass ratio of carbon fiber and the colloidal sol of gold is 2:1,
PH value is adjusted to 4-5, heating stirring at 80 DEG C, and it is aided with ultrasonic vibration reaction 20h；
(5) carbon fiber after dipping is placed in helium, 3h is calcined at 200 DEG C, obtained the carbon fiber loaded gold and urge
Agent.
Comparative example 1
Compared with Example 1, the volume ratio of methane, ethene, carbon monoxide and oxygen is 4:3:2:3, other preparation conditions
It is same as Example 1.
Comparative example 2
Compared with Example 1, the volume ratio of methane, ethene, carbon monoxide and oxygen is 1:1:4:2, other preparation conditions
It is same as Example 1.
Comparative example 3
Compared with Example 1, carbonaceous gas comprises only methane, and the volume ratio of methane and oxygen is 3:1, other preparation conditions
It is same as Example 1.
Comparative example 4
Compared with Example 1, carbonaceous gas comprises only ethene, and the volume ratio of ethene and oxygen is 3:1, other preparation conditions
It is same as Example 1.
Comparative example 5
Compared with Example 1, carbonaceous gas comprises only carbon monoxide, and the volume ratio of carbon monoxide and oxygen is 3:1, other
Preparation condition is same as Example 1.
Comparative example 6
Compared with Example 1, carbon-based supports use activated carbon, and other preparation process are same as Example 1.
Comparative example 7
Compared with Example 1, the mass ratio of the colloidal sol of carbon fiber and platinum is 20:1, other preparation conditions and the phase of embodiment 1
Together.
Comparative example 8
Compared with Example 1, the mass ratio of the colloidal sol of carbon fiber and platinum is 5:4, other preparation conditions and the phase of embodiment 1
Together.
The sign of carbon fiber loaded noble metal catalyst
The carbon-based load prepared using Scanning Electron microscope and Porosimetry to embodiment 1-5 and comparative example 1-8 is expensive
Metallic catalyst is characterized, and the results are shown in Table 1.
The sign of 1 carbon-based supported precious metal catalyst of table
Contrasted from embodiment 1-5, when the volume ratio of methane, ethene, carbon monoxide and oxygen is 1:1:2:When 1, prepare
Carbon fiber it is regularly arranged in a tubular form, the minimum 12nm of particle diameter, specific surface area is up to 980m2/ g, it can be used as a kind of excellent
Carbon-based supports carried noble metal, dispersive property is good, and noble metal is uniformly point wherein.
Compared with Example 1, the volume ratio of comparative example 1-2 methane, ethene, carbon monoxide and oxygen is unreasonable, prepares
Carbon fiber it is in irregular shape, particle diameter is larger, specific surface area reduce, to the dispersed poor of noble metal；Comparative example 3-5 uses into
Divide single carbonaceous gas, the carbon fiber of preparation is in irregular shape, and particle diameter reaches micron order, and specific surface area is remarkably decreased, your gold
Category can not it is dispersed in the carbon fibers, be focusing only on carbon fiber certain a part；Comparative example 6 uses activated carbon as carbon-based,
The specific surface area of activated carbon is small, and noble metal can not be dispersed in activated carbon；Comparative example 7-8 carbon fiber and noble metal colloidal sol
Mass ratio it is unreasonable, although prepare carbon fiber particle diameter is small, specific surface area is big, tactical rule, noble metal skewness
It is even.
The yield and catalytic performance of carbon-based supported precious metal catalyst
The yield and catalytic performance of carbon-based supported precious metal catalyst prepared by embodiment 1-5 and comparative example 1-8 are shown in Table 2.
