CN104607201A - Ordered mesoporous LaCoO3 and LaMnO3 supported nano Ag catalyst and preparation and application thereof - Google Patents
Ordered mesoporous LaCoO3 and LaMnO3 supported nano Ag catalyst and preparation and application thereof Download PDFInfo
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- CN104607201A CN104607201A CN201410785849.4A CN201410785849A CN104607201A CN 104607201 A CN104607201 A CN 104607201A CN 201410785849 A CN201410785849 A CN 201410785849A CN 104607201 A CN104607201 A CN 104607201A
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Abstract
The invention discloses an ordered mesoporous LaCoO3 and LaMnO3 supported nano Ag catalyst and preparation and application thereof, and belongs to transition-metal oxide supported nano noble metal catalyst. The ordered mesoporous LaCoO3 and LaMnO3 and the ordered mesoporous LaCoO3 and LaMnO3 supported nano Ag / LaCoO3 and Ag / LaMnO3 are respectively prepared by vacuum assisted hard template method, and exhibit good activity and stability in CO catalytic oxidation. The ordered mesoporous LaCoO3 and LaMnO3 supported nano Ag catalyst has the characteristics of easily obtained and chip raw material, easy preparation process, controllable the particle size and pore diameter of the product, and the like.
Description
Technical field
The present invention relates to a kind of LaCoO adopting the infusion process of vacuum aided hard template method and vacuum aided to prepare three-dimensional ordered mesoporous respectively
3and LaMnO
3and loaded Ag (Ag/LaCoO
3, Ag/LaMnO
3) preparation method of catalyst, and the catalytic performance to CO oxidation.Relating in particular to a kind of ordered meso-porous silicon oxide that adopts is that the vacuum aided template of hard template prepares order mesoporous LaCoO respectively
3and LaMnO
3and Ag/LaCoO
3, Ag/LaMnO
3preparation method, and to CO oxidation catalytic performance, belong to transition metal oxide nano-noble-metal-loaded catalyst field.
Background technology
Along with the development of economic society and the progress of science and technology, problem of environmental pollution is on the rise.CO, NO of existing in air
x, the venomous injurant confrontation people such as hydrocarbon and PM healthy and life security cause serious threat.CO is discharged into a kind of air pollutants maximum in air, causes serious threat to the healthy of people.When the content of CO in air is 2.0 × 10
-5during mol/L, in 2 h, people just there will be dizzy vomiting phenomenon, when content reaches 5.4 × 10
-4during mol/L, will in 1 min ~ 3 min causing death.
Catalytic oxidation removes CO the best way, and wherein catalyst is the most key.According to current bibliographical information, it is more adopt the precious metal catalyst oxidation CO such as Pd, Pt, Rh, Au that people study, and its expensive, resource scarcity, relatively these noble metals, the relative low price of silver catalyst, therefore has more application prospect.Only there is a small amount of bibliographical information carried silver catalyst to prepare and be applied to the research in CO oxidation, as with Al
2o
3[Oh S H et al., Carbon Monoxide Removal from Hydrogen-Rich Fuel Cell Feedstreams by Selective Catalytic Oxidation. Journal of Catalysis, 1993,142 (1): 254 – 262], Co or Mn [G ü ld ü r C et al., Selective carbon monoxide oxidation over Ag-based composite oxides. International Journal of Hydrogen Energy, 2002,27 (2): 219-224], SiO
2[Qu Z P et al., Formation of subsurface oxygen species and its high activity toward CO oxidation over silver catalysts. Journal of Catalysis, 2005,229 (2): 446-458] etc. for the loaded Ag catalyst of carrier goes out better catalytic activity to CO oxidation performance, but stability is all poor.Therefore, the Ag catalyst preparing high activity and stability is still rich in high challenge.Order mesoporous ABO
3there is larger specific area, good heat endurance and excellent catalytic activity.The pore passage structure of this uniqueness is beneficial to diffusion, the simultaneously more accessible active sites of reactant molecule and active component.Therefore, order mesoporous ABO
3it is ideal carrier material [89].Existing bibliographical information ABO
3the report of load gold catalyst, as Jia etc. finds Au/LaCoO
3[M.L. Jia et al., Shen. The stability study of Au/La-Co-O catalysts for CO oxidation. Catal. Lett., 2010,134:87-92] and Au/LaMnO
3[M.L. Jia et al., Activity and deactivation behavior of Au/LaMnO
3catalysts for CO oxidation. J. Rare Earth, 2011,29:213-216] catalyst all demonstrates excellent catalytic activity and stability for CO oxidation.But ABO
3the report of loaded Ag catalyst is also fewer.
