CN101455975A - Porous carbon nanometer fiber-supported nanocrystal catalyst and preparation method thereof - Google Patents
Porous carbon nanometer fiber-supported nanocrystal catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention provides a porous-carbon nano-fiber supported nano-grain catalyst and a preparation method thereof. A porous polyacrylonitrile-based carbon nano-fiber supported nano-grain catalyst is prepared by adopting an electrostatic spinning process, constant-tension hot stretching, preoxidation and chemical activation at a temperature between 500 and 1,000 DEG C. Porous-carbon nano-fiber has the diameter between 100 and 500 nanometers, the aperture between 1 and 500 nanometers, the porosity between 0.1 and 1.0 cm<3>/g and the specific surface area between 100 and 2,000 m<2>/g, and catalyst particles supported on the surface of the nano-fiber has the aperture between 1 and 100 nanometers and the weight percentage content between 1 and 40 percent. The preparation method has the advantage of simple process, and can prepare the porous-carbon nano-fiber supported nano-grain catalyst with high porosity, large specific surface area, strong adsorption activity and catalytic efficiency through the chemical activation at a low temperature.
Description
Technical field
The present invention relates to a kind of porous carbon nanometer fiber-supported nanocrystal catalyst and preparation method thereof, the nano material of preparation can be specifically related to photochemical catalyst, bactericide, ammonia synthesis catalyst, polymerization catalyst etc. as the catalyst of heterogeneous catalytic reaction.
Background technology
Carbon nano-fiber is a kind of nano material of one dimension, have huge specific area and draw ratio, and there is a large amount of surface atoms to be in metastable state, thereby possessed small-size effect, surface or special nature such as interfacial effect, quantum size effect, therefore be widely used in carrier such as catalyst nano particles such as silver, titanium dioxide.
In carried by nano carbon fiber nanocrystal catalyst, carbon nano-fiber can the adsorption and enrichment reactant, and the reactant transfer of absorption can be reacted to nanocrystal activity of such catalysts point place, bring into play the usefulness of " absorption-transfer-catalytic reaction ", thereby can improve the catalytic efficiency of catalyst.Porosity, pore size and distribution thereof that carbon nano-fiber directly depends on fiber surface to the absorption and the desorption performance of reactant, this be because carbon nano-fiber can only the absorbing molecules diameter less than the reactant in aperture.But, the surface of conventional carbon nano-fiber only has the micropore of a small amount of aperture less than 2nm, can only faint suction-operated be arranged to small-molecule substances such as acetone, toluene, formaldehyde, and to big molecular dye, bacterium, viral equal diameter up to tens in addition the macromolecular substances of hundreds of nanometer have suction-operated hardly, therefore research and development have a large amount of mesopores (aperture are 2～50nm) and the porous carbon nanofiber of macropore (aperture is greater than 50nm) structure and the catalyst of load thereof, will have very important practical significance.
The method for preparing porous carbon nanometer fiber-supported nanocrystal catalyst has chemical deposition (CN200610148268.5), electrophoretic deposition, ion sputtering method etc., but its complex process, and the catalyst granules that deposition or sputter are got on stops up the hole on the fiber surface easily, reduces the adsorption activity of porous carbon nanofiber.Method of electrostatic spinning is a kind of simple relatively, the effective ways of the continuous nano-fibre that the preparation diameter is evenly distributed, the report of preparation porous carbon nanofiber is seen " Chan Kim; Bui Thi Nhu Ngoc; KapSeung Yang; Masashito Kojima; Yoong Ahm Kim; Yong Jung Kim, Morinobu Endo, Sung Chul Yang, Self-Sustained Thin Webs Consisting of Porous CarbonNanofibers for Supercapacitors via the Electrospinning ofPolyacrylonitrile Solutions Containing Zinc Chloride, AdvancedMaterials, 2007,19,2341-2346 ".This method is to pass through ZnCl
2The catalytic activation effect and impel the polyacrylonitrile nano fiber in carbonisation, to form a large amount of micropores and central hole structure.But, in spinning solution, add ZnCl
2After the metal ion activation agent, metal ion can cause the reunion or the precipitation of catalyst precursor, is difficult for making the spinning solution of homogeneous, thereby is difficult to prepare porous carbon nanometer fiber-supported nanocrystal catalyst.Chinese patent CN 1884643A discloses a kind of method for preparing polyacrylonitrile-radical mesopore-macropore carbon nano-fiber by pyrolytic reaction under excessive temperature (even up to 1800 ℃) and priming reaction.But so high temperature both had been unfavorable for obtaining the catalyst of suitable crystallite dimension and crystal phase structure, lost photocatalytic activity as anatase titanium dioxide will all changing rutile titanium dioxide into more than 800 ℃; Will produce more energy consumption again, be unfavorable for saving energy resource consumption and reduce production costs, so this method also is not suitable for preparing porous carbon nanometer fiber-supported nanocrystal catalyst.Up to now, do not see that the application method of electrostatic spinning prepares the bibliographical information and the invention/utility patent of porous carbon nanometer fiber-supported nanocrystal catalyst.
