CN104707604A - Preparation method of metal or metal oxide particle-containing CeO2 fiber catalyst - Google Patents
Preparation method of metal or metal oxide particle-containing CeO2 fiber catalyst Download PDFInfo
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- CN104707604A CN104707604A CN201510052280.5A CN201510052280A CN104707604A CN 104707604 A CN104707604 A CN 104707604A CN 201510052280 A CN201510052280 A CN 201510052280A CN 104707604 A CN104707604 A CN 104707604A
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Abstract
The invention discloses a preparation method of a metal or metal oxide particle-containing CeO2 fiber catalyst, and belongs to the field of preparation of nanocatalysts. The novel fiber-based supported catalyst is obtained by adopting a cocatalyst CeO2 fiber as a supporter to support a main catalyst metal or metal oxide nanoparticle. The method comprises the following steps: 1, respectively dissolving a CeO2 precusor, a polymer and a metal or metal salt in a solvent, magnetically stirring, and mixing and stirring to obtain a spinning precursor solution; 2, carrying out an electrostatic spinning technology to make metal or metal CeO2/polymer supported composite precursor fibers; and 3, carrying out high temperature calcining and hydrogen reduction to obtain the metal or metal oxide nanoparticle/CeO2 fiber supported catalyst. The method is simple and easy, and the metal or metal oxide particle has good dispersibility and large specific surface area; and the catalyst high the characteristics of high catalysis activity and easy recovery, and has wide application prospect in the future catalysis industry.
Description
Technical field
The present invention relates to the CeO of a kind of containing metal or metal oxide particle
2the preparation method of fiber catalyst, belongs to nanocatalyst preparing technical field.
Background technology
At catalytic field, common traditional catalyst comprises containing a large amount of noble metal, non-ferrous metal or its oxide.These catalyst are widely used in the chemical reactions such as hydrogenation, oxidation, dehydrogenation, methanol decomposition, reformation and transformationreation, but because these noble metals are expensive, how researchers improve its catalytic activity and catalytic efficiency while being devoted to reduce catalyst amount always, and implement effectively to reclaim.Wherein these noble metal nanometers, can catalytic activity be significantly improved, but simultaneously because the catalyst granules of nano-scale is expensive, be difficult to be separated with product, random discharge also causes very large pollution to environment, needs these catalyst to carry out reclaiming and recycling.For this problem, loaded catalyst obtains researchers and more and more pays close attention to.Loaded catalyst mainly refers to and loads on certain carrier by some nano-noble metals or its oxide particle, and carrier can make active component obtain higher specific area, reduces consumption, can improve catalytic efficiency, can also solve recovery problem.
Conventional carrier has CNT, carbon fiber, silicon dioxide fibre, aluminium oxide, molecular sieve etc., the metal nanoparticle of load in common carrier is uniformly dispersed, particle diameter is little, specific area is large, easily recycling, but when carrying out catalytic reaction, also need to add some catalyst aids and come auxiliary major catalyst raising catalytic efficiency and catalytic activity, and common carrier is just in order to support catalyst is used, itself is without any the function relevant with catalytic action, can not cocatalyst.The function that ceria can strengthen catalyst as co-catalyst in some catalytic reactions improves catalytic efficiency greatly.At present, researchers adopt coprecipitation and infusion process to prepare NiO/CeO always
2, Co/CeO
2even load catalyst, but catalyst prepared by these conventional methods exists with spheric granules substantially, especially active high nanoscopic catalyst particles, is very easy to assemble, is difficult to dispersed in the solution, affects its catalytic effect.
The appearance of electrospun nanofibers technology, provides a kind of method more simple and applied widely for preparing loaded catalyst.The nanofiber prepared by electrospinning process has that diameter is little, meso-porous nano structure, specific area are comparatively large, and the features such as morphology controllable, are a kind of more promising material thus the especially catalyst carrier that is widely used.At present, but also there is not been reported lead-to help composite nano-catalyst by electrostatic spinning technique preparation.
The present invention lead-helps composite nano-catalyst by electrostatic spinning technique preparation, for carrier with co-catalyst cerium oxide fibre, load primary catalyst metal or metal oxide nanoparticles, we co-catalyst is compound to major catalyst together with prepare tencel based supported catalyst.Main feature of the present invention is: fibrous matrix is CeO
2, fiber itself has the effect of load matrix and co-catalyst concurrently simultaneously; The particle of load is major catalyst, and nano level major catalyst can disperse uniformly at fiber surface, avoids assembling.The specific area of composite catalyst of the present invention is larger than conventional load catalyst simultaneously, molecule contacts easier and catalyzed in the solution, improves catalytic efficiency.Tencel based supported catalyst of the present invention has broad application prospects in the catalysis industry in future.
Summary of the invention:
The object of this invention is to provide the CeO of a kind of containing metal or metal oxide particle
2the preparation method of fine catalyst.The present invention is with co-catalyst CeO
2fiber is carrier, and carried metal or metal oxide nanoparticles, by electrostatic spinning technique, obtain tencel based supported catalyst, metal in this catalyst or metal oxide nanoparticles good dispersion, particle diameter is little and specific area large, and this supported catalyst easily reclaims.