This patent adopts vacuum-assisted infusion, has successfully prepared the LaCoO with ordered mesopore structure
3or LaMnO
3, and its carried silver catalyst is applied in CO catalytic oxidation, up to now, there is no document or patent report and cross Ag/meso LaCoO synthesized by this patent
3with Ag/meso LaMnO
3the Synthesis and applications of material.
Summary of the invention
The object of this invention is to provide order mesoporous LaCoO
3and LaMnO
3and loaded with nano Ag catalyst A g/LaCoO
3, Ag/LaMnO
3vacuum aided hard template method.
Order mesoporous LaCoO
3and LaMnO
3the preparation method of loaded with nano Ag catalyst, is characterized in that, comprise the steps:
(1) order mesoporous LaCoO is prepared
3and LaMnO
3: get lanthanum nitrate hexahydrate and cobalt nitrate hexahydrate joins stirring and dissolving in absolute ethyl alcohol, wherein nitric hydrate lanthanum: cobalt nitrate hexahydrate: ethanol is 12.5mmol:12.5mmol:6mL or nitric hydrate lanthanum: manganese nitrate: ethanol is 12.5mmol:12.5mmol:5 mL, form precursor liquid A, for subsequent use;
(2) be respectively hard template with ordered mesoporous silica dioxide, be placed in the bottle,suction vacuumized, and keep vacuum state 1 hour, upper end uses the rubber stopper seal that dropping funel is housed;
(3) precursor liquid A is placed in dropping funel, under vacuum state slowly in instillation template, continues to be evacuated to dry after dripping off;
(4) step (3) gained sample is transferred in crystallising dish, is placed in 50
ocontinue dry in C vacuum drying chamber;
(5) grinding is sieved, and is placed in tubular type kiln roasting, in air atmosphere, with 1
oc/min is warming up to 650
oc, and keep 2 hours;
(6) product that step (5) obtains is placed in the beaker of the NaOH filling 2 moL/L, repeatedly stirs in a water bath, suction filtration, dry finally by vacuum drying oven, obtain the LaCoO of ordered mesopore structure
3and LaMnO
3;
(7) Ag/LaCoO is prepared
3, Ag/LaMnO
3catalyst: take silver nitrate and be dissolved in absolute ethyl alcohol, wherein silver nitrate: absolute ethyl alcohol is 0.46 mmol:10mL; Stirring and dissolving, forms precursor liquid B, for subsequent use; With the mesoporous LaCoO that step (6) is obtained
3and LaMnO
3be respectively carrier, be placed in the bottle,suction vacuumized, and keep vacuum 1 hour, upper end uses the rubber stopper seal that dropping funel is housed; Afterwards precursor liquid B is placed in dropping funel, under vacuum state, slowly instills carrier LaCoO
3or LaMnO
3in, drip off rear maintenance vacuum state 1 hour; The solution of transfer bottle,suction, in crystallising dish, is placed on 50
oin C vacuum drying chamber, after dry 12 hours, be placed in tubular type kiln roasting, first at 5% H
2/ Ar, flow is: 80mL/min, reduces, with 5 under atmosphere
oc/min is warming up to 300
oc, and keep 2 hours, after at air, flow is: 80mL/min, is oxidized, with 5 under atmosphere
oc/min is warming up to 500
oc, and keep 2 hours, obtain order mesoporous LaCoO
3and LaMnO
3the nanometer Ag catalyst of load.
Step (1) described template is the silica with ordered mesopore structure.
Step (4) described drying time is 12 hours.
Step (5) described air velocity is 100 mL/min.
