CN104525203B - A kind of Co3O4The preparation method of/NiO composite mesopore nanoparticle and application - Google Patents
A kind of Co3O4The preparation method of/NiO composite mesopore nanoparticle and application Download PDFInfo
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Abstract
The invention discloses a kind of Co3O4The preparation method of/NiO composite mesopore nanoparticle and application, its method is to adopt Co3O4Nanoparticle is scattered in distilled water, adds Ni (NO3)2 .6H2O, stirs and is slowly added dropwise NaOH solution, after magnetic agitation, is placed in reactor, is washed by products therefrom after reaction, dries, calcines, obtains Co3O4/ NiO composite mesopore nanoparticle；Its application is gained nanoparticle is 60～200 DEG C of catalytic activation methane in temperature, opens the c h bond in methane molecule.Co prepared by the present invention3O4/ NiO composite mesopore nano particle diameter is little, Co3O4Dispersion is high, and pattern is homogeneous；Cheaper starting materials is easy to get, and cost is low, and step is easy, it is easy to operation；Can at low-temperature catalyzed Methane Activation.
Description
Technical field
The present invention relates to the preparation field of composite nano materials, be specifically related to one and prepare Co by hydro-thermal method3O4The preparation method of/NiO composite mesopore nanoparticle, and this Co3O4The application in the methyl hydride catalyzed activation of/NiO composite mesopore nanoparticle.
Background technology
Methyl hydride catalyzed activating technology is the wide variety of technology in economic field, world in recent years various countries, but owing to methane has the nonpolar molecule being similar to noble gas, c h bond can up to 435KJ/mol, and thermodynamically highly stable, this makes methane be little to provide activity group.How to make so stable molecule be activated in a mild condition and then realize rationally converting always concerned, being still very challenging problem so far.
Nano transition metal oxides causes the concern of people due to its electricity, magnetics and catalysis characteristics, is especially widely used in the nano NiO of catalytic field, Co3O4Noticeable especially.The application on catalytic methane activates of both metal-oxides mainly has methane couple reaction, reforming reaction, partial oxidation reaction, combustion reaction etc..When being applied to catalytic methane activation, NiO, Co3O4Mainly there are three kinds: directly with pure NiO, Co3O4As catalyst；With NiO, Co3O4Load to and other carrier makees catalyst；With NiO, Co3O4As carrier by other metal load to NiO, Co3O4On as catalyst.These catalyst are all atresias.
In recent years, about nano NiO, Co3O4The report of study on the synthesis emerges in an endless stream, and has developed multiple method for preparing different-shape, different size of NiO, Co3O4.Wherein the most typically there are hydro-thermal (solvent thermal) method, direct precipitation method, circumfluence method, electrodeposition process etc..It is applied to the load-type nickel of methane activation, Co catalysts, and synthetic method Ni-based, cobalt-base catalyst is mostly coprecipitation, sol-gal process, circumfluence method, hydro-thermal method；And about Co3O4It is little that the synthetic method of/NiO composite catalyst is reported.Once there is " SanchaiKuboonandYunHangHuInd, Eng.Chem.Res.2011,50,2,015 2020 ", calcined Ni (NO at 600 DEG C-700 DEG C3)2、Co(NO3)2Mixture obtain NiO-CoO and Ni3O4-Co3O4Composite oxides, but these are also all pore-free materials, its catalytic performance are not studied.Also have " LIANGQingQin1, LIYueMing2&LIJingHong, ChinSciBullNovember (2012) Vol.57No.32 ", utilize Ni (NO3)2·6H2O、Co(NO3)2·6H2O, HMT direct precipitation method synthesis NiO/Co3O4Composite nano plate, and it is carried out electro-chemical test.It addition, also have " HyeonWooCho, JiHyunNam, JeongHoPark, KwangManKim, JangMyounKo, KoreanChem.Soc.2012, Vol.33, No.123993 ", with 1MCo (NO3)2·6H2O and 1MNi (NO3)2·6H2Nickel foam is carried out coating by the mixed liquor of O, after dry, calcining, prepares Co-NiO/Ni electrode, and it is circulated volt-ampere, testing impedance.