Technical scheme of the present invention is as follows:
The CeO of a kind of containing metal or metal oxide particle
2the preparation method of fiber catalyst, concrete steps are as follows:
Step 1:(1) take the CeO of 1 ~ 6g respectively
2the solvent of presoma and 2 ~ 10g, after mixing, lower magnetic force stirs 5 ~ 12h, allows CeO
2presoma is fully hydrolyzed, and obtains CeO
2sol solution; (2) high polymer of 0.5 ~ 5g is dissolved in 2 ~ 15g solvent, magnetic stirring apparatus stirs 5 ~ 12h, form the solution of homogeneous transparent; (3) by 0.05 ~ 0.5g metal or dissolving metal salts in 0.5 ~ 3g solvent through ultrasonic 1 ~ 4h, form stable homogeneous solution; (4) finally by these three kinds of solution mix and blend 0.5 ~ 2h extremely uniformly liquid, electrostatic spinning precursor liquid is;
Step 2: obtained electrostatic spinning precursor liquid is injected electrostatic spinning apparatus is 5 ~ 20KV by regulating spinning voltage, advance speed to be 0.1 ~ 3mL/h and receiving range is 5 ~ 30cm, prepares the CeO that load has metal or slaine
2the compound precursor fiber of/high polymer;
Step 3: according to one of following two kinds of modes supported catalyst:
(1) metal oxide particle/CeO
2fiber-loaded catalyst
The compound precursor fiber upper step prepared is placed in Muffle furnace, and be warming up to 600 ~ 1000 DEG C of calcinings with 5 ~ 10 DEG C/min speed in air atmosphere, calcination time is 1 ~ 10h, finally obtains metal oxide nanoparticles/CeO
2the supported catalyst of fiber.
(2) metallic/CeO
2fiber-loaded catalyst
The compound precursor fiber upper step prepared is placed in Muffle furnace, and under air or nitrogen atmosphere, be warming up to 600 ~ 1000 DEG C of calcinings with 5 ~ 10 DEG C/min speed, calcination time is 1 ~ 10h; Then reduce in a hydrogen atmosphere, pressure is 0.5 ~ 5KPa, and temperature is 300 ~ 900 DEG C, and the time is 0.5 ~ 5h, finally obtains metal nanoparticle/CeO
2the supported catalyst of fiber.
The principle that the present invention relates to is mainly: by CeO
2presoma obtained CeO in a mild condition
2colloidal sol; Metal or slaine are uniformly dispersed in a solvent after ultrasonic; By above-mentioned two kinds of dissolution homogeneity mixing, under the High Pressure of electrostatic spinning, prepare the CeO that load has metal or slaine
2the compound precursor fiber of/high polymer.In spinning process, because metallic is within the very short processbearing astrocyte time, very difficultly to assemble, so can be evenly dispersed in fiber.Again through high-temperature calcination, one is burnt by the organic principle of high polymer, and two is make CeO
2the molecules immobilized CeO being cross-linked into tridimensional network of colloidal sol
2fiber, metallic sinters at CeO with certain chemical form
2fiber surface.
The CeO adopted in the present invention
2presoma be cerous nitrate, cerous carbonate, cerous ammonium nitrate, cerous acetate, cerous acetate, cerous sulfate or ammonium sulfate cerium.
The high polymer adopted in the present invention is polymethyl methacrylate, polycarbonate, polyvinyl alcohol, polyvinylpyrrolidone, PLA, PEO, polycaprolactone, polyacrylic acid, poly-3-hydroxybutyrate or PGA.
Solvent is adopted to be the mixture of one or more solvents in deionized water, ethanol, trifluoroethanol, formic acid, triethanolamine, acetic acid, acetone, hexafluoroisopropanol, ethyl acetate, oxolane, carrene, chloroform, DMF, dimethyl sulfoxide (DMSO) in the present invention.
Adopt in the present invention metal or slaine for containing aluminium, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, molybdenum, ruthenium, rhodium, palladium, osmium, iridium, platinum, gold or its compound.
In step 3 of the present invention, metal nanoparticle is at CeO
2load capacity on fiber is 1wt.% ~ 30wt.%.
In step 3 described in the present invention, the particle diameter of metal or metal oxide nanoparticles is 5 ~ 100nm, and fibre diameter is 30 ~ 1000nm, and specific area is 100 ~ 500m
2/ g.
Advantage of the present invention is the fiber base loaded with nano catalyst adopting the method to prepare, and metal nanoparticle is evenly distributed on CeO
2fiber surface, the nano particle of metal or metal oxide is not easily reunited.And metal nanoparticle and CeO
2fiber is sintered together in high-temperature burning process, difficult drop-off.The specific surface of fiber base supported catalyst is large, and catalytic efficiency is high.
Beneficial effect of the present invention
(1) preparation method of the present invention is simple and easy to do, and cost is low.
(2) metal prepared of the present invention or metal oxide nanoparticles are carried on CeO
2fiber surface is dispersed, particle diameter is little, specific area is large.
(3) of the present invention being combined with each other by master-co-catalyst by electrostatic spinning technique is prepared into tencel based supported catalyst, has high catalytic activity and easy recovery feature, has broad application prospects at following catalytic field.
Accompanying drawing explanation
Fig. 1 is Pd/CeO prepared by the present invention's (embodiment 1)
2eSEM (SEM) figure of the supported catalyst of fiber
Fig. 2 is Rh/CeO prepared by the present invention's (embodiment 5)
2eSEM (SEM) figure of the load rice catalyst of fiber
Fig. 3 is Ni/CeO prepared by the present invention's (embodiment 7)
2transmission electron microscope (TEM) figure of the supported catalyst of fiber
Fig. 4 is Co/CeO prepared by the present invention's (embodiment 10)
2eSEM (SEM) figure of the supported catalyst of fiber
Detailed description of the invention:
In following examples, all processes of carrying out operating in solution all need hierarchy of control temperature to be less than 100 DEG C.
In following examples, all gas introduced in carrier gas all measures with the percent by volume of gas.
