CN106179368B - A kind of higher LaCoO with core-shell structure of catalytic performance3@La(OH)3Composite catalyst and preparation method thereof - Google Patents
A kind of higher LaCoO with core-shell structure of catalytic performance3@La(OH)3Composite catalyst and preparation method thereof Download PDFInfo
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- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
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Abstract
The present invention discloses a kind of higher LaCoO with core-shell structure of catalytic performance3@La(OH)3Composite catalyst and preparation method thereof is electrostatic spinning alkali cleaning in-situ synthesis.It is characterized in that：The composite catalyst catalytic performance is higher, has core-shell structure, La (OH)3For shell, Ca-Ti ore type LaCoO3For core.The preparation method uses method of electrostatic spinning synthesis Ca-Ti ore type LaCoO first3Nanofiber, then with strong base solution to LaCoO3Nanofiber carries out alkali cleaning processing, and lye, drying is finally washed with deionized water, obtains LaCoO3@La(OH)3Composite catalyst.It prepares that the temperature needed for catalyst is relatively low, energy saving and simple for process using this method, the catalytic performance of catalyst can be improved, be conducive to the popularization and application of perofskite type oxide.
Description
Technical field
The present invention relates to a kind of preparations and application of perofskite type oxide composite catalyst, and in particular to uses Static Spinning
The combination of silk technology and alkali cleaning, fabricated in situ have the LaCoO of core-shell structure3@La(OH)3Composite catalyst.
Background technology
A large amount of discharges of volatile organic matter (VOCs) can cause serious environmental pollution, both may be directly to health
It damages, it is also possible to be converted into photochemical fog or PM2.5, cause secondary pollution.Therefore the removal of VOCs is environmental protection
One of great subject under discussion.Catalytic oxidation is low with initiation temperature, save the energy, is applied widely, treatment effeciency is high and nothing two
The advantages that secondary pollution, becomes mainstream and developing direction that current VOCs is administered.Noble metal catalyst has higher urge to VOCs
Change oxidability, but its resource scarcity, expensive, and thermal stability is poor, researcher has been devoted to selection noble metal
The substitute of catalyst.Perofskite type oxide (general formula ABO3) it is relatively inexpensive, composition it is flexible and changeable, have higher catalysis
Performance and thermal stability are expected to the substitute as noble metal catalyst, are current research hotspots.
However, the relatively low reason of perofskite type oxide catalytic performance limits its industrial applications.Specific surface area is low to be
Therefore the primary factor for causing perofskite type oxide catalytic performance low is to promote Ca-Ti ore type oxygen by promoting specific surface area
One of compound catalytic performance effective way.Sum up, researcher mainly promotes Ca-Ti ore type by following three approach
The reference area of oxide：(1) crystallization temperature is reduced.It can be effectively inhibited by reducing the crystallization temperature of perofskite type oxide
The growth of crystal grain, to make perofskite type oxide keep large specific surface area.(2) load method.Perofskite type oxide is born
It is loaded on the carrier with high specific surface area, its dispersion degree can be improved, prevent high temperature sintering, to promote its specific surface area
And catalytic performance.(3) novel method for synthesizing is used.Such as nanometer casting method and method of electrostatic spinning can be synthesized with special knot
The higher catalyst of structure, specific surface, can be obviously improved the catalytic performance of perofskite type oxide.Perofskite type oxide is carried out
Structural modification is another effective ways for promoting its catalytic performance.Method of modifying common at present has：(1) metal ion replaces
Method.Perofskite type oxide (ABO3) catalytic activity depend primarily on B bits element, to A/B bit elements carry out part substitution or
It replaces, the electronic structure of B ions can be changed, enhance Oxygen mobility, and then promote the catalytic performance of perofskite type oxide；
(2) halogen doping.Studies have shown that by halide ion (F-Or Cl-) it is doped to ABO3Lattice in be adjusted B it is cationic each
Oxidation state ratio increases the mobility of Lattice Oxygen, to promote the catalytic oxidation performance of perofskite type oxide.In addition, multigroup
Point composite algorithm also can effectively promote perofskite type oxide catalytic performance.In recent years studies have shown that a small amount of noble metal is born
It is loaded in Ca-Ti ore type oxide surface, obtained noble metal-perovskite composite catalyst can not only promote the catalysis of perovskite
Performance also has preferable stability.