Summary of the invention
The purpose of the present invention aims to provide for catalytic methane priming reaction, can realize the low-temperature activation of methane, and preparation process is simple to operation, and cheaper starting materials is easy to get, size uniformity, regular appearance, Co3O4The Co that dispersion is high3O4/ NiO composite mesopore nanoparticle preparation method and application.
The concrete technical scheme realizing the object of the invention is:
A kind of Co3O4The preparation method of/NiO composite mesopore nanoparticle, the method includes step in detail below:
A) by Co (CH3COO)2Solution is placed in 70 DEG C of water-baths, NaOH solution is slowly added thereto, magnetic agitation 60～120min；It is cooled to after room temperature until solution, obtains Co (OH) through filtering, washing2Precipitation；After drying, Co (OH)2Calcine in Muffle furnace, obtain Co3O4Nanoparticle；Wherein, described Co (CH3COO)2Solution concentration 0.20～0.50mol/L；Described NaOH solution concentration is 1.0～4.0mol/L；Co (CH3COO)2Solution and NaOH solution volume ratio are 4～12:1～2；Described calcining heat is 180～300 DEG C, and calcination time is 0.5～3h；
B) Co that step a) is prepared3O4Nanoparticle in distilled water, adds Ni (NO by ultrasonic disperse afterwards3)2 .6H2O, Ni (NO3)2 .6H2O solution concentration is 0.1～0.4mol/L, stirs and is slowly added dropwise 0.2～0.75mol/LNaOH solution, after magnetic agitation 10～40min, is placed in reactor, in an oven 160～220 DEG C of conditioned response 15～24h；Products therefrom is washed, dries, 200～400 DEG C of calcining 0.5～4h, obtain Co3O4/ NiO composite mesopore nanoparticle；Wherein, described Co3O4Nanoparticle adding proportion is 0.01-0.50 according to the mol ratio of cobalt Yu nickel；Distilled water and NaOH solution volume ratio are 1～2:2～1.
Described obtain Co3O4The hexagonal laminated structure of/NiO composite mesopore nanoparticle, is of a size of 10～100nm.
The application of a kind of above-mentioned nanoparticle, this nanoparticle is as catalyst Methane Activation；Its catalytic activation reaction gas is CH4And O2；VCH4:VO2Being 2～8:1, the air speed of methane gas is 33.32～101.60ml/g.min, and the consumption of catalyst is determined according to the air speed of methane gas；Catalyst is 60～200 DEG C of catalytic activation methane in temperature, opens the c h bond in methane molecule.
The catalytic reaction of the present invention carries out in fixed bed reactors, and the consumption of catalyst is determined according to the air speed of methane gas；Reaction gas is CH4And O2, VCH4:VO2=2～8:1.Utilizing high pressure micro-inverse spectrum that reactor is heated up, reaction temperature adopts the method for staged intensification, first starts reaction from room temperature, then raises 10 DEG C every time and carries out test until product CO2Appearance, be the activation temperature of methane.With H2For carrier gas, column temperature is 40 DEG C, and bridge stream is 120mA, adopts six-way valve sampling, adopts single gas circuit Thermal Conductivity.Chromatogram detects CO2During peak and the C-H of provable methane be opened, generate C-O product, namely reaction temperature at this moment can be identified as the temperature of methane activation.
The Co of the present invention3O4/ NiO composite mesopore nanoparticle has prominent catalysis activity, can be 60 DEG C～200 DEG C catalytic activation methane in temperature, open the c h bond in methane molecule, hence it is evident that be better than other catalyst for catalytic methane activation.
Advantages of the present invention:
(1), prepared Co3O4/ NiO composite mesopore nano particle diameter is little, Co3O4Dispersion is high, and pattern is homogeneous.
, the cheaper starting materials of prepared material be easy to get, cost is low, and step is easy, it is easy to operation.
(3), prepared material can at low-temperature catalyzed Methane Activation.
Accompanying drawing explanation
Fig. 1 is the embodiment of the present invention 6 gained Co3O4The XRD diffracting spectrum of nanoparticle；
Fig. 2 is the embodiment of the present invention 6 gained Co3O4The XRD diffracting spectrum of/NiO composite mesopore nanoparticle；
Fig. 3 is the embodiment of the present invention 6 gained Co3O4Transmission electron microscope (TEM) picture of/NiO composite mesopore nanoparticle.