Summary of the invention
The invention provides a kind of porous carbon nanometer fiber-supported nanocrystal catalyst and preparation method thereof, not only technology is simple, and under lower temperature, just can activate the carried by nano carbon fiber nanocrystal catalyst that obtains having loose structure and high-specific surface area, help catalyst and have suitable crystallite dimension and crystal phase structure, also can save energy resource consumption and reduce production costs.
In the porous carbon nanometer fiber-supported nanocrystal catalyst of the present invention, the particle diameter of catalyst is 1～100nm, and weight percent content is 1～40%; And the diameter of porous carbon nanofiber is 100～500nm, and the aperture is 1～500nm, and porosity is 0.1～1.0cm
3/ g, specific area is 100～2000m
2/ g.
In the porous carbon nanometer fiber-supported nanocrystal catalyst of the present invention, the porous carbon nanofiber is a kind of carbon nano-fiber with loose structure, have the hole slot that the aperture is 1～100nm on the surface of carbon nano-fiber, and since mutually heap-shaped to become the aperture be the hole of 10～500nm.
In the porous carbon nanometer fiber-supported nanocrystal catalyst of the present invention, the shape of cross section of porous carbon nanofiber can be circular, oval or other non-circular shape.
In the porous carbon nanometer fiber-supported nanocrystal catalyst of the present invention, the mutual stacked form of porous carbon nanofiber can be non-woven mat, alignment films or other irregular stacked form.
In the porous carbon nanometer fiber-supported nanocrystal catalyst of the present invention, the nanocrystal catalyst comprises that particle diameter is that noble metal catalysts such as the silver, palladium, ruthenium, platinum, rhodium, nickel, iridium, osmium, gold of 1～20nm and particle diameter are one or more combinations in the catalyst of transition metal oxide such as the titanium oxide, zinc oxide, tin oxide, zirconia, lanthana, antimony oxide, vanadium oxide, molybdenum oxide, niobium oxide, chromium oxide, nickel oxide, manganese oxide, cobalt oxide, cerium oxide, bismuth oxide of 10～100nm.
The preparation method of porous carbon nanometer fiber-supported nanocrystal catalyst of the present invention is:
(a) with noble metal or catalyst of transition metal oxide presoma and polymer dissolution in organic solvent, be made into the spinning solution of homogeneous, wherein the molar concentration of catalyst precursor is 0.1～1mol/L, the mass concentration of polymer is 8～15%;
(b) adopt the method for electrostatic spinning preparation to contain the polymer nanofiber felt/film of catalyst precursor, wherein the syringe needle internal diameter is 0.5～1.5mm, the electrostatic potential that applies is 10～20kV, and the flow of spinning solution is 0.3～1.0mL/h, and receiving range is 10～30cm;
(c) electro spinning nano fiber felt/film is carried out hot drawing-off under constant tension force, in 230～300 ℃ of following air, carry out pre-oxidation 1h again, obtain the stabilisation nanofiber;
(d) the stabilisation nanofiber be impregnated in activator solution after, under certain activation temperature and activation phenomenon, activate again, and through the washing after then can obtain porous carbon nanometer fiber-supported nanocrystal catalyst.
The polymer of the preparation porous carbon nanofiber described in the preparation method of the present invention is polyacrylonitrile or acrylonitrile and the copolymer that contains the monomer of active unsaturated double-bond, and the monomer that wherein contains active unsaturated double-bond comprises one or more combinations in itaconic acid and derivative thereof, esters of acrylic acid, acrylic amide, vinyl, vinyl esters, the dienes; Corresponding organic solvent comprises one or more combinations in dimethyl formamide, dimethylacetylamide, dimethyl sulfoxide (DMSO), oxolane, the chloroform.