Embodiment 1
1, take 6.0g cerous nitrate and the mixing of 10.0g deionized water respectively, then magnetic agitation 12h, allows cerous nitrate fully be hydrolyzed, obtains CeO
2sol solution; 5.0g polyvinylpyrrolidone (PVP) is dissolved in 5.0g dimethyl sulfoxide (DMSO) (DMSO) and 10.0gN, in the mixed solvent of dinethylformamide (DMF), magnetic stirring apparatus stirs 12h, to the solution forming homogeneous transparent; Then by 0.3g catalyst palladium bichloride (PdCl
2) be dispersed in 3.0g DMF through ultrasonic process 4h be uniform and stable solution; Finally by these three kinds of solution mix and blend 0.5h to uniform liquid, the spinning precursor liquid that namely electrostatic spinning is used;
2, by 1 will be obtained electrostatic spinning precursor liquid inject electrostatic spinning apparatus, be 20KV by regulating spinning voltage, to advance speed to be 1mL/h and receiving range be 20cm, preparing load has PdCl
2ceO
2the compound precursor fiber of/high polymer;
3, the compound precursor fiber that 2 prepare is contained in crucible and is placed in Muffle furnace, be warming up to 800 DEG C of calcining 4h with 10 DEG C/min speed in air atmosphere, finally naturally cool to room temperature.Then the sample after calcining being put in reactor logical hydrogen atmosphere reduction, is 5KPa at pressure, and temperature is reduce 0.5h at 300 DEG C, namely obtains Pd/CeO
2the supported catalyst of fiber.
4, getting the sample obtained in 0.1g step 3, be put into acrylic acid catalytic hydrogenation in reactor, is 30kPa at pressure, and at 80 DEG C of temperature, react in nitrogen atmosphere, evaluating catalyst the results are shown in Table 1.The differential responses time hydrogenation efficiency of 1h, 3h and 6h is 64.9%, 80.3%, 92.3% respectively.
Embodiment 2
1, taking 6.0g cerous nitrate is dissolved in 5.0g deionized water and 5.0g alcohol mixed solvent, and then magnetic agitation 12h, allows cerous nitrate fully be hydrolyzed, obtain CeO
2sol solution; 50g polyvinylpyrrolidone (PVP) is dissolved in 5.0g dimethyl sulfoxide (DMSO) (DMSO) and 10.0gN, in the mixed solvent of dinethylformamide (DMF), magnetic stirring apparatus stirs 12h, to the solution forming homogeneous transparent; Then by 0.3g catalyst palladium bichloride (PdCl
2) be dispersed in 3.0g DMF through ultrasonic process 3h be uniform and stable solution; Finally by these three kinds of solution mix and blend 0.5h to uniform liquid, the spinning precursor liquid that namely electrostatic spinning is used;
2, by 1 will be obtained electrostatic spinning precursor liquid inject electrostatic spinning apparatus, be 20KV by regulating spinning voltage, to advance speed to be 1.0mL/h and receiving range be 20cm, preparing load has PdCl
2ceO
2the compound precursor fiber of/high polymer;
3, the compound precursor fiber that 2 prepare is contained in crucible and is placed in Muffle furnace, be warming up to 800 DEG C of calcining 4h with 10 DEG C/min speed in air atmosphere, finally naturally cool to room temperature.Then the sample after calcining being put in reactor logical hydrogen atmosphere reduction, is 5KPa at pressure, and temperature is reduce 0.5h at 300 DEG C, namely obtains Pd/CeO
2the supported catalyst of fiber.
4, getting the sample obtained in 0.1g step 3, be put into acrylic acid catalytic hydrogenation in reactor, is 30kPa at pressure, and at 80 DEG C of temperature, react in nitrogen atmosphere, evaluating catalyst the results are shown in Table 1.The differential responses time hydrogenation efficiency of 1h, 3h and 6h is 60.5% respectively,
74.4％，87.9％。
Embodiment 3
1, taking 6.0g cerous nitrate is dissolved in 10.0g ethanol, and then magnetic agitation 12h, allows cerous nitrate fully be hydrolyzed, obtain CeO
2sol solution; 5.0g polyvinylpyrrolidone (PVP) is dissolved in 10.0g ethanol, magnetic stirring apparatus stirs 12h, to the solution forming homogeneous transparent; Then by 0.3g catalyst palladium bichloride (PdCl
2) be dispersed in 3.0g DMF through ultrasonic process 2h be uniform and stable solution; Finally by these three kinds of solution mix and blend 0.5h to uniform liquid, the spinning precursor liquid that namely electrostatic spinning is used;
2, by 1 will be obtained electrostatic spinning precursor liquid inject electrostatic spinning apparatus, be 20KV by regulating spinning voltage, to advance speed to be 1.0mL/h and receiving range be 20cm, preparing load has PdCl
2ceO
2the compound precursor fiber of/high polymer;
3, the compound precursor fiber that 2 prepare is contained in crucible and is placed in Muffle furnace, be warming up to 800 DEG C of calcining 4h with 10 DEG C/min speed in air atmosphere, finally naturally cool to room temperature.Then the sample after calcining being put in reactor logical hydrogen atmosphere reduction, is 5KPa at pressure, and temperature is reduce 0.5h at 300 DEG C, namely obtains Pd/CeO
2the supported catalyst of fiber.
4, getting the sample obtained in 0.1g step 3, be put into acrylic acid catalytic hydrogenation in reactor, is 30kPa at pressure, and at 80 DEG C of temperature, react in nitrogen atmosphere, evaluating catalyst the results are shown in Table 1.The differential responses time hydrogenation efficiency of 1h, 3h and 6h is 53.2%, 69.1%, 82.5% respectively.
Comparative example 1
1,6.0g cerous nitrate and 0.3g catalyst palladium bichloride (PdCl is taken respectively
2), adopt equi-volume impregnating to prepare PdCl
2/ CeO
2presoma.
2, the PdCl prepared 1
2/ CeO
2presoma is contained in crucible and is placed in Muffle furnace, is warming up to 800 DEG C of high-temperature calcination 4h in air atmosphere, finally naturally cools to room temperature with 10 DEG C/min speed.Then the sample after calcining being put in reactor logical hydrogen atmosphere reduction, is 5KPa at pressure, and temperature is reduce 0.5h at 300 DEG C, namely obtains Pd/CeO
2the supported catalyst of fiber.
3, getting the sample obtained in 0.1g step 4, be put into acrylic acid catalytic hydrogenation in reactor, is 30kPa at pressure, and at 80 DEG C of temperature, react in nitrogen atmosphere, evaluating catalyst the results are shown in Table 1.The differential responses time hydrogenation efficiency of 1h, 3h and 6h is 50.5%, 65.5%, 78.2% respectively.