Detailed description of the invention
Describe the present invention in detail below in conjunction with embodiment and accompanying drawing, but the present invention is not limited to this.
Embodiment 1
a)Co3O4The preparation of nanoparticle
By 30ml0.5mol/LCo (CH3COO)2Solution is placed in 70 DEG C of water-baths, is slowly added thereto by 20ml4mol/LNaOH solution, magnetic agitation 60min.It is cooled to after room temperature until solution, obtains Co (OH) through filtration washing step2Precipitation.After drying, Co (OH)2Calcine in Muffle furnace.Calcining heat is 180 DEG C, and calcination time is 3h, can obtain Co after calcining3O4Nanoparticle.
b)Co3O4The preparation of/NiO composite mesopore nanoparticle
By 0.0056gCo3O4Ultrasonic disperse, in 30ml distilled water, adds 3.49gNi (NO3)2 .6H2O, is slowly added dropwise the 60mlNaOH solution containing 1.80gNaOH after stirring.After stirring 10min, moving in 100ml reactor, 160 DEG C keep 15h, and respectively with after distilled water, washing with alcohol, 60 DEG C dry, and 200 DEG C of calcining 4h obtain Co3O4/ NiO composite mesopore nanoparticle.
C) Co prepared by 1.30g is taken3O4/ NiO composite mesopore nanoparticle is applied to catalytic methane activation, at VCH4:VO2When=2:1, CO when temperature is 110 DEG C, can be observed from chromatogram2Peak, it was demonstrated that now in methane, C-H is opened.That is 110 DEG C time Co3O4/ NiO composite mesopore nanoparticle can catalytic activation methane, open C-H.
Embodiment 2
a)Co3O4The preparation of nanoparticle
By 60ml0.2mol/LCo (CH3COO)2Solution is placed in 70 DEG C of water-baths, is slowly added thereto by 5ml1mol/LNaOH solution, magnetic agitation 120min.It is cooled to after room temperature until solution, obtains Co (OH) through filtration washing step2Precipitation.After drying, Co (OH)2Calcine in Muffle furnace.Calcining heat is 300 DEG C, and calcination time is 1h, can obtain Co after calcining3O4Nanoparticle.
B) Co3O4The preparation of/NiO composite mesopore nanoparticle
By 0.0291gCo3O4Ultrasonic disperse, in 60ml distilled water, adds 1.74gNi (NO3)2 .6H2O, is slowly added dropwise the 30mlNaOH solution containing 0.24gNaOH after stirring.After stirring 30min, moving in 100ml reactor, 160 DEG C keep 24h, and respectively with after distilled water, washing with alcohol, 60 DEG C dry, and 400 DEG C of calcining 0.5h obtain Co3O4/ NiO composite mesopore nanoparticle.
C) Co prepared by 0.48g is taken3O4/ NiO composite mesopore nanoparticle is applied to catalytic methane activation, at VCH4:VO2When=2:1, CO when temperature is 140 DEG C, can be observed from chromatogram2Peak, it was demonstrated that now in methane, C-H is opened.That is 140 DEG C time Co3O4/ NiO composite mesopore nanoparticle can catalytic activation methane, open C-H.
Embodiment 3
a)Co3O4The preparation of nanoparticle
By 40ml0.25mol/LCo (CH3COO)2Solution is placed in 70 DEG C of water-baths, is slowly added thereto by 10ml2mol/LNaOH solution, magnetic agitation 60min.It is cooled to after room temperature until solution, obtains Co (OH) through filtration washing step2Precipitation.After drying, Co (OH)2Calcine in Muffle furnace.Calcining heat is 200 DEG C, and calcination time is 1h, can obtain Co after calcining3O4Nanoparticle.
B) Co3O4The preparation of/NiO composite mesopore nanoparticle
By 0.5520gCo3O4Ultrasonic disperse, in 40ml distilled water, adds 2.00gNi (NO3)2 .6H2O, is slowly added dropwise the 40mlNaOH solution containing 0.80gNaOH after stirring.After stirring 40min, moving in 100ml reactor, 180 DEG C keep 15h, and respectively with after distilled water, washing with alcohol, 60 DEG C dry, and 250 DEG C of calcining 1h obtain Co3O4/ NiO composite mesopore nanoparticle.