The hot drawing-off of permanent tension force described in the preparation method of the present invention is that electro spinning nano fiber felt/film is carried out hot drawing-off 5～30min under 120～150 ℃ and constant tension force, is 1～20MPa along the size of the vertical tension force that applies of fibrofelt/film.
Activator described in the preparation method of the present invention comprises one or more combinations that can not react each other in phosphoric acid, boric acid, sulfonic acid, sulfuric acid, nitric acid, zinc chloride, potassium hydroxide, NaOH, potash, potassium sulfate, the potassium sulfide, the concentration of activator solution is 0.5～5mol/L, and the stabilisation nanofiber is 1～6h at the dip time of activator solution.
Activation phenomenon described in the preparation method of the present invention is an ammonia, and the flow velocity of ammonia is 1～100mL/min.
Activation temperature described in the preparation method of the present invention is 500～1000 ℃, and intensification and cooling are respectively 1～5 ℃/min and 1～20 ℃/min, and soak time is 1～6h.
The loose structure of porous carbon nanometer fiber-supported nanocrystal catalyst of the present invention is characterized by SEM and full-automatic specific area fast and lacunarity analysis instrument, and the content of the nanocrystal catalyst of institute's load is analyzed by surperficial power spectrum EDAX and characterized on the porous carbon nanofiber surface.
Effect of the present invention: adopt method of electrostatic spinning, the hot drawing-off of permanent tension force, pre-oxidation and chemical activation method to obtain porous carbon nanometer fiber-supported nanocrystal catalyst.The porous carbon nanofiber has a large amount of mesopores, and (aperture is 2～50nm) and macropore (aperture is greater than 50nm), and has higher porosity and specific area.In addition, activate under lower temperature, just can obtain to have the carbon nano-fiber of loose structure, the nanocrystal catalyst that had both helped institute's load has suitable crystallite dimension and crystal phase structure, helps saving energy resource consumption again and reduces production costs.Method of the present invention is simple, is suitable for suitability for industrialized production.
Description of drawings
Fig. 1 is the SEM SEM figure of the nano-fibre supported titanium phosphate doped titanium dioxide photocatalyst of embodiment 1 described porous carbon;
Fig. 2 is the surperficial power spectrum EDAX figure of the nano-fibre supported titanium phosphate doped titanium dioxide photocatalyst of embodiment 1 described porous carbon;
Fig. 3 is the surperficial power spectrum EDAX figure of embodiment nano-fibre supported silver of 2 described porous carbons and titanium dioxide bicomponent catalyst.
The specific embodiment
The present invention will be described in detail below by embodiment:
Embodiment 1
It is in polyacrylonitrile/dimethyl formamide solution of 10% that the 8mL butyl titanate is dissolved in the 50mL mass concentration, and the ultrasonic agitation spinning solution that is made into homogeneous is used for electrostatic spinning then.In the electrostatic spinning process, selecting internal diameter for use is No. 12 injection needles of 1.1mm, the electrostatic potential that applies is 15kV, the flow of spinning solution is 0.5mL/h, receiving range between metal roller and the syringe needle is 20cm, cylinder external diameter linear velocity is 10m/s, obtains the nanofiber mats/film of certain thickness partial parallel orientation through the spinning of 5h.Electro spinning nano fiber felt/film is carried out the hot drawing-off 15min of permanent tension force under 135 ℃, be 10MPa along the size of the vertical tension force that applies of fibrofelt/film, and in 250 ℃ of following air, carry out pre-oxidation 1h again, obtain the stabilisation nanofiber.At last, in concentration the H of 2mol/L with the stabilisation nanofiber
3PO
4Flood 2h in the solution, taking-up is placed in the activation furnace under 600 ℃ and ammonia atmosphere and activates 2h, the flow velocity of ammonia is 10mL/min, intensification and cooling rate are respectively 3 ℃/min and 10 ℃/min, cooling is taken out and is repeatedly washed through the HCl of 1mol/L solution and deionized water, then can obtain the nano-fibre supported titanium phosphate doped titanium dioxide photocatalyst of porous carbon (seeing shown in Figure 1), wherein the particle diameter of titanium dioxide is about 40nm, weight percent content is about 20% (seeing shown in Figure 2), crystalline phase is Detitanium-ore-type and rutile-type mixing crystal formation, and both ratios are 3:1; The diameter of porous carbon nanofiber is 100～300nm, and the aperture is 1～200nm, and porosity is about 0.5cm
3/ g, specific area is about 1000m
2/ g.