Embodiment 4
1, taking 3.0g cerous nitrate is dissolved in 5.0g ethanol, then at magnetic agitation 8h, allows cerous nitrate fully be hydrolyzed, obtains CeO
2sol solution; 0.5g polyvinylpyrrolidone (PVP) is dissolved in 2.0g deionized water, magnetic stirring apparatus stirs 8h, to the solution forming homogeneous transparent; Then 0.2g radium chloride (RhCl
3) to be dissolved in 2.0g ethanol through ultrasonic process 1h to homogeneous solution; Finally by these three kinds of solution mix and blend 0.5h to uniform liquid, the spinning precursor liquid that namely electrostatic spinning is used;
2, by 1 will be obtained electrostatic spinning precursor liquid inject electrostatic spinning apparatus, be 8KV by regulating spinning voltage, to advance speed to be 0.1mL/h and receiving range be 5cm, preparing load has RhCl
3ceO
2the compound precursor fiber of/high polymer;
3, the compound precursor fiber that 2 prepare is contained in crucible and is placed in Muffle furnace, be warming up to 600 DEG C of calcining 10h with 5 DEG C/min speed in air atmosphere, finally naturally cool to room temperature.Then the sample after calcining being put in reactor logical hydrogen atmosphere reduction, is 3KPa at pressure, and temperature is reduce 1h at 900 DEG C, namely obtains Rh/CeO
2the supported catalyst of fiber.
4, getting the sample obtained in 0.1g step 3, be put into epoxidation of styrene in reactor, is 2kPa at pressure, and at 300 DEG C of temperature, react in a nitrogen atmosphere, evaluating catalyst the results are shown in Table 2.Cinnamic maximum conversion is 2.0% respectively; The TOF of reaction is 6.2h
-1; The most high selectivity of epoxy product and benzaldehyde is 95.0%, 5.0% respectively.
Embodiment 5
1, take 3.0g cerous nitrate be dissolved in 5.0g go dried up in, then magnetic agitation 8h, allows cerous nitrate fully be hydrolyzed, obtains CeO
2sol solution; 0.5g polyvinylpyrrolidone (PVP) is dissolved in 1.0g ethanol and 1.0g deionized water, magnetic stirring apparatus stirs 8h, to the solution forming homogeneous transparent; Then 0.2g radium chloride (RhCl
3) to be dissolved in 2.0g DMF through ultrasonic process 1h to homogeneous solution; Finally by these three kinds of solution mix and blend 0.5h to uniform liquid, the spinning precursor liquid that namely electrostatic spinning is used;
2, by 1 will be obtained electrostatic spinning precursor liquid inject electrostatic spinning apparatus, be 8KV by regulating spinning voltage, to advance speed to be 0.1mL/h and receiving range be 5cm, preparing load has RhCl
3ceO
2the compound precursor fiber of/high polymer;
3, the compound precursor fiber that 2 prepare is contained in crucible and is placed in Muffle furnace, be warming up to 600 DEG C of calcining 10h with 5 DEG C/min speed in air atmosphere, finally naturally cool to room temperature.Then the sample after calcining being put in reactor logical hydrogen atmosphere reduction, is 3KPa at pressure, and temperature is reduce 1h at 900 DEG C, namely obtains Rh/CeO
2the supported catalyst of fiber.
4, getting the sample obtained in 0.1g step 3, be put into epoxidation of styrene in reactor, is 2kPa at pressure, and at 300 DEG C of temperature, react in a nitrogen atmosphere, evaluating catalyst the results are shown in Table 2.Cinnamic maximum conversion is 2.8% respectively; The TOF of reaction is 7.3h
-1; The most high selectivity of epoxy product and benzaldehyde is 92.2%, 7.8% respectively.
Embodiment 6
1, take 3.0g cerous nitrate and be dissolved in going in the alcohol mixed solvent of dried up and 2.0g of 3.0g, then magnetic agitation 8h, allows cerous nitrate fully be hydrolyzed, obtains CeO
2sol solution; 0.5g polyvinylpyrrolidone (PVP) is dissolved in 2.0g ethanol, and magnetic stirring apparatus stirs 8h, to the solution forming homogeneous transparent; Then 0.2g radium chloride (RhCl
3) to be dissolved in 2.0g DMF through ultrasonic process 1h to homogeneous solution; Finally by these three kinds of solution mix and blend 0.5h to uniform liquid, the spinning precursor liquid that namely electrostatic spinning is used;
2, by 1 will be obtained electrostatic spinning precursor liquid inject electrostatic spinning apparatus, be 8KV by regulating spinning voltage, to advance speed to be 0.1mL/h and receiving range be 5cm, preparing load has RhCl
3ceO
2the compound precursor fiber of/high polymer;
3, the compound precursor fiber that 2 prepare is contained in crucible and is placed in Muffle furnace, be warming up to 600 DEG C of calcining 10h with 5 DEG C/min speed in air atmosphere, finally naturally cool to room temperature.Then the sample after calcining being put in reactor logical hydrogen atmosphere reduction, is 3KPa at pressure, and temperature is reduce 1h at 900 DEG C, namely obtains Rh/CeO
2the supported catalyst of fiber.
4, getting the sample obtained in 0.1g step 3, be put into epoxidation of styrene in reactor, is 2kPa at pressure, and at 300 DEG C of temperature, react in a nitrogen atmosphere, evaluating catalyst the results are shown in Table 2.Cinnamic maximum conversion is 3.4% respectively; The TOF of reaction is 9.1h
-1; The most high selectivity of epoxy product and benzaldehyde is 89.0%, 89.0% respectively.
Comparative example 2
1,3.0g cerous nitrate and 0.2g radium chloride (RhCl is taken respectively
3), adopt equi-volume impregnating to prepare RhCl
3/ CeO
2presoma.