C) take materials application prepared by 0.80g to activate in catalytic methane, at VCH4:VO2When=2:1, CO when temperature is 90 DEG C, can be observed from chromatogram2Peak, it was demonstrated that now in methane, C-H is opened.That is 90 DEG C time Co3O4/ NiO composite mesopore nanoparticle can catalytic activation methane, open C-H.
Embodiment 4
A) by 40ml0.25mol/LCo (CH3COO)2Solution is placed in 70 DEG C of water-baths, is slowly added thereto by 10ml2mol/LNaOH solution, magnetic agitation 60min.It is cooled to after room temperature until solution, obtains Co (OH) through filtration washing step2Precipitation.After drying, Co (OH)2Calcine in Muffle furnace.Calcining heat is 200 DEG C, and calcination time is 1h, can obtain Co after calcining3O4Nanoparticle.
B) Co3O4The preparation of/NiO composite mesopore nanoparticle
By 0.0056gCo3O4Ultrasonic disperse, in 40ml distilled water, adds 2.00gNi (NO3)2 .6H2O, is slowly added dropwise the 40mlNaOH solution containing 0.46gNaOH after stirring.After stirring 15min, moving in 100ml reactor, 180 DEG C keep 15h, and respectively with after distilled water, washing with alcohol, 60 DEG C dry, and 250 DEG C of calcining 1h obtain Co3O4/ NiO composite mesopore nanoparticle.
C) Co prepared by 0.50g is taken3O4/ NiO composite mesopore nanoparticle is applied to catalytic methane activation, at VCH4:VO2When=3:1, CO when temperature is 130 DEG C, can be observed from chromatogram2Peak, it was demonstrated that now in methane, C-H is opened.That is 130 DEG C time Co3O4/ NiO composite mesopore nanoparticle can catalytic activation methane, open C-H.
Embodiment 5
A) by 40ml0.25mol/LCo (CH3COO)2Solution is placed in 70 DEG C of water-baths, is slowly added thereto by 10ml2mol/LNaOH solution, magnetic agitation 60min.It is cooled to after room temperature until solution, obtains Co (OH) through filtration washing step2Precipitation.After drying, Co (OH)2Calcine in Muffle furnace.Calcining heat is 200 DEG C, and calcination time is 1h, can obtain Co after calcining3O4Nanoparticle.
B) Co3O4The preparation of/NiO composite mesopore nanoparticle
By 0.0160gCo3O4Ultrasonic disperse, in 40ml distilled water, adds 2.00gNi (NO3)2 .6H2O, is slowly added dropwise the 40mlNaOH solution containing 0.55gNaOH after stirring.After stirring 15min, moving in 100ml reactor, 180 DEG C keep 15h, and respectively with after distilled water, washing with alcohol, 60 DEG C dry, and 250 DEG C of calcining 1h obtain Co3O4/ NiO composite mesopore nanoparticle.
C) Co prepared by 0.69g is taken3O4/ NiO composite mesopore nanoparticle is applied to catalytic methane activation, at VCH4:VO2When=8:1, CO when temperature is 150 DEG C, can be observed from chromatogram2Peak, it was demonstrated that now in methane, C-H is opened.That is 150 DEG C time Co3O4/ NiO composite mesopore nanoparticle can catalytic activation methane, open C-H.
Embodiment 6
A) by 40ml0.25mol/LCo (CH3COO)2Solution is placed in 70 DEG C of water-baths, is slowly added thereto by 10ml2mol/LNaOH solution, magnetic agitation 60min.It is cooled to after room temperature until solution, obtains Co (OH) through filtration washing step2Precipitation.After drying, Co (OH)2Calcine in Muffle furnace.Calcining heat is 200 DEG C, and calcination time is 1h, can obtain Co after calcining3O4Nanoparticle.Gained Co3O4The XRD diffracting spectrum of nanoparticle is shown in Fig. 1.