The yield and catalytic performance of 2 carbon-based supported precious metal catalyst of table
| Numbering | Yield (%) | Catalytic performance (%) |
| Embodiment 1 | 99.8 | 99.5 |
| Embodiment 2 | 99.2 | 98.8 |
| Embodiment 3 | 98.6 | 98.1 |
| Embodiment 4 | 97.8 | 97.9 |
| Embodiment 5 | 97.5 | 97.3 |
| Comparative example 1 | 76.3 | 34.1 |
| Comparative example 2 | 77.4 | 35.2 |
| Comparative example 3 | 43.5 | 26.7 |
| Comparative example 4 | 46.7 | 29.4 |
| Comparative example 5 | 45.2 | 27.4 |
| Comparative example 6 | 65.3 | 28.2 |
| Comparative example 7 | 99.2 | 47.9 |
| Comparative example 8 | 98.9 | 50.1 |
Carbon fiber loaded noble metal catalyst yield prepared by the embodiment of the present invention is higher than 97%, and catalytic performance is higher than
97%；Comparative example 1-5 is unreasonable because of the species and volume of carbonaceous gas so that the yield of carbon fiber loaded noble metal catalyst shows
Write and decline, catalytic performance substantially reduces；Comparative example 6 uses activated carbon, and particle diameter is big, specific surface area is small, dispersive property as carbon-based
Difference, it have impact on the catalytic performance of noble metal；Comparative example 7-8 prepare carbon fiber particle diameter is small, specific surface area is big, tactical rule, but
It is noble metal skewness so that the catalytic performance of catalyst is decreased obviously.
In summary, the preparation method of carbon fiber loaded noble metal catalyst of the invention, methane, ethene and an oxygen are used
Change the mixed gas of carbon as carbonaceous gas, with oxygen in rational proportion, the carbon fiber structural rule of preparation, particle diameter
It is small, specific surface area is big, dispersive property is good, the carbon fiber loaded noble metal catalyst yield using the carbon fiber as carbon-based preparation
Height, catalytic performance are excellent.
Applicant states that the present invention illustrates the method detailed of the present invention, but not office of the invention by above-described embodiment
It is limited to above-mentioned method detailed, that is, does not mean that the present invention has to rely on above-mentioned method detailed and could implemented.Art
Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to each raw material of product of the present invention
Addition, selection of concrete mode etc., within the scope of all falling within protection scope of the present invention and disclosing.
Claims (10)
1. a kind of preparation method of carbon fiber loaded noble metal catalyst, it is characterised in that comprise the following steps：
(1) carbonaceous gas and oxygen are passed through into catalyst, reacts 18-32h at 500-1000 DEG C, carbon fiber is made；
(2) stabilizer and reducing agent are added into precious metal solution, 2-20h is reacted at 60-120 DEG C, obtains noble metal colloidal sol；
(3) equi-volume impregnating and/or excessive infusion process are used, by impregnated carbon fiber in the noble metal colloidal sol, adjusts pH
Value to 4-5, heating stirring is simultaneously aided with ultrasonic vibration reaction 5-20h；
(4) carbon fiber after dipping is placed in inert gas and calcined, obtain the carbon fiber loaded noble metal catalyst.
2. preparation method according to claim 1, it is characterised in that step (1) described catalyst is born including gama-alumina
Load nickel, gama-alumina load iron or gama-alumina load the combination of any one or at least two in dilval, preferably
Dilval is loaded for gama-alumina；
Preferably, the volume ratio of step (1) carbonaceous gas and the oxygen is (1-5):1, preferably 3:1；
Preferably, step (1) described carbonaceous gas includes at least two combination in methane, ethene or carbon monoxide, preferably
For the combination of methane, ethene and carbon monoxide；
Preferably, the volume ratio of the methane, ethene and carbon monoxide is (1-3):(1-2):2, preferably 2:1:2；
Preferably, the temperature of step (1) described reaction is 500-800 DEG C, preferably 650 DEG C；
Preferably, the time of step (1) described reaction is 20-30h, preferably 25h；
Preferably, the particle diameter of step (1) described carbon fiber is 10-50nm；
Preferably, the specific surface area of step (1) described carbon fiber is 200-1000m2/g。
3. preparation method according to claim 1 or 2, it is characterised in that step (2) described noble metal include platinum, ruthenium,
Any of palladium, rhodium, iridium or gold or at least two combination, preferably platinum；
Preferably, step (2) described stabilizer includes polyethylene glycol, polyvinyl pyridine, polyvinyl alcohol, positive esters of silicon acis or citric acid
In sodium any one or at least two combination, preferably polyethylene glycol；
Preferably, step (2) described reducing agent includes hydrogen, acetaldehyde, carbon monoxide, polyethylene glycol or PVP
In any one or at least two combination, preferably acetaldehyde；
Preferably, the temperature of step (2) described reaction is 80-110 DEG C, preferably 100 DEG C；
Preferably, the time of step (2) described reaction is 5-15h, preferably 8h.