Step (6) described bath temperature is 50 DEG C, and oven drying temperature is 50 DEG C.
In step (7), Ag load factor is 5%.
A kind of order mesoporous LaCoO
3and LaMnO
3loaded with nano Ag catalyst, is characterized in that, prepares according to above-mentioned arbitrary described method.
Described order mesoporous LaCoO
3and LaMnO
3the application that loaded with nano Ag catalyst is oxidized at catalyzing carbon monoxide, is placed on above-mentioned catalyst the gaseous mixture passing into carbon monoxide and air in continuous-flow fixed bed device and reacts; Reaction pressure is normal pressure ~ 1 atm, and reaction velocity is 30000 mL/ (gh), and in air and carbon mono oxide mixture, the concentration of carbon monoxide is 1%.
The present invention has cheaper starting materials and is easy to get, and preparation process is simple, products therefrom pattern, particle diameter and the feature such as aperture is controlled.
Ag/LaCoO prepared by the present invention
3, Ag/LaMnO
3(x=1-9%) there is the feature of ordered mesopore structure and excellent catalytic activity, in CO catalytic oxidation field, there is good application prospect.
Accompanying drawing explanation
Fig. 1 is Ag/LaCoO
3the XRD figure of (embodiment 1 and 5).
Fig. 2 is the TEM figure of embodiment 1.
Fig. 3 is the TEM figure of embodiment 2.
Fig. 4 is Ag/LaCoO
3activity curve (embodiment 1,3,5).
Fig. 5 is Ag/LaMnO
3activity curve (embodiment 2,4,6).
Fig. 6 is Ag/LaMnO
3(160
oand Ag/LaCoO C)
3(130
oc) stability curve (embodiment 5 and 6).
Detailed description of the invention
Embodiment 1:
Reference literature [Zhao DY et al.,
science , 279 (1998) 548] and synthesis SBA-15.Take 1.5 g SBA-15 and be placed in bottle,suction, use the plug seal bottle,suction with dropping funel, dropping funel is gone to sealing state, be evacuated to vacuum and reach 0.1 MPa, and keep this vacuum 1 h.
Take 4.06 g nitric hydrate lanthanum (La (NO
3)
3h
2o molecular weight is 324.9) and 3.6378 g cobalt nitrate hexahydrates be dissolved in 6 mL absolute ethyl alcohols, be stirred to dissolving.This solution is transferred in above-mentioned dropping funel, rotating piston, slowly instills in SBA-15, after dripping off to solution, continue to vacuumize, until solution is drained, be transferred in crystallising dish.Crystallising dish is placed in 50
odry 12 h are continued in C vacuum drying chamber.Take out sample, grinding is sieved, and sample is placed in crucible, in tube furnace, under air (flow: 100 mL/min) atmosphere, with 1
othe speed of C/min rises to 650
oc, and keep 2 h at such a temperature, gained sample is placed in the beaker of the NaOH filling 2 moL/L, 50
oc stirs repeatedly, suction filtration, finally by 50
oc vacuum drying oven is dry, obtains the LaCoO of ordered mesopore structure
3.
Take the LaCoO of 1 g ordered mesopore structure
3be placed in bottle,suction, use the plug seal bottle,suction with dropping funel, dropping funel is gone to sealing state, be evacuated to vacuum and reach 0.1 MPa, and keep this vacuum 1 h.Take 0.08g silver nitrate (AgNO
3) be dissolved in 10 mL absolute ethyl alcohols, be stirred to dissolving.Be transferred to by this solution in above-mentioned dropping funel, rotating piston, slowly instills LaCoO
3in, after dripping off to solution, continue to vacuumize, until solution is drained, be transferred in crystallising dish.Crystallising dish is placed in 50
odry 12 h are continued in C vacuum drying chamber.Take out sample, grinding is sieved, and sample is placed in little porcelain boat, first at 5% H
2/ Ar(flow is: 80mL/min) under atmosphere reduction (with 5
oc/min is warming up to 300
oc, and keep 2 h), after under air (flow is: 100mL/min) atmosphere oxidation (with 5
oc/min is warming up to 500
oc, and keep 2 h), obtain the LaCoO of ordered mesopore structure
3the 5%Ag/LaCoO of load
3catalyst.The temperature of CO conversion 90% is 140
oc.