B) Co3O4The preparation of/NiO composite mesopore nanoparticle
By 0.0056gCo3O4Ultrasonic disperse, in 40ml distilled water, adds 2.00gNi (NO3)2 .6H2O, is slowly added dropwise the 40mlNaOH solution containing 0.55gNaOH after stirring.After stirring 15min, moving in 100ml reactor, 180 DEG C keep 18h, and respectively with after distilled water, washing with alcohol, 60 DEG C dry, and 250 DEG C of calcining 1h obtain Co3O4/ NiO composite mesopore nanoparticle.Gained Co3O4The XRD diffracting spectrum of/NiO composite mesopore nanoparticle is shown in Fig. 2；Described obtain Co3O4The hexagonal laminated structure of/NiO composite mesopore nanoparticle, is of a size of 10～100nm and sees Fig. 3.
C) Co prepared by 0.50g is taken3O4/ NiO composite mesopore nanoparticle is applied to catalytic methane activation, at VCH4:VO2When=2:1, CO when temperature is 60 DEG C, can be observed from chromatogram2Peak, it was demonstrated that now in methane, C-H is opened.That is 60 DEG C time Co3O4/ NiO composite mesopore nanoparticle can catalytic activation methane, open C-H.
Embodiment 7
A) by 40ml0.25mol/LCo (CH3COO)2Solution is placed in 70 DEG C of water-baths, is slowly added thereto by 10ml2mol/LNaOH solution, magnetic agitation 60min.It is cooled to after room temperature until solution, obtains Co (OH) through filtration washing step2Precipitation.After drying, Co (OH)2Calcine in Muffle furnace.Calcining heat is 200 DEG C, and calcination time is 1h, can obtain Co after calcining3O4Nanoparticle.
B) Co3O4The preparation of/NiO composite mesopore nanoparticle
By 0.0056gCo3O4Ultrasonic disperse, in 40ml distilled water, adds 2.00gNi (NO3)2 .6H2O, is slowly added dropwise the 40mlNaOH solution containing 0.55gNaOH after stirring.After stirring 15min, moving in 100ml reactor, 180 DEG C keep 18h, and respectively with after distilled water, washing with alcohol, 60 DEG C dry, and 250 DEG C of calcining 1h obtain Co3O4/ NiO composite mesopore nanoparticle.
C) take composite mesopore nanoparticle prepared by 0.50g and be applied to catalytic methane activation, at VCH4:VO2When=3:1, CO when temperature is 100 DEG C, can be observed from chromatogram2Peak, it was demonstrated that now in methane, C-H is opened.That is 100 DEG C time Co3O4/ NiO composite mesopore nanoparticle can catalytic activation methane, open C-H.
Embodiment 8
A) by 40ml0.25mol/LCo (CH3COO)2Solution is placed in 70 DEG C of water-baths, is slowly added thereto by 10ml2mol/LNaOH solution, magnetic agitation 60min.It is cooled to after room temperature until solution, obtains Co (OH) through filtration washing step2Precipitation.After drying, Co (OH)2Calcine in Muffle furnace.Calcining heat is 200 DEG C, and calcination time is 1h, can obtain Co after calcining3O4Nanoparticle.
B) Co3O4The preparation of/NiO composite mesopore nanoparticle
By 0.0276gCo3O4Ultrasonic disperse, in 40ml distilled water, adds 2.00gNi (NO3)2 .6H2O, is slowly added dropwise the 40mlNaOH solution containing 0.55gNaOH after stirring.After stirring 15min, moving in 100ml reactor, 180 DEG C keep 18h, and respectively with after distilled water, washing with alcohol, 60 DEG C dry, and 250 DEG C of calcining 1h obtain Co3O4/ NiO composite mesopore nanoparticle.
C) Co prepared by 0.54g is taken3O4/ NiO composite mesopore nanoparticle is applied to catalytic methane activation, at VCH4:VO2When=8:1, CO when temperature is 90 DEG C, can be observed from chromatogram2Peak, it was demonstrated that now in methane, C-H is opened.That is 90 DEG C time Co3O4/ NiO composite mesopore nanoparticle can catalytic activation methane, open C-H.