Multicomponent composite algorithm is current one of the research direction for promoting perofskite type oxide catalytic performance.But report at present
More is noble metal-perovskite composite catalyst, and infusion process is usually used in carrying method, it is understood that there may be active component is moved
It moves, the problems such as dispersion degree is poor, load factor is relatively low.
Invention content
In view of the above problems, it is higher with core-shell structure that the purpose of the present invention is to provide a kind of catalytic performances
LaCoO3@La(OH)3Composite catalyst and preparation method thereof --- electrostatic spinning-alkali cleaning in-situ synthesis, this method is using by force
Etching alkaline solution LaCoO3Nanofiber shows in-situ preparation La (OH)3Crystal forms the composite material with core-shell structure, carries
Rise LaCoO3Catalytic oxidation performance.
Use technical solution as follows to achieve the purpose of the present invention：A kind of catalytic performance is higher with core-shell structure
LaCoO3@La(OH)3Composite catalyst, it is characterised in that：The LaCoO3@La(OH)3Composite catalyst has higher urge
Change performance and special structure --- core-shell structure, La (OH)3For shell, Ca-Ti ore type LaCoO3For core.
The higher LaCoO with core-shell structure of a kind of catalytic performance of the present invention3@La(OH)3Composite catalyst,
It is characterized in that, is prepared by following methods comprising following steps：
1）Lanthanum nitrate, cobalt nitrate, polyvinylpyrrolidone and citric acid are dissolved in N, N- dimethyl by magnetic agitation
In formamide solvent, electrostatic spinning precursor solution is prepared；
2）The electrostatic spinning precursor solution that step 1) is prepared is made by composite nano fiber using method of electrostatic spinning, then
It places it in and preserves 8~15 h in drier；
3）Composite nano fiber prepared by step 2) is placed in Muffle furnace, is calcined in air atmosphere, obtains calcium
Titanium ore type LaCoO3；
4）The Ca-Ti ore type LaCoO with strong base solution prepared by step 3)3Alkali cleaning is carried out, then with deionized water centrifuge washing
It is neutrality to supernatant, sample is finally dried to 12~24 h at 70~90 DEG C, obtains LaCoO3@La(OH)3Composite catalyzing
Agent.
In the electrostatic spinning precursor solution, the ratio between lanthanum element and the amount of cobalt element substance are 1:1, the total matter of nitrate
(g) is measured with the volume (mL) of solvent N,N-dimethylformamide than being 0.03~0.04:1, the amount for the lemon acid substance being added
It it is 2~4 times of lanthanum element, polyvinylpyrrolidone quality (g) and volume (mL) ratio of solvent n,N-Dimethylformamide are
0.07~0.12:1.
A kind of higher LaCoO with core-shell structure of catalytic performance as claimed in claim 1 or 23@La(OH)3It is compound to urge
Agent, it is characterised in that：The electrostatic spinning voltage is 23 kV, and charging rate is 1.0 mL/h, and temperature is 43 DEG C, stainless
Draw point head internal diameter is 1 mm, and it is 15 cm to receive distance, and it is 8~10 h to continue the Electrospun time.
The heating rate of composite nano fiber calcining is 2~8 DEG C/min, and calcining thermostat temperature is 500 DEG C, calcines constant temperature
Time is 4 h；The strong base solution is the NaOH solution or KOH solution of brand-new, a concentration of 2~10 mol/L, LaCoO3's
Quality (g) and volume (mL) ratio of strong base solution are 0.004~0.01:1；Solution constantly carries out magnetic force and stirs in alkaline cleaning procedure
It mixes, at 50~80 DEG C, the alkali cleaning time is 3~9 h, after alkali cleaning, is washed away lye with deionized water for temperature control, until
Cleaning solution is in neutrality.