4. according to the preparation method described in claim any one of 1-3, it is characterised in that step (3) carbon fiber with it is described
The mass ratio of noble metal colloidal sol is 10:(1-5), preferably 10:(3-4)；
Preferably, the temperature of step (3) described heating is 40-80 DEG C, preferably 60 DEG C；
Preferably, the time of step (3) described reaction is 8-15h, preferably 10h.
5. according to the preparation method described in claim any one of 1-4, it is characterised in that step (4) described inert gas includes
In nitrogen, helium or argon gas any one or at least two combination, preferably argon gas；
Preferably, the temperature of step (4) described calcining is 200-400 DEG C, preferably 300 DEG C；
Preferably, the time of step (4) calcining is 3-5h, preferably 4h.
6. according to the preparation method described in claim any one of 1-5, it is characterised in that also include purifying after step (1)
The step of with activated carbon fiber；
Preferably, the purifying specifically includes with activated carbon fiber：
(1 ') is dried after carbon fiber is washed into 3-5h in NaOH solution；
(2 ') are dried after carbon fiber is washed into 5-6h in HCl solution；
Carbon fiber is carried out oxidation processes by (3 ') in atmosphere, is then stripped using ethanol, the carbon fiber of obtained activation.
7. preparation method according to claim 6, it is characterised in that the concentration of the NaOH solution described in step (1 ') is 3-
6M, preferably 5M；
Preferably, the time of step (the 1 ') washing is 4h；
Preferably, the temperature of step (the 1 ') washing is 90-120 DEG C, preferably 100 DEG C；
Preferably, the concentration of step (the 2 ') HCl solution is 3-6M, preferably 5M；
Preferably, the time of step (the 2 ') washing is 5.5h；
Preferably, the temperature of step (the 2 ') washing is 80-100 DEG C, preferably 85 DEG C；
Preferably, the temperature of step (the 3 ') oxidation processes is 100-220 DEG C, preferably 180 DEG C；
Preferably, the time of step (the 3 ') oxidation processes is 3-5h, preferably 4h；
Preferably, the time of step (the 3 ') extracting is 5-10h, preferably 8h.
8. according to the preparation method described in claim any one of 1-7, it is characterised in that comprise the following steps：
(1) it is (1-5) according to volume ratio into gamma-alumina catalyst:1 is passed through carbonaceous gas and oxygen, at 500-1000 DEG C
Lower reaction 18-32h, obtained particle diameter is 10-50nm, specific surface area 200-1000m2/ g carbon fiber；
(2) at 90-120 DEG C, carbon fiber is washed into 3-5h in the NaOH solution that concentration is 3-6M, is then cooled to 80-100
DEG C, carbon fiber is washed into 5-6h in the HCl solution that concentration is 3-6M, after drying, by carbon fiber oxidation processes 3- in atmosphere
5h, then using ethanolic extraction 5-10h, the carbon fiber of obtained activation；
(3) stabilizer and reducing agent are added into precious metal solution, 2-20h is reacted at 60-120 DEG C, obtains noble metal colloidal sol；
(4) equi-volume impregnating and/or excessive infusion process are used, by the impregnated carbon fiber of activation in the noble metal colloidal sol,
The mass ratio of carbon fiber and noble metal colloidal sol is 10:(1-5), regulation pH value is to 4-5, heating stirring at 40-80 DEG C, and is aided with super
Sound concussion reaction 5-20h；
(5) carbon fiber after dipping is placed in inert gas, 3-5h is calcined at 200-400 DEG C, obtained the carbon fiber and bear
Supported noble metal catalyst.
A kind of 9. carbon fiber loaded noble metal catalyst that preparation method as described in claim any one of 1-8 is prepared.
10. a kind of carbon fiber loaded noble metal catalyst as claimed in claim 9 is used to prepare fuel cell.
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| CN115888698A (en) * | 2022-11-10 | 2023-04-04 | 西部金属材料股份有限公司 | Basalt fiber-loaded noble metal nano catalyst and preparation method thereof |
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