2, the RhCl prepared 1
3/ CeO
2presoma is contained in crucible and is placed in Muffle furnace, is warming up to 600 DEG C of high-temperature calcination 4h in air atmosphere, finally naturally cools to room temperature with 5 DEG C/min speed.Then the sample after calcining being put in reactor logical hydrogen atmosphere reduction, is 3KPa at pressure, and temperature is reduce 1h at 900 DEG C, namely obtains Rh/CeO
2the supported catalyst of fiber.
3, getting the sample obtained in 0.1g step 2, be put into epoxidation of styrene in reactor, is 2kPa at pressure, and at 300 DEG C of temperature, react in a nitrogen atmosphere, evaluating catalyst the results are shown in Table 2.Cinnamic maximum conversion is 4.6% respectively; The TOF of reaction is 12.3h
-1; The most high selectivity of epoxy product and benzaldehyde is 81.0%, 19.0% respectively.
Embodiment 7
1, take 4.0g cerous nitrate to be dissolved in 6.0g and to go in dried up and 2.0g alcohol mixed solvent, then magnetic agitation 9h, allows cerous nitrate fully be hydrolyzed, obtains CeO
2sol solution; 1.4g polyvinylpyrrolidone (PVP) is dissolved in 2.0g dimethyl sulfoxide (DMSO) (DMSO) and 4.0gN, and dinethylformamide (DMF), magnetic stirring apparatus stirs 9h, to the solution forming homogeneous transparent; Then 0.1g nickel nitrate (Ni (NO
3)
2) to be dissolved in 1.0g ethanol through ultrasonic process 2h to homogeneous solution; Finally by these three kinds of solution mix and blend 2h to uniform liquid, the spinning precursor liquid that namely electrostatic spinning is used;
2, by 1 will be obtained electrostatic spinning precursor liquid inject electrostatic spinning apparatus, be 15KV by regulating spinning voltage, to advance speed to be 3.0mL/h and receiving range be 30cm, preparing load has Ni (NO
3)
2ceO
2the compound precursor fiber of/high polymer;
3, the compound precursor fiber that 2 prepare is contained in crucible and is placed in Muffle furnace, be warming up to 800 DEG C of calcining 5h with 8 DEG C/min speed in air atmosphere, finally naturally cool to room temperature.Then the sample after calcining being put in reactor logical hydrogen atmosphere reduction, is 2.5KPa at pressure, and temperature is reduce 4h at 500 DEG C, namely obtains Ni/CeO
2the supported catalyst of fiber.
4, getting the sample obtained in 0.1g step 3 is put into methane carbon dioxide reformation in autoclave, and at pressure 1.5kPa, at 600 DEG C of temperature, 1:1:2 ventilating methane, carbon dioxide and argon gas react in molar ratio, and evaluating catalyst the results are shown in Table 3.CH
4, CO
2maximum conversion be 62.1%, 64.87% respectively; H
2, CO most high selectivity be 78.2%, 82.1% respectively.
Embodiment 8
1, take 4.0g cerous nitrate to be dissolved in 6.0g and to go in dried up and 2.0g alcohol mixed solvent, then magnetic agitation 9h, allows cerous nitrate fully be hydrolyzed, obtains CeO
2sol solution; 1.4g polyvinylpyrrolidone (PVP) is dissolved in 6.0g ethanol, magnetic stirring apparatus stirs 9h, to the solution forming homogeneous transparent; Then 0.1g nickel nitrate (Ni (NO
3)
2) to be dissolved in 1.0g DMSO through ultrasonic process 2h to homogeneous solution; Finally by these three kinds of solution mix and blend 2h to uniform liquid, the spinning precursor liquid that namely electrostatic spinning is used;
2, by 1 will be obtained electrostatic spinning precursor liquid inject electrostatic spinning apparatus, be 15KV by regulating spinning voltage, to advance speed to be 3.0mL/h and receiving range be 30cm, preparing load has Ni (NO
3)
2ceO
2the compound precursor fiber of/high polymer;
3, the compound precursor fiber that 2 prepare is contained in crucible and is placed in Muffle furnace, be warming up to 800 DEG C of calcining 5h with 8 DEG C/min speed in air atmosphere, finally naturally cool to room temperature.Then the sample after calcining being put in reactor logical hydrogen atmosphere reduction, is 2.5KPa at pressure, and temperature is reduce 4h at 500 DEG C, namely obtains Ni/CeO
2the supported catalyst of fiber.
4, getting the sample obtained in 0.1g step 3 is put into methane carbon dioxide reformation in autoclave, and at pressure 1.5kPa, at 600 DEG C of temperature, 1:1:2 ventilating methane, carbon dioxide and argon gas react in molar ratio, and evaluating catalyst the results are shown in Table 3.CH
4, CO
2maximum conversion be 58.3%, 62.4% respectively; H
2, CO most high selectivity be 72.5%, 76.3% respectively.
Comparative example 3
1,4.0g cerous nitrate and 0.1g nickel nitrate (Ni (NO is taken respectively
3)
2), adopt equi-volume impregnating to prepare Ni (NO
3)
2/ CeO
2presoma.
2, the Ni (NO prepared 1
3)
2/ CeO
2presoma is contained in crucible and is placed in Muffle furnace, is warming up to 800 DEG C of high-temperature calcination 5h in air atmosphere, finally naturally cools to room temperature with 8 DEG C/min speed.Then the sample after calcining being put in reactor logical hydrogen atmosphere reduction, is 2.5KPa at pressure, and temperature is reduce 4h at 500 DEG C, namely obtains Ni/CeO
2the supported catalyst of fiber.
3, getting the sample obtained in 0.1g step 2 is put into methane carbon dioxide reformation in autoclave, and at pressure 1.5kPa, at 600 DEG C of temperature, 1:1:2 ventilating methane, carbon dioxide and argon gas react in molar ratio, and evaluating catalyst the results are shown in Table 3.CH
4, CO
2maximum conversion be 50.2%, 54.4% respectively; H
2, CO most high selectivity be 67.6%, 69.3% respectively.