The higher LaCoO with core-shell structure of a kind of catalytic performance of the present invention3@La(OH)3The system of composite catalyst
Preparation Method includes the following steps：
1）Lanthanum nitrate, cobalt nitrate, polyvinylpyrrolidone and citric acid are dissolved in N, N- dimethyl by magnetic agitation
In formamide solvent, electrostatic spinning precursor solution is prepared；
2）The electrostatic spinning precursor solution that step 1) is prepared is made by composite nano fiber using method of electrostatic spinning, then
It places it in and preserves 8~15 h in drier；
3）Composite nano fiber prepared by step 2) is placed in Muffle furnace, is calcined in air atmosphere, obtains calcium
Titanium ore type LaCoO3；
4）The Ca-Ti ore type LaCoO with strong base solution prepared by step 3)3Alkali cleaning is carried out, then with deionized water centrifuge washing
It is neutrality to supernatant, sample is finally dried to 12~24 h at 70~90 DEG C, obtains LaCoO3@La(OH)3Composite catalyzing
Agent.
Method as claimed in claim 6, it is characterised in that：In the electrostatic spinning precursor solution, lanthanum element with
The ratio between amount of cobalt element substance is 1:1, nitrate gross mass (g) and volume (mL) ratio of solvent n,N-Dimethylformamide are
0.03~0.04:1, the amount of the lemon acid substance being added is 2~4 times of lanthanum element, polyvinylpyrrolidone quality (g) with it is molten
The volume (mL) of agent N,N-dimethylformamide is than being 0.07~0.12:1.
The electrostatic spinning voltage is 23 kV, and charging rate is 1.0 mL/h, and temperature is 43 DEG C, in stainless steel syringe needle
Diameter is 1 mm, and it is 15 cm to receive distance, and it is 8~10 h to continue the Electrospun time.
The heating rate of above-mentioned composite nano fiber calcining is 2~8 DEG C/min, and calcining thermostat temperature is 500 DEG C, calcining
Constant temperature time is 4 h；The strong base solution be brand-new NaOH solution or KOH solution, a concentration of 2~10 mol/L,
LaCoO3Quality (g) and strong base solution volume (mL) than being 0.004~0.01:1；In alkaline cleaning procedure solution constantly into
Row magnetic agitation, at 50~80 DEG C, the alkali cleaning time is 3~9 h, after alkali cleaning, is washed lye with deionized water for temperature control
It goes, until cleaning solution is in neutrality.
Specifically, the higher LaCoO with core-shell structure of a kind of catalytic performance of the present invention3@La(OH)3It is compound
The preparation method of catalyst, includes the following steps：
(1) lanthanum nitrate, cobalt nitrate, polyvinylpyrrolidone and citric acid are dissolved in N, N- dimethyl by magnetic agitation
In formamide solvent, electrostatic spinning precursor solution is prepared；
(2) the electrostatic spinning precursor solution that step (1) is prepared is made by composite nano fiber using method of electrostatic spinning, so
After place it in and preserve 8~15 h in drier；
(3) composite nano fiber prepared by step (2) is placed in Muffle furnace, is calcined, is obtained in air atmosphere
Ca-Ti ore type LaCoO3；
(4) the Ca-Ti ore type LaCoO with strong base solution prepared by step (3)3Alkali cleaning is carried out, then is washed with deionized water centrifugation
It is neutrality to wash to supernatant, and sample is finally dried to 12~24 h at 70~90 DEG C, obtains LaCoO3@La(OH)3It is compound to urge
Agent.
Preferably, in electrostatic spinning precursor solution described in step (1), the ratio between lanthanum element and the amount of cobalt element substance are
1:1, nitrate gross mass (g) and volume (mL) ratio of solvent n,N-Dimethylformamide are 0.03~0.04:1, it is added
The amount of lemon acid substance is 2~4 times of lanthanum element, polyvinylpyrrolidone quality (g) and solvent n,N-Dimethylformamide
Volume (mL) is than being 0.07~0.12:1.