Embodiment 2:
Reference literature [Zhao DY et al.,
science , 279 (1998) 548] and synthesis SBA-15.Take 2.0 g SBA-15 and be placed in bottle,suction, use the plug seal bottle,suction with dropping funel, dropping funel is gone to sealing state, be evacuated to vacuum and reach 0.1 MPa, and keep this vacuum 1 h.
The manganese nitrate solution taking 4.06 g nitric hydrate lanthanums and 6.25 g 50% is dissolved in 5 mL absolute ethyl alcohols, is stirred to dissolving.This solution is transferred in above-mentioned dropping funel, rotating piston, slowly instills in SBA-15, after dripping off to solution, continue to vacuumize, until solution is drained, be transferred in crystallising dish.Crystallising dish is placed in 50
odry 12 h are continued in C vacuum drying chamber.Take out sample, grinding is sieved, and sample is placed in crucible, in tube furnace, under air (flow: 100 mL/min) atmosphere, with 1
othe speed of C/min rises to 650
oc, and keep 2 h at such a temperature, gained sample is placed in the beaker of the NaOH filling 2 moL/L, 50
oc stirs repeatedly, suction filtration, finally by 50
oc vacuum drying oven is dry, obtains the LaMnO of ordered mesopore structure
3.
Take the LaMnO of 1 g three-dimensional ordered mesoporous structure
3be placed in bottle,suction, use the plug seal bottle,suction with dropping funel, dropping funel is gone to sealing state, be evacuated to vacuum and reach 0.1 MPa, and keep this vacuum 1 h.Take 0.08 g silver nitrate (AgNO
3) be dissolved in 10 mL absolute ethyl alcohols, be stirred to dissolving.Be transferred to by this solution in above-mentioned dropping funel, rotating piston, slowly instills LaCoO
3in, after dripping off to solution, continue to vacuumize, until solution is drained, be transferred in crystallising dish.Crystallising dish is placed in 50
odry 12 h are continued in C vacuum drying chamber.Take out sample, grinding is sieved, and sample is placed in little porcelain boat, first at 5% H
2/ Ar(flow is: 80mL/min) under atmosphere reduction (with 5
oc/min is warming up to 300
oc, and keep 2 h), after under air (flow is: 100mL/min) atmosphere oxidation (with 5
oc/min is warming up to 500
oc, and keep 2 h), obtain the LaMnO of ordered mesopore structure
3the 5%Ag/LaMnO of load
3catalyst, the temperature of CO conversion 90% is 200
oc
Embodiment 3:
Reference literature [R. M. Grudzien et al.,
appli. Surf. Sci., 253 (2007) 5660] SBA-16 is synthesized.Take 1.5 g SBA-16 and be placed in bottle,suction, use the plug seal bottle,suction with dropping funel, dropping funel is gone to sealing state, be evacuated to vacuum and reach 0.1 MPa, and keep this vacuum 1 h.
Take 4.06 g nitric hydrate lanthanums and 3.6378 g cobalt nitrate hexahydrates are dissolved in 6 mL absolute ethyl alcohols, be stirred to dissolving.This solution is transferred in above-mentioned dropping funel, rotating piston, slowly instills in SBA-16, after dripping off to solution, continue to vacuumize, until solution is drained, be transferred in crystallising dish.Crystallising dish is placed in 50
odry 12 h are continued in C vacuum drying chamber.Take out sample, grinding is sieved, and sample is placed in crucible, in tube furnace, under air (flow: 100 mL/min) atmosphere, with 1
othe speed of C/min rises to 650
oc, and keep 2 h at such a temperature, gained sample is placed in the beaker of the NaOH filling 2 moL/L, 50
oc stirs repeatedly, suction filtration, finally by 50
oc vacuum drying oven is dry, obtains the LaCoO of three-dimensional ordered mesoporous structure
3.