Embodiment 9
A) by 40ml0.25mol/LCo (CH3COO)2Solution is placed in 70 DEG C of water-baths, is slowly added thereto by 10ml2mol/LNaOH solution, magnetic agitation 60min.It is cooled to after room temperature until solution, obtains Co (OH) through filtration washing step2Precipitation.After drying, Co (OH)2Calcine in Muffle furnace.Calcining heat is 200 DEG C, and calcination time is 1h, can obtain Co after calcining3O4Nanoparticle.
B) Co3O4The preparation of/NiO composite mesopore nanoparticle
By 0.0552gCo3O4Ultrasonic disperse, in 40ml distilled water, adds 2.00gNi (NO3)2 .6H2O, is slowly added dropwise the 40mlNaOH solution containing 0.55gNaOH after stirring.After stirring 15min, moving in 100ml reactor, 180 DEG C keep 18h, and respectively with after distilled water, washing with alcohol, 60 DEG C dry, and 250 DEG C of calcining 1h obtain Co3O4/ NiO composite mesopore nanoparticle.
C) Co prepared by 0.98g is taken out3O4/ NiO composite mesopore nanoparticle is applied to catalytic methane activation, at VCH4:VO2When=3:1, CO when temperature is 80 DEG C, can be observed from chromatogram2Peak, it was demonstrated that now in methane, C-H is opened.That is 80 DEG C time Co3O4/ NiO composite mesopore nanoparticle can catalytic activation methane, open C-H.
Embodiment 10
A) by 40ml0.25mol/LCo (CH3COO)2Solution is placed in 70 DEG C of water-baths, is slowly added thereto by 10ml2mol/LNaOH solution, magnetic agitation 60min.It is cooled to after room temperature until solution, obtains Co (OH) through filtration washing step2Precipitation.After drying, Co (OH)2Calcine in Muffle furnace.Calcining heat is 200 DEG C, and calcination time is 1h, can obtain Co after calcining3O4Nanoparticle.
B) Co3O4The preparation of/NiO composite mesopore nanoparticle
By 0.0828gCo3O4Ultrasonic disperse, in 40ml distilled water, adds 2.00gNi (NO3)2 .6H2O, is slowly added dropwise the 40mlNaOH solution containing 0.55gNaOH after stirring.After stirring 15min, moving in 100ml reactor, 180 DEG C keep 18h, and respectively with after distilled water, washing with alcohol, 60 DEG C dry, and 250 DEG C of calcining 1h obtain Co3O4/ NiO composite mesopore nanoparticle.
C) take composite mesopore nanoparticle prepared by 1.30g and be applied to catalytic methane activation, at VCH4:VO2When=2:1, CO when temperature is 100 DEG C, can be observed from chromatogram2Peak, it was demonstrated that now in methane, C-H is opened.That is 100 DEG C time Co3O4/ NiO composite mesopore nanoparticle can catalytic activation methane, open C-H.
Embodiment 11
A) by 40ml0.25mol/LCo (CH3COO)2Solution is placed in 70 DEG C of water-baths, is slowly added thereto by 10ml2mol/LNaOH solution, magnetic agitation 60min.It is cooled to after room temperature until solution, obtains Co (OH) through filtration washing step2Precipitation.After drying, Co (OH)2Calcine in Muffle furnace.Calcining heat is 200 DEG C, and calcination time is 1h, can obtain Co after calcining3O4Nanoparticle.
B) Co3O4The preparation of/NiO composite mesopore nanoparticle
By 0.0552gCo3O4Ultrasonic disperse, in 40ml distilled water, adds 2.00gNi (NO3)2 .6H2O, is slowly added dropwise the 40mlNaOH solution containing 0.55gNaOH after stirring.After stirring 15min, moving in 100ml reactor, 180 DEG C keep 18h, and respectively with after distilled water, washing with alcohol, 60 DEG C dry, and 250 DEG C of calcining 1h obtain Co3O4/ NiO composite mesopore nanoparticle.
C) Co prepared by 1.30g is taken3O4/ NiO composite mesopore nanoparticle is applied to catalytic methane activation, at VCH4:VO2When=2:1, CO when temperature is 150 DEG C, can be observed from chromatogram2Peak, it was demonstrated that now in methane, C-H is opened.That is 150 DEG C time Co3O4/ NiO composite mesopore nanoparticle can catalytic activation methane, open C-H.