Preferably, the electrostatic spinning voltage of step (2) is 23 kV, charging rate is 1.0 mL/h, and temperature is 43 DEG C, no
The draw point head internal diameter that becomes rusty is 1 mm, and it is 15 cm to receive distance, and it is 8~10 h to continue the Electrospun time.
Preferably, the heating rate of step (3) composite nano fiber calcining is 2~8 DEG C/min, calcining thermostat temperature is
500 DEG C, calcining constant temperature time is 4 h；Strong base solution be brand-new NaOH solution or KOH solution, a concentration of 2~10 mol/L,
LaCoO3Quality (g) and strong base solution volume (mL) than being 0.004~0.01:1；In alkaline cleaning procedure solution constantly into
Row magnetic agitation, at 50~80 DEG C, the alkali cleaning time is 3~9 h, after alkali cleaning, is washed lye with deionized water for temperature control
It goes, until cleaning solution is in neutrality.
It can be seen from the above technical scheme that the present invention has the advantages that：
(1) LaCoO3@La(OH)3Composite catalyst has special microstructure --- core-shell structure, La (OH)3For
Shell, Ca-Ti ore type LaCoO3For core, La (OH)3With Ca-Ti ore type LaCoO3Compound effectively improve LaCoO3Catalytic performance；
(2) under the action of highly basic, LaCoO3Nanofiber shows in-situ preparation La (OH)3, formed with core-shell structure
LaCoO3@La(OH)3Composite catalyst, have many advantages, such as it is simple for process, it is easy to operate.
Description of the drawings
Fig. 1 is the TEM figures of the SEM figures of each sample prepared by embodiment and the sample of 9 h of non-alkali cleaning sample and alkali cleaning.
Fig. 2 is the XRD spectra of each sample prepared by embodiment.
Fig. 3 is each sample prepared by embodiment at different temperatures to the catalytic conversion figure of benzene.
Specific implementation mode
To be best understood from the present invention, the present invention is described further with reference to embodiment, but the present invention claims
The range of protection is not limited to the range of embodiment expression.
Embodiment
1) 0.3690 g La (NO accurately are weighed3)3·nH2O、0.3215 g Co(NO3)2·6H2O and 0.6965 g
C6H8O7·H2O (wherein the ratio between amount of substance of lanthanum element, cobalt element and citric acid La:Co:C6H8O7=1:1:3.0) in 50 mL
Conical flask in, and 2.000 g PVP and 20 mL DMF solutions are added, at room temperature, magnetic agitation is obtained to being completely dissolved
In aubergine, uniform electrostatic spinning precursor solution.
2) electrostatic spinning is carried out to the electrostatic spinning precursor solution that step 1) is prepared, condition is：1.0 mL/ of feed liquor rate
H, 23.0 kV of voltage, 43 DEG C of temperature, 1 mm of stainless steel syringe needle internal diameter receive 15 cm of distance, and the electrostatic spinning duration is 10
h.After electrostatic spinning, composite nano fiber is obtained, is placed on 12 h of room temperature preservation in drier.
3) composite nano fiber for obtaining step 2) is placed in crucible, is put into Muffle furnace and is calcined.With 5 DEG C/min's
Heating rate rises to 500 DEG C from room temperature, and 4 h of calcining at constant temperature obtains Ca-Ti ore type LaCoO3。
4) the Ca-Ti ore type LaCoO that 0.20 g steps 3) obtain is weighed34 parts of sample is separately added into a concentration of 2 M of 50 ml
NaOH solution (newly preparing), stir 3h, 5h, 7h and 9 h respectively in 60 DEG C of water-bath, be then centrifuged for, outwell supernatant
Liquid, with the multiple washing sample of distilled water, until solution supernatant is in neutrality.Water washed sample will be distilled to be placed on 80 in baking oven
DEG C drying 12 h, obtain final electrostatic spinning-alkali cleaning fabricated in situ have core-shell structure LaCoO3@La(OH)3Composite catalyzing
Agent sample.
