CN102513099B - Novel metal catalyst loaded by mesoporous carbon and preparation method thereof - Google Patents
Novel metal catalyst loaded by mesoporous carbon and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a novel metal catalyst loaded by mesoporous carbon and a preparation method thereof. The metal catalyst is composed of 0.01-90 wt% of metal grains and 10-99.99 wt% of mesoporous carbon carrier, wherein the mesoporous carbon carrier is made of a heteroatom-doped mesoporous carbon material; the heteroatom-doped mesoporous carbon material is prepared by the following steps of: taking ionic liquid containing heteroatoms as a monomer and mixing the ionic liquid with a template agent at a room temperature; and then calcining the mixture at a temperature in a range of 400-1000 DEG C for 1-6 hours and cooling the mixture to the room temperature; and finally, removing the template agent to obtain the heteroatom-doped mesoporous carbon material. The average grain diameter of the metal grains is 1-100 nm and the mass percentage of the heteroatoms in the mesoporous carbon material is 0.01-80 wt%. The catalyst provided by the invention is good for enhancing the catalytic activity of the catalyst by adjusting the valence state of nano metal through doping the heteroatoms including nitrogen, sulfur, phosphorus, boron, fluorine and the like, and depositing and dispersing on the metal on the surface of the carrier. Furthermore, the catalyst is simple in preparation and is stable for water, air and heat.
Description
Technical field
The invention belongs to the metallic catalyst field that material with carbon element supports, particularly a kind of New Type of Mesoporous material with carbon element, the metallic catalyst supported by this material and their preparation method.
Background technology
Meso-porous carbon material is a class non-silicon mesoporous material, it has large specific area and pore volume, good electric conductivity and the performance superior to most organic solvent inertia etc., and it is easily by calcining removing, in a lot of, there is complementarity with oxide material, therefore, make meso-porous carbon material be obtained in catalysis, absorption, separation, Chu Qing, electrochemistry etc. to apply widely.
The metallic catalyst that material with carbon element supports is the effective catalyst of the reaction such as catalytic hydrogenation and oxidation.As document (J.Catal.2010,270,9-15) supports the catalytic hydrogenation reaction of nano Pd particle particle for catalysis substituted benzene with activated carbon or carbon nano-fiber.Document (Green Chem.2010,12,1007-1011) describes and supports Pt nano particle particle with CNT and react for catalysis nitrobenzene reduction.Document (Chem.Commun.2008,999-1001.) describes a kind of carbon-supported nano Pd particle particle of water heat transfer, and be applied to phenol hydrogenation reduction prepare cyclohexanol.Document (Science, 2009,326,1250-1252.) describes the method for the sour catalytic reduction preparing cyclohexanone from phenol that combines of a kind of Pd/C and Lewis.Document (Chem.Commun.2003,1960-1961) has synthesized the catalyst such as Ru/C, Rh/C, Pd/C, Pt/C, and has investigated the activity of these catalyst in catalysis of phenol hydrogenation reaction and selective respectively.Although very extensive with the application of carbon-supported noble metal catalyst, but these catalyst also have its intrinsic weakness, as easy inactivation placed in atmosphere by catalyst, not high (the Chem.Commun.2003 of reaction selectivity in some selective reactions, 1960-1961), often need to add co-catalyst (Science, 2009 as catalyst, 326,1250-1252.) etc.These problems limit the application of this kind of catalyst, and therefore development of new has important actual application value to air and hydrothermally stable, high activity, metallic catalyst that the modification mesoporous carbon of high selectivity supports.
Summary of the invention
Technical problem to be solved by this invention overcomes the deficiencies in the prior art, provides the metallic catalyst that a kind of New Type of Mesoporous is carbon-supported.
The preparation method of the metallic catalyst that the present invention also will provide a kind of New Type of Mesoporous carbon-supported simultaneously, the method is simple, and gained metallic catalyst has excellent air and hydrothermal stability and catalytic activity.
For solving above technical problem, a kind of technical scheme that the present invention takes is:
The metallic catalyst that a kind of New Type of Mesoporous is carbon-supported, it is made up of metallic 0.01wt% ~ 90wt% and mesoporous carbon carrier 10wt% ~ 99.99wt%, wherein, described mesoporous carbon carrier is made up of the meso-porous carbon material of Heteroatom doping, the meso-porous carbon material of this Heteroatom doping be with containing heteroatomic ionic liquid for monomer, at room temperature mix with template, then calcine 1 ~ 6 hour at 400 ~ 1000 DEG C, be cooled to room temperature, finally remove template to obtain, the average grain diameter of described metallic is 1 ~ 100nm, in described meso-porous carbon material, heteroatomic mass fraction is 0.01wt% ~ 80wt%.