Embodiment 2
It is in polyacrylonitrile/dimethyl formamide solution of 10% that 8mL butyl titanate and 0.2g silver nitrate are dissolved in the 60mL mass concentration, and the ultrasonic agitation spinning solution that is made into homogeneous is used for electrostatic spinning then.According to the electrostatic spinning process among the embodiment 1, hot drawing-off and pre-oxidation process, obtain the stabilisation nanofiber.At last, the stabilisation nanofiber in being the KOH solution of 1mol/L, concentration is flooded 2h, taking-up is placed in the activation furnace under 600 ℃ and ammonia atmosphere and activates 2h, the flow velocity of ammonia is 10mL/min, intensification and cooling rate are respectively 3 ℃/min and 10 ℃/min, cooling is taken out and is repeatedly washed through the HCl of 1mol/L solution and deionized water, then can obtain nano-fibre supported silver of porous carbon and titanium dioxide bicomponent catalyst, wherein Yin particle diameter is about 10nm, and weight percent content is about 2% (seeing shown in Figure 3); The particle diameter of titanium dioxide is about 35nm, and weight percent content is about 20% (seeing shown in Figure 3), and crystalline phase is Detitanium-ore-type and rutile-type mixing crystal formation, and both ratios are 3:1; And the diameter of porous carbon nanofiber is 100～300nm, and the aperture is 1～150nm, and porosity is about 0.4cm
3/ g, specific area is about 700m
2/ g.
Embodiment 3
It is in polyacrylonitrile/dimethyl formamide solution of 10% that the 4g silver nitrate is dissolved in the 50mL mass concentration, and the ultrasonic agitation spinning solution that is made into homogeneous is used for electrostatic spinning then.In the electrostatic spinning process, selecting internal diameter for use is No. 9 injection needles of 0.9mm, the electrostatic potential that applies is 12kV, the flow of spinning solution is 0.3mL/h, receiving range between metal roller and the syringe needle is 20cm, cylinder external diameter linear velocity is 10m/s, obtains the nanofiber mats/film of certain thickness partial parallel orientation through the spinning of 5h.Electro spinning nano fiber felt/film is carried out the hot drawing-off 10min of permanent tension force under 135 ℃, be 5MPa along the size of the vertical tension force that applies of fibrofelt/film, and in 250 ℃ of following air, carry out pre-oxidation 1h again, obtain the stabilisation nanofiber.At last, the stabilisation nanofiber in being the KOH solution of 1mol/L, concentration is flooded 2h, taking-up is placed in the activation furnace under 600 ℃ and ammonia atmosphere and activates 2h, the flow velocity of ammonia is 10mL/min, intensification and cooling rate are respectively 3 ℃/min and 10 ℃/min, cooling is taken out and is repeatedly washed through the HCl of 1mol/L solution and deionized water, then can obtain the nano-fibre supported silver catalyst of porous carbon.
Embodiment 4
It is in acrylonitrile methyl meth acrylat copolymer/dimethyl sulphoxide solution of 10% that the 8mL butyl titanate is dissolved in the 50mL mass concentration, and the ultrasonic agitation spinning solution that is made into homogeneous is used for electrostatic spinning then.According to the electrostatic spinning process among the embodiment 1, hot drawing-off and pre-oxidation process, obtain the stabilisation nanofiber.At last, the stabilisation nanofiber in being the KOH solution of 2mol/L, concentration is flooded 2h, taking-up is placed in the activation furnace under 500 ℃ and ammonia atmosphere and activates 2h, the flow velocity of ammonia is 10mL/min, intensification and cooling rate are respectively 3 ℃/min and 5 ℃/min, cooling is taken out and is repeatedly washed through the HCl of 1mol/L solution and deionized water, then can obtain the nano-fibre supported octahedrite type titanium dioxide photocatalyst of porous carbon.
Embodiment 5
It is in acrylonitrile methyl meth acrylat copolymer/dimethyl sulphoxide solution of 10% that the 3g ruthenium trichloride is dissolved in the 50mL mass concentration, and the ultrasonic agitation spinning solution that is made into homogeneous is used for electrostatic spinning then.According to the electrostatic spinning process among the embodiment 1, hot drawing-off and pre-oxidation process, obtain the stabilisation nanofiber.At last, in concentration the HNO of 2mol/L with the stabilisation nanofiber
3Flood 2h in the solution, taking-up is placed in the activation furnace under 600 ℃ and ammonia atmosphere and activates 2h, the flow velocity of ammonia is 20mL/min, intensification and cooling rate are respectively 2 ℃/min and 5 ℃/min, cooling is taken out and is repeatedly washed through the HCl of 1mol/L solution and deionized water, then can obtain the nano-fibre supported ruthenium-based ammonia synthetic catalyst of porous carbon.