Embodiment 12
A) by 40ml0.25mol/LCo (CH3COO)2Solution is placed in 70 DEG C of water-baths, is slowly added thereto by 10ml2mol/LNaOH solution, magnetic agitation 60min.It is cooled to after room temperature until solution, obtains Co (OH) through filtration washing step2Precipitation.After drying, Co (OH)2Calcine in Muffle furnace.Calcining heat is 200 DEG C, and calcination time is 1h, can obtain Co after calcining3O4Nanoparticle.
B) Co3O4The preparation of/NiO composite mesopore nanoparticle:
By 0.0056gCo3O4Ultrasonic disperse, in 40ml distilled water, adds 2.00gNi (NO3)2 .6H2O, is slowly added dropwise the 40mlNaOH solution containing 0.55gNaOH after stirring.After stirring 15min, moving in 100ml reactor, 180 DEG C keep 18h, and respectively with after distilled water, washing with alcohol, 60 DEG C dry, and 250 DEG C of calcining 1h obtain Co3O4/ NiO composite mesopore nanoparticle.
C) Co prepared by 0.50g is taken3O4/ NiO composite mesopore nanoparticle is applied to catalytic methane activation, at VCH4:VO2When=8:1, CO when temperature is 60 DEG C, can be observed from chromatogram2Peak, it was demonstrated that now in methane, C-H is opened.That is 60 DEG C time Co3O4/ NiO composite mesopore nanoparticle can catalytic activation methane, open C-H.
Embodiment 13
A) by 40ml0.25mol/LCo (CH3COO)2Solution is placed in 70 DEG C of water-baths, is slowly added thereto by 10ml2mol/LNaOH solution, magnetic agitation 60min.It is cooled to after room temperature until solution, obtains Co (OH) through filtration washing step2Precipitation.After drying, Co (OH)2Calcine in Muffle furnace.Calcining heat is 200 DEG C, and calcination time is 1h, can obtain Co after calcining3O4Nanoparticle.
B) Co3O4The preparation of/NiO composite mesopore nanoparticle
By 0.2760gCo3O4Ultrasonic disperse, in 40ml distilled water, adds 2.00gNi (NO3)2 .6H2O, is slowly added dropwise the 40mlNaOH solution containing 0.55gNaOH after stirring.After stirring 15min, moving in 100ml reactor, 180 DEG C keep 24h, and respectively with after distilled water, washing with alcohol, 60 DEG C dry, and 250 DEG C of calcining 1h obtain Co3O4/ NiO composite mesopore nanoparticle.
C) Co prepared by 0.69g is taken3O4/ NiO composite mesopore nanoparticle is applied to catalytic methane activation, at VCH4:VO2When=8:1, CO when temperature is 120 DEG C, can be observed from chromatogram2Peak, it was demonstrated that now in methane, C-H is opened.That is 120 DEG C time Co3O4/ NiO composite mesopore nanoparticle can catalytic activation methane, open C-H.
Embodiment 14
A) by 40ml0.25mol/LCo (CH3COO)2Solution is placed in 70 DEG C of water-baths, is slowly added thereto by 10ml2mol/LNaOH solution, magnetic agitation 60min.It is cooled to after room temperature until solution, obtains Co (OH) through filtration washing step2Precipitation.After drying, Co (OH)2Calcine in Muffle furnace.Calcining heat is 200 DEG C, and calcination time is 1h, can obtain Co after calcining3O4Nanoparticle.
B) Co3O4The preparation of/NiO composite mesopore nanoparticle
By 0.5520gCo3O4Ultrasonic disperse, in 40ml distilled water, adds 2.00gNi (NO3)2 .6H2O, is slowly added dropwise the 40mlNaOH solution containing 0.51gNaOH after stirring.After stirring 25min, moving in 100ml reactor, 220 DEG C keep 15h, and respectively with after distilled water, washing with alcohol, 60 DEG C dry, and 300 DEG C of calcining 2h obtain Co3O4/ NiO composite mesopore nanoparticle.