Fig. 1 schemes for the TEM of sample after the SEM figures and 9 h of non-alkali cleaning sample and alkali cleaning of each sample prepared by embodiment.From
Random arrangement before the composite fiber calcining that SEM it can be seen from the figure that electrostatic spinnings obtain, surface is smooth, fiber continuity
Good, diameter is between 200-400 nm；After calcining, phenomenon of rupture has occurred in fibre diameter, is contracted within the scope of 100-250 nm；
After sample handles the different time (3 h, 5 h, 7 h and 9 h) with NaOH solution, fiber surface has grown " villiform " substance.
Compare the sample of 9 h of non-alkali cleaning sample and alkali cleaning TEM figure, it can be seen that the sample fiber of non-alkali cleaning by nano particle accumulate and
At after 9 h of alkali cleaning, fiber surface occurs very much " folds " (being " villiform " substance that SEM is observed).
Fig. 2 is the XRD spectra of each sample prepared by embodiment.It can be seen that non-alkali cleaning LaCoO3Sample
XRD, which goes out peak position () and standard card (JCPDS No.18-0123), to be well matched with, and be the LaCoO of oblique hexagonal crystal system3。
And the sample (3 h, 5 h and 7 h) after alkali cleaning is in 2 θ=15.6°, 27.2°, 28.0°With 39.4°There is hexagonal phase La in place (●)
(OH)3Diffraction maximum (JCPDS No. 01-083-2034), it can thus be appreciated that alkali cleaning can dissolve LaCoO3The positions the A shape of nanofiber
At La (OH)3。
XRD illustrates LaCoO with SEM results3Nanofiber surface is after alkali cleaning is handled, Surface Creation " villiform "
Substance is La (OH)3, form the LaCoO with core-shell structure3@La(OH)3Composite catalyst.
Fig. 3 is each sample prepared by embodiment at different temperatures to the catalytic conversion of benzene.It by comparing can be with
It was found that the catalyst obtained after alkali cleaning --- LaCoO3@La(OH)3Composite catalyst catalytic performance and single Ca-Ti ore type
LaCoO3Compared to there is different degrees of raising.
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to the present patent application protection domain with
Modification should all belong to the covering scope of the present invention.
Claims (8)
1. a kind of higher LaCoO with core-shell structure of catalytic performance3@La(OH)3Composite catalyst, it is characterised in that：Described
LaCoO3@La(OH)3Composite catalyst has higher catalytic performance and special structure --- core-shell structure, La (OH)3For
Shell, Ca-Ti ore type LaCoO3For core；It is specifically prepared by following methods comprising following steps：
(1) lanthanum nitrate, cobalt nitrate, polyvinylpyrrolidone and citric acid are dissolved in N, N- dimethyl formyls by magnetic agitation
In amine solvent, electrostatic spinning precursor solution is prepared；
(2) the electrostatic spinning precursor solution that step (1) is prepared is made by composite nano fiber using method of electrostatic spinning, then will
It, which is placed in drier, preserves 8~15 h；
(3) composite nano fiber prepared by step (2) is placed in Muffle furnace, is calcined in air atmosphere, obtains calcium titanium
Mine type LaCoO3；
(4) the Ca-Ti ore type LaCoO with strong base solution prepared by step (3)3Alkali cleaning is carried out, then extremely with deionized water centrifuge washing
Supernatant is neutrality, and sample is finally dried to 12~24 h at 70~90 DEG C, obtains LaCoO3@La(OH)3Composite catalyst.