Claims (9)
1, a kind of porous carbon nanometer fiber-supported nanocrystal catalyst is characterized in that: the nanocrystal catalyst cupport is on the surface of porous carbon nanofiber, and wherein the particle diameter of catalyst is 1～100nm, and weight percent content is 1～40%; The diameter of porous carbon nanofiber is 100～500nm, and the aperture is 1～500nm, and porosity is 0.1～1.0cm
3/ g, specific area is 100～2000m
2/ g.
2, porous carbon nanometer fiber-supported nanocrystal catalyst according to claim 1, it is characterized in that: described porous carbon nanofiber is the carbon nano-fiber with loose structure, have the hole slot that the aperture is 1～100nm on the surface of fiber, and since mutually heap-shaped to become the aperture be the hole of 10～500nm.
3, porous carbon nanometer fiber-supported nanocrystal catalyst according to claim 1 is characterized in that: described nanocrystal catalyst comprises that particle diameter is that noble metal catalysts such as the silver, palladium, ruthenium, platinum, rhodium, nickel, iridium, osmium, gold of 1～20nm and particle diameter are one or more combinations in the catalyst of transition metal oxide such as the titanium oxide, zinc oxide, tin oxide, zirconia, lanthana, antimony oxide, vanadium oxide, molybdenum oxide, niobium oxide, chromium oxide, nickel oxide, manganese oxide, cobalt oxide, cerium oxide, bismuth oxide of 10～100nm.
4, the preparation method of porous carbon nanometer fiber-supported nanocrystal catalyst according to claim 1 is characterized in that may further comprise the steps:
(a) with general noble metal or catalyst of transition metal oxide presoma and polymer dissolution in organic solvent, be made into the spinning solution of homogeneous, wherein the molar concentration of catalyst precursor is 0.1～1mol/L, the mass concentration of polymer is 8～15%;
(b) adopt the method for electrostatic spinning preparation to contain the polymer nanofiber felt/film of catalyst precursor, wherein the syringe needle internal diameter is 0.5～1.5mm, the electrostatic potential that applies is 10～20kV, and the flow of spinning solution is 0.3～1.0mL/h, and receiving range is 10～30cm;
(c) with the hot drawing-off of permanent tension force in addition of electro spinning nano fiber felt/film, and in 230～300 ℃ of following air, carry out pre-oxidation 1h again, obtain the stabilisation nanofiber;
(d) the stabilisation nanofiber be impregnated in activator solution after, under certain activation temperature and activation phenomenon, activate again, and through the washing after then can obtain porous carbon nanometer fiber-supported nanocrystal catalyst.
5, preparation method according to claim 4, it is characterized in that: the polymer of described preparation carbon nano-fiber is polyacrylonitrile or acrylonitrile and the copolymer that contains the monomer of active unsaturated double-bond, and the monomer that wherein contains active unsaturated double-bond comprises one or more combinations in itaconic acid and derivative thereof, esters of acrylic acid, acrylic amide, vinyl, vinyl esters, the dienes; Corresponding organic solvent comprises one or more combinations in dimethyl formamide, dimethylacetylamide, dimethyl sulfoxide (DMSO), oxolane, the chloroform.
6, preparation method according to claim 4, it is characterized in that: the hot drawing-off of described permanent tension force is that electro spinning nano fiber felt/film is carried out hot drawing-off 5～30min under 120～150 ℃ and constant tension force, is 1～20MPa along the size of the vertical tension force that applies of fibrofelt/film.
7, preparation method according to claim 4, it is characterized in that: described activator comprises one or more combinations that can not react each other in phosphoric acid, boric acid, sulfonic acid, sulfuric acid, nitric acid, zinc chloride, potassium hydroxide, NaOH, potash, potassium sulfate, the potassium sulfide, the concentration of activator solution is 0.5～5mol/L, and the stabilisation nanofiber is 1～6h at the dip time of activator solution.
8, preparation method according to claim 4 is characterized in that: described activation phenomenon is an ammonia, and the flow velocity of ammonia is 1～100mL/min.
9, preparation method according to claim 4 is characterized in that: described activation temperature is 500～1000 ℃, and intensification and cooling are respectively 1～5 ℃/min and 1～20 ℃/min, and soak time is 1～6h.
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