According to a preferred aspect of the present invention, described metallic catalyst is made up of metallic 0.1wt% ~ 50wt% and described mesoporous carbon carrier 50wt% ~ 99.9wt%.In the meso-porous carbon material of described Heteroatom doping, heteroatomic mass fraction is preferably 0.1wt% ~ 30wt%.
According to the present invention, described hetero atom refers to element such as nitrogen, sulphur, phosphorus, boron, fluorine etc. outside de-carbon hydrogen-oxygen, is mainly derived from ionic liquid.Ionic liquid includes but not limited to imidazole type ion liquid, quaternary ammonium type ionic liquid and pyridine type ionic liquid etc., ionic liquid can be wherein any one, also can be the combination of the different ionic liquid of same type, can also be the combination of dissimilar different kinds of ions liquid, be not particularly limited.According to a concrete aspect of the present invention, described ionic liquid is preferably any combination that cation that formula (a) represents and formula (b) represent anion:
(b)N(CN)
2 -，BF
4 -，PF
6 -，Cl
-，Br
-，F
-，PO
4 3-，SO
4 2-，NO
3 -，CF
3SO
3 -，CF
3COO
-，EtOSO
3 -，MeOSO
3 -.
In described formula (a), n is the integer between 1 ~ 20, is preferably the integer between 1 ~ 12, is more preferably the integer between 1 ~ 6.
Typical ionic liquid can be such as 1-penta cyano group-3-methylimidazole hexafluorophosphate, 4-methyl-N-penta cyanopyridine tetrafluoroborate, 1-butyl-3-methylimidazole villaumite, 1-butyl-3-methylimidazole ethyl-sulfate salt etc.Although these ionic liquids mentioned and specifically not mention but the ionic liquid with the structure of the combination of above-mentioned formula (a) and formula (b) all can be prepared by known method by those skilled in the art or commercially available.
According to the present invention, in the meso-porous carbon material process preparing Heteroatom doping, the template of use for the various templates be applicable to, wherein can be preferably molecular sieve SBA-15, molecular sieve MCM-41 or Ludox Ludox HS.Template is generally by removing by ammonium acid fluoride or naoh treatment.
According to the present invention, described metal can one or more for being selected from Pd, Au, Ag, Pt, Ru, Rh, Ni, Cu, Fe, Co, Cr, W, Mo, Ti and Ta.
The another technical scheme that the present invention takes is: the preparation method of the metallic catalyst that a kind of New Type of Mesoporous is carbon-supported, this metallic catalyst is that the metallic 0.01wt% ~ 90wt% of 1 ~ 100nm and mesoporous carbon carrier 10wt% ~ 99.99wt% form by average grain diameter, and described method comprises the steps:
(1), with containing heteroatomic ionic liquid for monomer, make it at room temperature mix with template, then calcine 1 ~ 6 hour at 400 ~ 1000 DEG C, be cooled to room temperature, finally remove template and obtain the meso-porous carbon material of Heteroatom doping;
(2), adopt in ultrasonic method, deposition-precipitation, sol-gal process and Photodeposition any one metal supported on step (1) gained meso-porous carbon material, obtain the carbon-supported metallic catalyst of described New Type of Mesoporous.
Preferably, in step (1), described template can be molecular sieve SBA-15, molecular sieve MCM-41 or Ludox Ludox HS, and removes finally by by ammonium acid fluoride or naoh treatment
Step (2) preferably adopts comparatively easy ultrasonic method, be specially: with the oxide of the meso-porous carbon material of step (1) gained Heteroatom doping and described metal, halide or nitrate for raw material, be uniformly mixed under hyperacoustic condition, then with sodium borohydride solution by metallic reducing, filter, washing, dries and obtains the metallic catalyst that described New Type of Mesoporous is carbon-supported.
According to method of the present invention, the metal wherein mentioned, the definition containing heteroatomic ionic liquid is the same.