Take the LaCoO of 1 g three-dimensional ordered mesoporous structure
3be placed in bottle,suction, use the plug seal bottle,suction with dropping funel, dropping funel is gone to sealing state, be evacuated to vacuum and reach 0.1 MPa, and keep this vacuum 1 h.Take 0.08 g silver nitrate (AgNO
3) be dissolved in 10 mL absolute ethyl alcohols, be stirred to dissolving.Be transferred to by this solution in above-mentioned dropping funel, rotating piston, slowly instills LaCoO
3in, after dripping off to solution, continue to vacuumize, until solution is drained, be transferred in crystallising dish.Crystallising dish is placed in 50
odry 12 h are continued in C vacuum drying chamber.Take out sample, grinding is sieved, and sample is placed in little porcelain boat, first at 5% H
2/ Ar(flow is: 80mL/min) under atmosphere reduction (with 5
oc/min is warming up to 300
oc, and keep 2 h), after under air (flow is: 100mL/min) atmosphere oxidation (with 5
oc/min is warming up to 500
oc, and keep 2 h), obtain the LaCoO of three-dimensional ordered mesoporous structure
3the 5%Ag/LaCoO of load
3catalyst, the temperature of CO conversion 90% is 140
oc.
Embodiment 4:
Reference literature [R. M. Grudzien et al.,
appli. Surf. Sci., 253 (2007) 5660] SBA-16 is synthesized.Take 2.0 g SBA-16 and be placed in bottle,suction, use the plug seal bottle,suction with dropping funel, dropping funel is gone to sealing state, be evacuated to vacuum and reach 0.1 MPa, and keep this vacuum 1 h.
The manganese nitrate solution taking 4.06g nitric hydrate lanthanum and 6.25 g 50% is dissolved in 5 mL absolute ethyl alcohols, is stirred to dissolving.This solution is transferred in above-mentioned dropping funel, rotating piston, slowly instills in SBA-16, after dripping off to solution, continue to vacuumize, until solution is drained, be transferred in crystallising dish.Crystallising dish is placed in 50
odry 12 h are continued in C vacuum drying chamber.Take out sample, grinding is sieved, and sample is placed in crucible, with 1
othe speed of C/min rises to 650
oc, and keep 2 h at such a temperature, gained sample is placed in the beaker of the NaOH filling 2 moL/L, 50
oc stirs repeatedly, suction filtration, finally by 50
oc vacuum drying oven is dry, obtains the LaMnO of three-dimensional ordered mesoporous structure
3.
Take the LaMnO of 1 g three-dimensional ordered mesoporous structure
3be placed in bottle,suction, use the plug seal bottle,suction with dropping funel, dropping funel is gone to sealing state, be evacuated to vacuum and reach 0.1 MPa, and keep this vacuum 1 h.Take 0.08 g silver nitrate (AgNO
3) be dissolved in 10 mL absolute ethyl alcohols, be stirred to dissolving.Be transferred to by this solution in above-mentioned dropping funel, rotating piston, slowly instills LaCoO
3in, after dripping off to solution, continue to vacuumize, until solution is drained, be transferred in crystallising dish.Crystallising dish is placed in 50
odry 2 days are continued in C vacuum drying chamber.Take out sample, grinding is sieved, and sample is placed in little porcelain boat, first at 5% H
2/ Ar(flow is: 80mL/min) under atmosphere reduction (with 5
oc/min is warming up to 300
oc, and keep 2 h), after under air (flow is: 100mL/min) atmosphere oxidation (with 5
oc/min is warming up to 500
oc, and keep 2 h), obtain the LaMnO of three-dimensional ordered mesoporous structure
3the 5%Ag/LaMnO of load
3catalyst, the temperature of CO conversion 90% is 200
oc.
Embodiment 5:
Reference literature [R. Ryoo et al.,
chem Commun., (2003) 2136] KIT-6 is synthesized.Take 1.5 g KIT-6 and be placed in bottle,suction, use the plug seal bottle,suction with dropping funel, dropping funel is gone to sealing state, be evacuated to vacuum and reach 0.1 MPa, and keep this vacuum 1 h.