2. a kind of higher LaCoO with core-shell structure of catalytic performance as described in claim 13@La(OH)3Composite catalyst,
It is characterized in that：In the electrostatic spinning precursor solution, the ratio between lanthanum element and the amount of cobalt element substance are 1:1, nitrate
The volume mL ratios of gross mass g and solvent N,N-dimethylformamide are 0.03~0.04:1, the amount for the lemon acid substance being added
It is 2~4 times of lanthanum element, the volume mL ratios of polyvinylpyrrolidone quality g and solvent n,N-Dimethylformamide are 0.07~
0.12:1。
3. a kind of higher LaCoO with core-shell structure of catalytic performance as claimed in claim 1 or 23@La(OH)3Composite catalyzing
Agent, it is characterised in that：The electrostatic spinning voltage is 23 kV, and charging rate is 1.0 mL/h, and temperature is 43 DEG C, stainless steel
Syringe needle internal diameter is 1 mm, and it is 15 cm to receive distance, and it is 8~10 h to continue the Electrospun time.
4. a kind of higher LaCoO with core-shell structure of catalytic performance as claimed in claim 1 or 23@La(OH)3Composite catalyzing
Agent, it is characterised in that：The heating rate of composite nano fiber calcining is 2~8 DEG C/min, and calcining thermostat temperature is 500 DEG C, is forged
Burning constant temperature time is 4 h；The strong base solution be brand-new NaOH solution or KOH solution, a concentration of 2~10 mol/L,
LaCoO3Quality g and strong base solution volume mL ratios be 0.004~0.01:1；Solution constantly carries out magnetic in alkaline cleaning procedure
Power stirs, and at 50~80 DEG C, the alkali cleaning time is 3~9 h, after alkali cleaning, is washed away lye with deionized water for temperature control,
Until cleaning solution is in neutrality.
5. a kind of higher LaCoO with core-shell structure of catalytic performance3@La(OH)3The preparation method of composite catalyst, including such as
Lower step：
(1) lanthanum nitrate, cobalt nitrate, polyvinylpyrrolidone and citric acid are dissolved in N, N- dimethyl formyls by magnetic agitation
In amine solvent, electrostatic spinning precursor solution is prepared；
(2) the electrostatic spinning precursor solution that step (1) is prepared is made by composite nano fiber using method of electrostatic spinning, then will
It, which is placed in drier, preserves 8~15 h；
(3) composite nano fiber prepared by step (2) is placed in Muffle furnace, is calcined in air atmosphere, obtains calcium titanium
Mine type LaCoO3；
(4) the Ca-Ti ore type LaCoO with strong base solution prepared by step (3)3Alkali cleaning is carried out, then extremely with deionized water centrifuge washing
Supernatant is neutrality, and sample is finally dried to 12~24 h at 70~90 DEG C, obtains LaCoO3@La(OH)3Composite catalyst.
6. method as claimed in claim 5, it is characterised in that：In the electrostatic spinning precursor solution, lanthanum element and cobalt
The ratio between amount of elemental substance is 1:The volume mL ratios of 1, nitrate gross mass g and solvent n,N-Dimethylformamide are 0.03~
0.04:1, the amount for the lemon acid substance being added is 2~4 times of lanthanum element, polyvinylpyrrolidone quality g and solvent N, N- bis-
The volume mL ratios of methylformamide are 0.07~0.12:1.
7. such as method described in claim 5 or 6, it is characterised in that：The electrostatic spinning voltage is 23 kV, charging rate
For 1.0 mL/h, temperature is 43 DEG C, and stainless steel syringe needle internal diameter is 1 mm, and it is 15 cm to receive distance, and it is 8 to continue the Electrospun time
~10 h.
8. such as method described in claim 5 or 6, it is characterised in that：The heating rate of composite nano fiber calcining is 2~8
DEG C/min, calcining thermostat temperature is 500 DEG C, and calcining constant temperature time is 4 h；The strong base solution is the NaOH solution of brand-new
Or KOH solution, a concentration of 2~10 mol/L, LaCoO3Quality g and strong base solution volume mL ratios be 0.004~0.01:1；
Solution constantly carries out magnetic agitation in alkaline cleaning procedure, and at 50~80 DEG C, the alkali cleaning time is 3~9 h, alkali cleaning for temperature control
After, lye is washed away with deionized water, until cleaning solution is in neutrality.
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