Due to the utilization of technique scheme, the present invention compared with prior art has following advantage:
The carrier of metallic catalyst of the present invention adopts by the meso-porous carbon material containing heteroatomic ionic liquid being the Heteroatom doping that monomer is made, make it possible to obtain nano-sized metal particles in the deposition of carrier surface with dispersion by the heteroatomic doping regulation and control valence state of metal and metal, thus be conducive to strengthening its catalytic activity.In addition, the meso-porous carbon material carrying metal of Heteroatom doping is simple, and can adopt known various methods such as ultrasonic method, deposition-precipitation, prepared by sol-gal process and Photodeposition etc.Metallic catalyst of the present invention is to water, air and thermally-stabilised.As this catalyst was soaked for 1 week in water, catalyst has no obvious foamed phenomenon, and activity does not subtract in the hydrogenating reduction of nitrobenzene; Deposit its catalysis hydrogenation of chloronitrobenzene reducing activity after 5 months in atmosphere not subtract; Be heated to 550 degree in atmosphere, catalyst has no obvious decomposition.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention will be further described in detail, but the present invention is not limited to following examples.
Embodiment 1
The metal Pd catalyst that the present embodiment provides the meso-porous carbon material of a kind of nitrogen and phosphor codoping to support, it is prepared as follows:
(1), 1g 1-penta cyano group-3-methylimidazole hexafluorophosphoric acid ionic liquid is at room temperature mixed with 1.5g molecular sieve SBA-15, then 600 DEG C of calcinings 3 hours are warmed up to, removing SBA-15 is decomposed with ammonium acid fluoride after cool to room temperature, obtain the meso-porous carbon material 0.6g of nitrogen and phosphor codoping, elementary analysis shows that the mass content of nitrogen is 7.8%, the mass content of phosphorus is 0.2%, and its specific area is at 150 ~ 1200m
2/ g.
(2), by the meso-porous carbon material of 0.2g step (1) gained nitrogen and phosphor codoping join in 250mL beaker, add 50 ~ 100mL deionized water, ultrasonic vibration 5 ~ 30 minutes, then add the PdCl that 4ml concentration is 0.056mmol/ml
2the aqueous solution, ultrasonic vibration 5 ~ 30 minutes, finally adds 5mgNaBH
4, ultrasonic vibration 5 ~ 60 minutes, filters, washing, and dry, the nano metal Pd catalyst that the meso-porous carbon material obtaining nitrogen and phosphor codoping supports, the size of Pd particle is in 1 ~ 100 nanometer range, and average grain diameter is 5nm.This catalyst was soaked for 1 week in water, and catalyst has no obvious foamed phenomenon, and activity does not subtract in the hydrogenating reduction of nitrobenzene; Deposit its catalysis hydrogenation of chloronitrobenzene reducing activity after 5 months in atmosphere not subtract; Be heated to 550 degree in atmosphere, catalyst has no obvious decomposition.
Embodiment 2
The metal A u catalyst that the present embodiment provides a kind of nitrogen, boron, fluorin-doped meso-porous carbon material supports, it is prepared as follows:
(1), 1g 4-methyl-N-penta cyanopyridine tetrafluoroborate is at room temperature mixed with 2g Ludox HS 40 Ludox, then 800 DEG C of calcinings 3 hours are warmed up to, divide with ammonium acid fluoride after cool to room temperature and take off template Ludox-41 Ludox, obtain nitrogen, boron, fluorin-doped meso-porous carbon material 0.5g, elementary analysis shows that the mass fraction of nitrogen in material is 5.6%, the mass fraction of boron is 0.2%, and the mass fraction of fluorine is 0.1%, and its specific area is at 150 ~ 1200m
2/ g.
(2), 0.3g step (1) gained nitrogen, boron, fluorin-doped meso-porous carbon material are joined in 250mL beaker, add 50 ~ 100mL deionized water, ultrasonic vibration 5 ~ 30 minutes, then the aqueous solution of chloraurate that 3ml concentration is 0.037mmol/ml is added, ultrasonic vibration 5 ~ 30 minutes, finally adds 7mgNaBH
4ultrasonic vibration 5 ~ 60 minutes, filter, washing, dry, obtain nitrogen, metal A u catalyst that boron, fluorin-doped meso-porous carbon material support, the size of Au particle is in 1 ~ 60 nanometer range, and average grain diameter is 8nm, and this catalyst was soaked for 1 week in water, catalyst has no obvious foamed phenomenon, and activity does not subtract in the hydrogenating reduction of nitrobenzene; Deposit its catalysis hydrogenation of chloronitrobenzene reducing activity after 5 months in atmosphere not subtract; Be heated to 550 degree in atmosphere, catalyst has no obvious decomposition.