Embodiment 9
1, take 1.0g cerous acetate be dissolved in 2.0g go dried up in, then magnetic agitation 10h, allows cerous acetate fully be hydrolyzed, obtains CeO
2sol solution; 0.5g polyvinylpyrrolidone (PVP) is dissolved in 2.0g ethanol, magnetic stirring apparatus stirs 10h, to the solution forming homogeneous transparent; Then 0.05g cobalt nitrate (Co (NO
3)
2) to be dissolved in 0.5g deionized water through ultrasonic process 3h to homogeneous solution; Finally by these three kinds of solution mix and blend 2h to uniform liquid, the spinning precursor liquid that namely electrostatic spinning is used;
2, by 1 will be obtained electrostatic spinning precursor liquid inject electrostatic spinning apparatus, be 18KV by regulating spinning voltage, to advance speed to be 1.0mL/h and receiving range be 20cm, preparing load has Co (NO
3)
2ceO
2the compound precursor fiber of/high polymer;
3, the compound precursor fiber that 2 prepare is contained in crucible and is placed in Muffle furnace, be warming up to 1000 DEG C of calcining 4h with 10 DEG C/min speed in air atmosphere, finally naturally cool to room temperature.Then the sample after calcining being put in reactor logical hydrogen atmosphere reduction, is 4KPa at pressure, and temperature is reduce 5h at 600 DEG C, namely obtains Co/CeO
2the supported catalyst of fiber.
4, get the sample obtained in 0.1g step 3, at 1000 DEG C of temperature, 1:3 leads to the mixed solution of second alcohol and water in molar ratio, more logical nitrogen reacts, and evaluating catalyst the results are shown in Table 1.C
2h
5the maximum conversion of OH is 68.35% respectively; H
2, CO, CO
2, CH
4most high selectivity be 70.33%, 7.92% respectively, 13.55%, 7.33%.
Embodiment 10
1, taking 1.0g cerous acetate is dissolved in 2.0g ethanol, and then magnetic agitation 10h, allows cerous acetate fully be hydrolyzed, obtain CeO
2sol solution; 0.5g polyvinylpyrrolidone (PVP) is dissolved in 2.0gDMF, magnetic stirring apparatus stirs 10h, to the solution forming homogeneous transparent; Then 0.05g cobalt nitrate (Co (NO
3)
2) to be dissolved in 0.5g deionized water through ultrasonic process 3h to homogeneous solution; Finally by these three kinds of solution mix and blend 2h to uniform liquid, the spinning precursor liquid that namely electrostatic spinning is used;
2, by 1 will be obtained electrostatic spinning precursor liquid inject electrostatic spinning apparatus, be 18KV by regulating spinning voltage, to advance speed to be 1.0mL/h and receiving range be 20cm, preparing load has Co (NO
3)
2ceO
2the compound precursor fiber of/high polymer;
3, the compound precursor fiber that 2 prepare is contained in crucible and is placed in Muffle furnace, be warming up to 1000 DEG C of calcining 4h with 10 DEG C/min speed in air atmosphere, finally naturally cool to room temperature.Then the sample after calcining being put in reactor logical hydrogen atmosphere reduction, is 4KPa at pressure, and temperature is reduce 5h at 600 DEG C, namely obtains Co/CeO
2the supported catalyst of fiber.
4, get the sample obtained in 0.1g step 3, at 1000 DEG C of temperature, 1:3 leads to the mixed solution of second alcohol and water in molar ratio, more logical nitrogen reacts, and evaluating catalyst the results are shown in Table 1.C
2h
5the maximum conversion of OH is 65.93% respectively; H
2, CO, CO
2, CH
4most high selectivity be 68.14%, 7.69% respectively, 11.65%, 8.90%.
Comparative example 4
1,1.0g cerous nitrate and 0.05g cobalt nitrate (Co (NO is taken respectively
3)
2), adopt equi-volume impregnating to prepare Co (NO
3)
2/ CeO
2presoma.
2, the Co (NO prepared 1
3)
2/ CeO
2presoma is contained in crucible and is placed in Muffle furnace, is warming up to 1000 DEG C of high-temperature calcination 4h in air atmosphere, finally naturally cools to room temperature with 10 DEG C/min speed.Then the sample after calcining being put in reactor logical hydrogen atmosphere reduction, is 4KPa at pressure, and temperature is reduce 5h at 600 DEG C, namely obtains Co/CeO
2the supported catalyst of fiber.
3, get the sample obtained in 0.1g step 2, at 1000 DEG C of temperature, 1:3 leads to the mixed solution of second alcohol and water in molar ratio, more logical nitrogen reacts, and evaluating catalyst the results are shown in Table 1.C
2h
5the maximum conversion of OH is 59.21% respectively; H
2, CO, CO
2, CH
4most high selectivity be 62.88%, 6.45% respectively, 10.33%, 10.34%.
Embodiment 11
1, taking 5.0g cerous acetate is dissolved in 8.0g ethanol, and then magnetic agitation 10h, allows cerous acetate fully be hydrolyzed, obtain CeO
2sol solution; 1.5g polyvinyl alcohol (PVA) is dissolved in 5.0g ethanol, magnetic stirring apparatus stirs 10h, to the solution forming homogeneous transparent; Then 0.1g Argent grain (Ag) to be dissolved in 3g ethanol through ultrasonic process 4h to homogeneous solution; Finally by these three kinds of solution mix and blend 2h to uniform liquid, the spinning precursor liquid that namely electrostatic spinning is used;
2, by 1 will be obtained electrostatic spinning precursor liquid inject electrostatic spinning apparatus, being 16KV by regulating spinning voltage, advancing speed to be 1.0mL/h and receiving range to be 20cm, to prepare the CeO that load has Ag
2the compound precursor fiber of/high polymer;
3, the compound precursor fiber that 2 prepare is contained in crucible and is placed in Muffle furnace, be warming up to 800 DEG C of calcining 4h with 10 DEG C/min speed in a nitrogen atmosphere, finally naturally cool to room temperature.Then the sample after calcining being put in reactor logical hydrogen atmosphere reduction, is 4KPa at pressure, and temperature is reduce 5h at 600 DEG C, namely obtains Ag/CeO
2the supported catalyst of fiber.