C) Co prepared by 0.35g is taken3O4/ NiO composite mesopore nanoparticle is applied to catalytic methane activation, at VCH4:VO2When=8:1, CO when temperature is 180 DEG C, can be observed from chromatogram2Peak, it was demonstrated that now in methane, C-H is opened.That is 180 DEG C time Co3O4/ NiO composite mesopore nanoparticle can catalytic activation methane, open C-H.
Embodiment 15
A) by 40ml0.25mol/LCo (CH3COO)2Solution is placed in 70 DEG C of water-baths, is slowly added thereto by 10ml2mol/LNaOH solution, magnetic agitation 60min.It is cooled to after room temperature until solution, obtains Co (OH) through filtration washing step2Precipitation.After drying, Co (OH)2Calcine in Muffle furnace.Calcining heat is 200 DEG C, and calcination time is 1h, can obtain Co after calcining3O4Nanoparticle.
B) Co3O4The preparation of/NiO composite mesopore nanoparticle
By 0.0113gCo3O4Ultrasonic disperse, in 40ml distilled water, adds 2.00gNi (NO3)2 .6H2O, is slowly added dropwise the 40mlNaOH solution containing 0.55gNaOH after stirring.After stirring 40min, moving in 100ml reactor, 220 DEG C keep 18h, and respectively with after distilled water, washing with alcohol, 60 DEG C dry, and 250 DEG C of calcining 2h obtain Co3O4/ NiO composite mesopore nanoparticle.
C) Co prepared by 0.35g is taken3O4/ NiO composite mesopore nanoparticle is applied to catalytic methane activation, at VCH4:VO2When=3:1, CO when temperature is 200 DEG C, can be observed from chromatogram2Peak, it was demonstrated that now in methane, C-H is opened.That is 200 DEG C time Co3O4/ NiO composite mesopore nanoparticle can catalytic activation methane, open C-H.
Claims (3)
1. a Co3O4The preparation method of/NiO composite mesopore nanoparticle, it is characterised in that the method includes step in detail below:
A) by Co (CH3COO)2Solution is placed in 70 DEG C of water-baths, NaOH solution is slowly added thereto, magnetic agitation 60～120min；It is cooled to after room temperature until solution, obtains Co (OH) through filtering, washing2Precipitation；After drying, Co (OH)2Calcine in Muffle furnace, obtain Co3O4Nanoparticle；Wherein, described Co (CH3COO)2Solution concentration 0.20～0.50mol/L；Described NaOH solution concentration is 1.0～4.0mol/L；Co (CH3COO)2Solution and NaOH solution volume ratio are 4～12:1～2；Described calcining heat is 180～300 DEG C, and calcination time is 0.5～3h；
B) Co that step a) is prepared3O4Nanoparticle in distilled water, adds Ni (NO by ultrasonic disperse afterwards3)2 .6H2O, Ni (NO3)2 .6H2O concentration is 0.1～0.4mol/L, stirs and is slowly added dropwise 0.2～0.75mol/LNaOH solution, after magnetic agitation 10～40min, is placed in reactor, in an oven 160～220 DEG C of conditioned response 15～24h；Products therefrom is washed, dries, 200～400 DEG C of calcining 0.5～4h, obtain Co3O4/ NiO composite mesopore nanoparticle；Wherein, described Co3O4Nanoparticle adding proportion is 0.01～0.50 according to the mol ratio of cobalt Yu nickel；Distilled water and NaOH solution volume ratio are 1～2:2～1.
2. preparation method according to claim 1, it is characterised in that described in obtain Co3O4The hexagonal laminated structure of/NiO composite mesopore nanoparticle, is of a size of 10～100nm.
3. the Co that preparation method according to claim 1 obtains3O4The application of/NiO composite mesopore nanoparticle, it is characterised in that this nanoparticle is as catalyst Methane Activation；Its catalytic activation reaction gas is CH4And O2；VCH4:VO2Being 2～8:1, the air speed of methane gas is 33.32～101.60ml/g.min, and the consumption of catalyst is determined according to the air speed of methane gas；Catalyst is 60～200 DEG C of catalytic activation methane in temperature, opens the c h bond in methane molecule.
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| CN113368858B (en) * | 2020-03-08 | 2023-03-10 | 天津大学 | Cobaltosic oxide-nickel oxide double-layer mesoporous nanotube composite material and preparation method and application thereof |
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