Embodiment 3
The Pt metal catalyst that the present embodiment provides a kind of nitrogen, boron, fluorin-doped meso-porous carbon material supports, it is prepared as follows:
(1), 1g 1-butyl-3-methylimidazole villaumite is at room temperature mixed with 1.5g MCM-41, then 400 DEG C of calcinings 3 hours are warmed up to, divide with ammonium acid fluoride after cool to room temperature and take off template MCM-41, obtain the meso-porous carbon material 0.6g of N doping, its specific area is at 150 ~ 1200m
2/ g.
(2), the meso-porous carbon material of 0.3g N doping is joined in 250mL beaker, add 50 ~ 100mL deionized water, ultrasonic vibration 5 ~ 30 minutes, then add the chloroplatinic acid aqueous solution that 10ml concentration is 0.038mmol/ml, ultrasonic vibration 5 ~ 30 minutes, finally adds 7mg NaBH
4, ultrasonic vibration 5 ~ 60 minutes, filters, and washing is dried, and obtains nitrogen, Pt metal catalyst that boron, fluorin-doped meso-porous carbon material support, and the size of Pt particle is in 1 ~ 100 nanometer range, and average grain diameter is 3nm.This catalyst was soaked for 1 week in water, and catalyst has no obvious foamed phenomenon, and activity does not subtract in the hydrogenating reduction of nitrobenzene; Deposit its catalysis hydrogenation of chloronitrobenzene reducing activity after 5 months in atmosphere not subtract; Be heated to 550 degree in atmosphere, catalyst has no obvious decomposition.
Embodiment 4
The metal A u catalyst that the present embodiment provides the meso-porous carbon material of a kind of nitrogen, sulphur, phosphor codoping to support, it is prepared as follows:
(1), 0.5g 1-butyl-3-methylimidazole ethyl-sulfate salt, 0.5g1-penta cyano group-3-methylimidazole hexafluorophosphate are at room temperature mixed with 1.5g SBA-15, then 600 DEG C of calcinings 3 hours are warmed up to, divide with ammonium acid fluoride after cool to room temperature and take off template SBA-15, obtain the meso-porous carbon material 0.7g of nitrogen, sulphur and phosphor codoping, elementary analysis shows that the mass content of nitrogen is 10.5%, the mass content of sulphur is 0.5%, the mass content of phosphorus is 0.3%, and its specific area is at 150 ~ 1200m
2/ g.
(2), the meso-porous carbon material of 0.3g step (1) gained nitrogen, sulphur and phosphor codoping is joined in 250mL beaker, add 50 ~-100mL deionized water, ultrasonic vibration 5 ~ 30 minutes, then the chloroplatinic acid aqueous solution that 3ml concentration is 0.038mmol/ml is added, ultrasonic vibration 5 ~ 30 minutes, finally add 7mgNaBH4, ultrasonic vibration 5 ~ 60 minutes, filter, washing, dries, the metal A u catalyst that the meso-porous carbon material obtaining nitrogen, sulphur and phosphor codoping supports, the size of Au particle is in 1 ~ 60 nanometer range, and average grain diameter is 7nm.This catalyst was soaked for 1 week in water, and catalyst has no obvious foamed phenomenon, and activity does not subtract in the hydrogenating reduction of nitrobenzene; Deposit its catalysis hydrogenation of chloronitrobenzene reducing activity after 5 months in atmosphere not subtract; Be heated to 550 degree in atmosphere, catalyst has no obvious decomposition.
Embodiment 5
The metallic Ni catalyst that the present embodiment provides the meso-porous carbon material of a kind of nitrogen and phosphor codoping to support, it is prepared as follows:
(1), 1g 1-penta cyano group-3-methylimidazole hexafluorophosphoric acid ionic liquid is at room temperature mixed with 1.5g SBA-15, then 600 DEG C of calcinings 3 hours are warmed up to, divide with ammonium acid fluoride after cool to room temperature and take off template SBA-15, obtain the meso-porous carbon material 0.6g of nitrogen and phosphor codoping, elementary analysis shows that nitrogen content is 11.3%, phosphorus content is 0.2%, and its specific area is at 150 ~ 1200m
2/ g.