Embodiment 12
1, take 6.0g cerous acetate to be dissolved in 6.0g and to go in dried up and 4.0g alcohol mixed solvent, then magnetic agitation 9h, allows cerous acetate fully be hydrolyzed, obtains CeO
2sol solution; 1.7g polyvinyl alcohol (PVA) is dissolved in 7.0g ethanol, magnetic stirring apparatus stirs 9h, to the solution forming homogeneous transparent; Then 0.5g nickel nitrate (Ni (NO
3)
2) to be dissolved in 2.0g ethanol through ultrasonic process 4h to homogeneous solution; Finally by these three kinds of solution mix and blend 2h to uniform liquid, the spinning precursor liquid that namely electrostatic spinning is used;
2, by 1 will be obtained electrostatic spinning precursor liquid inject electrostatic spinning apparatus, be 16KV by regulating spinning voltage, to advance speed to be 1.0mL/h and receiving range be 20cm, preparing load has Ni (NO
3)
2ceO
2the compound precursor fiber of/high polymer;
3, the compound precursor fiber that 2 prepare is contained in crucible and is placed in Muffle furnace, be warming up to 800 DEG C of calcining 5h with 5 DEG C/min speed in air atmosphere, finally naturally cool to room temperature, namely obtain NiO/CeO
2the supported catalyst of fiber.
Embodiment 13
1, taking 6.0g cerous acetate is dissolved in 10.0g ethanol, and then magnetic agitation 10h, allows cerous acetate fully be hydrolyzed, obtain CeO
2sol solution; 1.6g polyvinyl alcohol (PVA) is dissolved in 6.0g ethanol, magnetic stirring apparatus stirs 10h, to the solution forming homogeneous transparent; Then 0.4g cobalt nitrate (Co (NO
3)
2) to be dissolved in 2g ethanol through ultrasonic process 3h to homogeneous solution; Finally by these three kinds of solution mix and blend 2h to uniform liquid, the spinning precursor liquid that namely electrostatic spinning is used;
2, by 1 will be obtained electrostatic spinning precursor liquid inject electrostatic spinning apparatus, be 16KV by regulating spinning voltage, to advance speed to be 1.0mL/h and receiving range be 20cm, preparing load has Co (NO
3)
2ceO
2the compound precursor fiber of/high polymer;
3, the compound precursor fiber that 2 prepare is contained in crucible and is placed in Muffle furnace, be warming up to 1000 DEG C of calcining 4h with 10 DEG C/min speed in air atmosphere, finally naturally cool to room temperature, namely obtain Co
3o
4/ CeO
2the supported catalyst of fiber.
Embodiment 14
1, taking 5.0g cerous acetate is dissolved in 8.0g ethanol, and then magnetic agitation 10h, allows cerous acetate fully be hydrolyzed, obtain CeO
2sol solution; 1.5g polyvinyl alcohol (PVA) is dissolved in 5.0g ethanol, magnetic stirring apparatus stirs 10h, to the solution forming homogeneous transparent; Then 0.3g zinc nitrate (Zn (NO
3)
2) to be dissolved in 4g ethanol through ultrasonic process 3h to homogeneous solution; Finally by these three kinds of solution mix and blend 2h to uniform liquid, the spinning precursor liquid that namely electrostatic spinning is used;
2, by 1 will be obtained electrostatic spinning precursor liquid inject electrostatic spinning apparatus, be 16KV by regulating spinning voltage, to advance speed to be 1.0mL/h and receiving range be 20cm, preparing load has Zn (NO
3)
2ceO
2the compound precursor fiber of/high polymer;
3, the compound precursor fiber that 2 prepare is contained in crucible and is placed in Muffle furnace, be warming up to 900 DEG C of calcining 4h with 10 DEG C/min speed in air atmosphere, finally naturally cool to room temperature, namely obtain ZnO/CeO
2the supported catalyst of fiber.
Embodiment 15
1, taking 5.0g cerous acetate is dissolved in 8.0g ethanol, and then magnetic agitation 10h, allows cerous acetate fully be hydrolyzed, obtain CeO
2sol solution; 1.5g polyvinyl alcohol (PVA) is dissolved in 5.0g ethanol, magnetic stirring apparatus stirs 10h, to the solution forming homogeneous transparent; Then 0.2g copper nitrate (Cu (NO
3)
2) to be dissolved in 3g ethanol through ultrasonic process 3h to homogeneous solution; Finally by these three kinds of solution mix and blend 2h to uniform liquid, the spinning precursor liquid that namely electrostatic spinning is used;
2, by 1 will be obtained electrostatic spinning precursor liquid inject electrostatic spinning apparatus, be 16KV by regulating spinning voltage, to advance speed to be 1.0mL/h and receiving range be 20cm, preparing load has Cu (NO
3)
2ceO
2the compound precursor fiber of/high polymer;
3, the compound precursor fiber that 2 prepare is contained in crucible and is placed in Muffle furnace, be warming up to 900 DEG C of calcining 4h with 10 DEG C/min speed in air atmosphere, finally naturally cool to room temperature, namely obtain CuO/CeO
2the supported catalyst of fiber.