(2), by the meso-porous carbon material of 0.2g step (1) gained nitrogen and phosphor codoping join in 250mL beaker, add 50 ~ 100mL deionized water, ultrasonic vibration 5 ~ 30 minutes, then add the NiCl that 30ml concentration is 0.078mmol/ml
2the aqueous solution, ultrasonic vibration 5 ~ 30 minutes, finally adds 5mgNaBH4, ultrasonic vibration 5 ~ 60 minutes, filter, washing, dry, the nano metal Ni catalyst that the meso-porous carbon material obtaining nitrogen and phosphor codoping supports, the size of Ni particle is in 1 ~ 100 nanometer range, and average grain diameter is 6nm.This catalyst was soaked for 1 week in water, and catalyst has no obvious foamed phenomenon, and activity does not subtract in the hydrogenating reduction of nitrobenzene; Deposit its catalysis hydrogenation of chloronitrobenzene reducing activity after 5 months in atmosphere not subtract; Be heated to 550 degree in atmosphere, catalyst has no obvious decomposition.
Embodiment 6
The metal Pd catalyst that the present embodiment provides the meso-porous carbon material of a kind of nitrogen and sulphur codope to support, it is prepared as follows:
(1), 1g 1-butyl-3-methylimidazole ethyl-sulfate salt is at room temperature mixed with 1.5g SBA-15, then 600 DEG C of calcinings 3 hours are warmed up to, divide with ammonium acid fluoride after cool to room temperature and take off template SBA-15, obtain the meso-porous carbon material 0.7g of nitrogen and sulphur codope, elementary analysis shows that nitrogen content is 9.8%, sulfur content is 0.6%, and its specific area is at 150 ~ 1200m
2/ g.
(2), the meso-porous carbon material of 0.3g step (1) gained nitrogen and sulphur codope is joined in 250mL beaker, add 50 ~ 100mL deionized water, then the PdCl2 aqueous solution that 40ml concentration is 0.056mmol/ml is added, adding a certain amount of alkali regulates the pH of solution to about 10 as the NaOH aqueous solution, after pH value is stable, add 7mg NaBH
4, filter after continuing to stir 2h, washing, dry, the metal Pd catalyst that the meso-porous carbon material obtaining nitrogen and sulphur codope supports, the size of Pd particle is in 1 ~ 100 nanometer range, and average grain diameter is 5nm.This catalyst was soaked for 1 week in water, and catalyst has no obvious foamed phenomenon, and activity does not subtract in the hydrogenating reduction of nitrobenzene; Deposit its catalysis hydrogenation of chloronitrobenzene reducing activity after 5 months in atmosphere not subtract; Be heated to 550 degree in atmosphere, catalyst has no obvious decomposition.
Embodiment 7
The metal Pd catalyst that the present embodiment provides the meso-porous carbon material of a kind of nitrogen, sulphur, phosphor codoping to support, it is prepared as follows:
(1), 0.5g 1-butyl-3-methylimidazole ethyl-sulfate salt, 0.5g1-penta cyano group-3-methylimidazole hexafluorophosphate are at room temperature mixed with 1.5g SBA-15, then 600 DEG C of calcinings 3 hours are warmed up to, divide with ammonium acid fluoride after cool to room temperature and take off template SBA-15, obtain the meso-porous carbon material 0.7g of nitrogen, sulphur, phosphor codoping, elementary analysis shows that nitrogen content is 9.7%, sulfur content is 0.3%, and phosphorus content is 0.1%, and its specific area is at 150 ~ 1200m
2/ g.
(2), by the meso-porous carbon material of 0.3g step (1) gained nitrogen, sulphur, phosphor codoping join in 250mL beaker, add 50 ~ 100mL deionized water, then add the PdCl that 15ml concentration is 0.056mmol/ml
2the aqueous solution, adding a certain amount of alkali such as NaOH aqueous solution regulates the pH of solution to about 10,0.1 ~ 1h is shone with visible ray after pH value is stable, filter, washing, dries, and obtains the metal Pd catalyst that supports of meso-porous carbon material of nitrogen, sulphur, phosphor codoping, the size of Pd particle is in 1 ~ 100 nanometer range, and average grain diameter is 3.5nm.This catalyst was soaked for 1 week in water, and catalyst has no obvious foamed phenomenon, and activity does not subtract in the hydrogenating reduction of nitrobenzene; Deposit its catalysis hydrogenation of chloronitrobenzene reducing activity after 5 months in atmosphere not subtract; Be heated to 550 degree in atmosphere, catalyst has no obvious decomposition.
The Pd/C catalyst application of above-described embodiment 1 ~ 7 gained catalyst and business is prepared in the reaction of aniline in nitrobenzene, be specially: the catalyst 25mg that supports of Example 1 ~ 7 and existing mesoporous carbon respectively, nitrobenzene 10ml, under room temperature and atmospheric hydrogen condition, react 24 hours, record the catalyst that the catalyst of embodiment 1 ~ 7 and existing mesoporous carbon support turn over number (TON) be followed successively by 5125mol (nitrobenzene)/mol (palladium); 625mol (nitrobenzene)/mol Au (gold); 7120mol (nitrobenzene)/mol Pt (platinum); 720mol (nitrobenzene)/mol Au (gold); 5640mol (nitrobenzene)/mol Ni (nickel); 6630mol (nitrobenzene)/mol Pd (palladium); 6785mol (nitrobenzene)/mol Pd (palladium) and 3215mol (nitrobenzene)/mol Pd (palladium).
Above-described embodiment, only for technical conceive of the present invention and feature are described, its object is to person skilled in the art can be understood content of the present invention and implement according to this, can not limit the scope of the invention with this.All equivalences done according to Spirit Essence of the present invention change or modify, and all should be encompassed within protection scope of the present invention.
Claims (7)
1. the metallic catalyst that supports of a mesoporous carbon, it is made up of metallic 0.01wt% ~ 90wt% and mesoporous carbon carrier 10wt% ~ 99.99wt%, it is characterized in that: described mesoporous carbon carrier is made up of the meso-porous carbon material of Heteroatom doping, the meso-porous carbon material of described Heteroatom doping be with containing heteroatomic ionic liquid for monomer, at room temperature mix with template, then calcine 1 ~ 6 hour at 400 ~ 1000 DEG C, be cooled to room temperature, finally remove template to obtain, the average grain diameter of described metallic is 1 ~ 100nm;
Described ionic liquid is any combination that the cation that represents of formula (a) and formula (b) represent anion:
(b)N(CN)
2 -，BF
4 -，PF
6 -，Cl
-，Br
-，F
-，PO
4 3-，SO
4 2-，NO
3 -，CF
3SO
3 -，CF
3COO
-，EtOSO
3 -，MeOSO
3 -.
In described formula (a), n is the integer between 1 ~ 20;
In the meso-porous carbon material of described Heteroatom doping, heteroatomic mass fraction is 0.1wt% ~ 30wt%.
2. the metallic catalyst that supports of mesoporous carbon according to claim 1, is characterized in that: described metallic catalyst is made up of metallic 0.1wt% ~ 50wt% and described mesoporous carbon carrier 50wt% ~ 99.9wt%.
3. the metallic catalyst that supports of mesoporous carbon according to claim 1 and 2, is characterized in that: described template is molecular sieve SBA-15, molecular sieve MCM-41 or Ludox Ludox HS, and finally by with ammonium acid fluoride or naoh treatment removing.
4. the metallic catalyst that supports of mesoporous carbon according to claim 1 and 2, is characterized in that: described metal be selected from Pd, Au, Ag, Pt, Ru, Rh, Ni, Cu, Fe, Co, Cr, W, Mo, Ti and Ta one or more.
5. the preparation method of metallic catalyst that supports of a mesoporous carbon, described metallic catalyst is that the metallic 0.01wt% ~ 90wt% of 1 ~ 100nm and mesoporous carbon carrier 10wt% ~ 99.99wt% form by average grain diameter, it is characterized in that: described method comprises the steps:
(1), according to claim 1, with containing heteroatomic ionic liquid for monomer, it is made at room temperature to mix with template, then calcine 1 ~ 6 hour at 400 ~ 1000 DEG C, be cooled to room temperature, finally remove the meso-porous carbon material that template obtains Heteroatom doping, in the meso-porous carbon material of described Heteroatom doping, heteroatomic mass fraction is 0.1wt% ~ 30wt%.
(2), adopt in ultrasonic method, deposition-precipitation, sol-gal process and Photodeposition any one metal is supported the metallic catalyst obtaining described mesoporous carbon and support on the meso-porous carbon material of step (1) gained Heteroatom doping.
6. the preparation method of metallic catalyst that supports of mesoporous carbon according to claim 5, it is characterized in that: step (2) adopts ultrasonic method, be specially: with the oxide of the meso-porous carbon material of step (1) gained Heteroatom doping and described metal, halide or nitrate for raw material, be uniformly mixed under hyperacoustic condition, then with sodium borohydride solution by metallic reducing, filter, washing, dries and obtains the metallic catalyst that described mesoporous carbon supports.
7. the preparation method of the metallic catalyst that the mesoporous carbon according to claim 5 or 6 supports, it is characterized in that: in step (1), described template is molecular sieve SBA-15, molecular sieve MCM-41 or Ludox Ludox HS, and removes finally by by ammonium acid fluoride or naoh treatment.
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