Table 1 Pd/CeO
2the supported catalyst of fiber is to acrylic acid hydrogenation efficiency
Table 2 Rh/CeO
2the performance evaluation that the supported catalyst of fiber reacts epoxidation of styrene
Table 3.Ni/CeO
2the supported catalyst of fiber is to the performance evaluation of methane carbon dioxide reformation catalyst
Table 4.Co/CeO
2the supported catalyst of fiber is to the performance evaluation of ethanol steam reforming catalyst
Table 5 metal or metal oxide particle/CeO
2the relevant parameter of the supported catalyst of fiber
| Embodiment | Average grain diameter/nm | BET/m 2/g |
| Embodiment 1 | 20.2 | 367.9 |
| Embodiment 2 | 21.5 | 344.0 |
| Embodiment 3 | 20.6 | 347.5 |
| Comparative example 1 | 60.4 | 99.2 |
| Embodiment 4 | 43.3 | 274.7 |
| Embodiment 5 | 46.7 | 268.5 |
| Embodiment 6 | 44.9 | 254.1 |
| Comparative example 2 | 70.1 | 84.3 |
| Embodiment 7 | 10.2 | 221.9 |
| Embodiment 8 | 9.8 | 225.4 |
| Comparative example 3 | 50.3 |
| Embodiment 9 | 50.4 | 169.5 |
| Embodiment 10 | 52.2 | 159.7 |
| Comparative example 4 |
| Embodiment 11 | 60.7 | 130.3 |
| Embodiment 12 | 11.7 | 389.4 |
| Embodiment 13 | 55.8 | 241.7 |
| Embodiment 14 | 34.8 | 235.8 |
| Embodiment 15 | 39.0 | 201.5 |
From the data in table 1-table 5, the metallic/CeO prepared with equal-volume infusion method
2the metal of supported catalyst or metal oxide particle particle diameter large, specific area is little, carries out Catalysis experiments experiment, catalyst efficiency and activity low.The metal that the present invention adopts electrostatic spinning technique to prepare or metal oxide particle/CeO
2metal or the metal oxide particle particle diameter of the supported catalyst of fiber are little, and specific area is large, carries out Catalysis experiments, catalytic efficiency and activity high, there is good stability in use simultaneously.Embodiment 11-embodiment 15 carries out Catalysis experiments also can obtain same catalytic effect.
Claims (7)
1. the CeO of a containing metal or metal oxide particle
2the preparation method of fiber catalyst, is characterized in that specifically carrying out according to following steps:
Step 1:(1) take the CeO of 1 ~ 6g respectively
2the solvent of presoma and 2 ~ 10g, magnetic agitation 5 ~ 12h after mixing, allows CeO
2presoma is fully hydrolyzed, and obtains CeO
2sol solution; (2) high polymer of 0.5 ~ 5g is dissolved in 2 ~ 15g solvent, magnetic stirring apparatus stirs 5 ~ 12h, form the solution of homogeneous transparent; (3) by 0.05 ~ 0.5g metal or dissolving metal salts in 0.5 ~ 3g solvent through ultrasonic 1 ~ 4h, form stable homogeneous solution; (4) finally by these three kinds of solution mix and blend 0.5 ~ 2h extremely uniformly liquid, electrostatic spinning precursor liquid is;
Step 2: obtained electrostatic spinning precursor liquid is injected electrostatic spinning apparatus is 5 ~ 20KV by regulating spinning voltage, advance speed to be 0.1 ~ 3mL/h and receiving range is 5 ~ 30cm, prepares the CeO that load has metal or slaine
2the compound precursor fiber of/high polymer;
Step 3: according to one of following two kinds of modes supported catalyst:
(1) metal oxide particle/CeO
2fiber-loaded catalyst
The compound precursor fiber upper step prepared is placed in Muffle furnace, and be warming up to 600 ~ 1000 DEG C of calcinings with 5 ~ 10 DEG C/min speed in air atmosphere, calcination time is 1 ~ 10h, finally obtains metal oxide nanoparticles/CeO
2the supported catalyst of fiber.
(2) metallic/CeO
2fiber-loaded catalyst
The compound precursor fiber upper step prepared is placed in Muffle furnace, under air or nitrogen atmosphere, be warming up to 600 ~ 1000 DEG C of high-temperature calcinations with 5 ~ 10 DEG C/min speed, and calcination time is 1 ~ 10h; Then reduce in a hydrogen atmosphere, pressure is 0.5 ~ 5KPa, and temperature is 300 ~ 900 DEG C, and the time is 0.5 ~ 5h, finally obtains metal nanoparticle/CeO
2the supported catalyst of fiber.
2. the CeO of a kind of containing metal according to claim 1 or metal oxide particle
2the preparation method of fiber catalyst, is characterized in that: the CeO adopted in described step 1
2presoma is cerous nitrate, cerous carbonate, cerous ammonium nitrate, cerous acetate, cerous acetate, cerous sulfate or ammonium sulfate cerium.
3. the CeO of a kind of containing metal according to claim 1 or metal oxide particle
2the preparation method of fiber catalyst, is characterized in that: the high polymer adopted in described step 1 is polymethyl methacrylate, polycarbonate, polyvinyl alcohol, polyvinylpyrrolidone, PLA, PEO, polycaprolactone, polyacrylic acid, poly-3-hydroxybutyrate or PGA.
4. the CeO of a kind of containing metal according to claim 1 or metal oxide particle
2the preparation method of fiber catalyst, it is characterized in that: the solvent adopted in described step 1 is the mixture of one or more solvents in deionized water, ethanol, trifluoroethanol, formic acid, triethanolamine, acetic acid, acetone, hexafluoroisopropanol, ethyl acetate, oxolane, carrene, chloroform, DMF, dimethyl sulfoxide (DMSO).
5. the CeO of a kind of containing metal according to claim 1 or metal oxide particle
2the preparation method of fiber catalyst, is characterized in that: the metal adopted in described step 1 or slaine are for containing aluminium, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, molybdenum, ruthenium, rhodium, palladium, osmium, iridium, platinum, gold or its compound.
6. the CeO of a kind of containing metal according to claim 1 or metal oxide particle
2the preparation method of fiber catalyst, is characterized in that: in described step 3, metal nanoparticle is at CeO
2load capacity on fiber is 1% ~ 30%.
7. the CeO of a kind of containing metal according to claim 1 or metal oxide particle
2the preparation method of fiber catalyst, is characterized in that: in described step 3, the particle diameter of metal nanoparticle is 5 ~ 100nm, and fibre diameter is 30 ~ 1000nm, and specific area is 100 ~ 500m
2/ g.
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