Take 4.06 g nitric hydrate lanthanums and 3.6378 g cobalt nitrate hexahydrates are dissolved in 6 mL absolute ethyl alcohols, be stirred to dissolving.This solution is transferred in above-mentioned dropping funel, rotating piston, slowly instills in KIT-6, after dripping off to solution, continue to vacuumize, until solution is drained, be transferred in crystallising dish.Crystallising dish is placed in 50
odry 12 h are continued in C vacuum drying chamber.Take out sample, grinding is sieved, and sample is placed in crucible, in tube furnace under air (flow velocity is 100 mL/min) atmosphere with 1
othe speed of C/min rises to 650
oc, and keep 2 h at such a temperature, gained sample is placed in the beaker of the NaOH filling 2 moL/L, 50
oc stirs repeatedly, suction filtration, finally by 50
oc vacuum drying oven is dry, obtains the LaCoO of three-dimensional ordered mesoporous structure
3.
Take the LaCoO of 1 g three-dimensional ordered mesoporous structure
3be placed in bottle,suction, use the plug seal bottle,suction with dropping funel, dropping funel is gone to sealing state, be evacuated to vacuum and reach 0.1 MPa, and keep this vacuum 1 h.Take 0.08 g silver nitrate (AgNO
3) be dissolved in 10 mL absolute ethyl alcohols, be stirred to dissolving.Be transferred to by this solution in above-mentioned dropping funel, rotating piston, slowly instills LaCoO
3in, after dripping off to solution, continue to vacuumize, until solution is drained, be transferred in crystallising dish.Crystallising dish is placed in 50
odry 2 days are continued in C vacuum drying chamber.Take out sample, grinding is sieved, and sample is placed in little porcelain boat, first at 5% H
2/ Ar(flow is: 80mL/min) under atmosphere reduction (with 5
oc/min is warming up to 300
oc, and keep 2 h), after under air (flow is: 100mL/min) atmosphere oxidation (with 5
oc/min is warming up to 500
oc, and keep 2 h), obtain the LaCoO of three-dimensional ordered mesoporous structure
3the 5%Ag/LaCoO of load
3catalyst, the temperature of CO conversion 90% is 140
oc.130
oduring C, CO conversion ratio is active in significant change in 80%, 12h.
Embodiment 6:
Reference literature [R. Ryoo et al.,
chem Commun., (2003) 2136] KIT-6 is synthesized.Take 2.0 g KIT-6 and be placed in bottle,suction, use the plug seal bottle,suction with dropping funel, dropping funel is gone to sealing state, be evacuated to vacuum and reach 0.1 MPa, and keep this vacuum 1 h.
The manganese nitrate solution taking 4.06 g nitric hydrate lanthanums and 6.25 g 50% is dissolved in 5 mL absolute ethyl alcohols, is stirred to dissolving.This solution is transferred in above-mentioned dropping funel, rotating piston, slowly instills in KIT-6, after dripping off to solution, continue to vacuumize, until solution is drained, be transferred in crystallising dish.Crystallising dish is placed in 50
odry 12 h are continued in C vacuum drying chamber.Take out sample, grinding is sieved, and sample is placed in crucible, in tube furnace under air (flow velocity is 100 mL/min) atmosphere, with 1
othe speed of C/min rises to 650
oc, and keep 2 h at such a temperature, gained sample is placed in the beaker of the NaOH filling 2 moL/L, 50
oc stirs repeatedly, suction filtration, finally by 50
oc vacuum drying oven is dry, obtains the LaMnO of three-dimensional ordered mesoporous structure
3.
Take the LaMnO of 1 g three-dimensional ordered mesoporous structure
3be placed in bottle,suction, use the plug seal bottle,suction with dropping funel, dropping funel is gone to sealing state, be evacuated to vacuum and reach 0.1 MPa, and keep this vacuum 1 h.Take 0.08 g silver nitrate (AgNO
3) be dissolved in 10 mL absolute ethyl alcohols, be stirred to dissolving.Be transferred to by this solution in above-mentioned dropping funel, rotating piston, slowly instills LaCoO
3in, after dripping off to solution, continue to vacuumize, until solution is drained, be transferred in crystallising dish.Crystallising dish is placed in 50
odry 12 h are continued in C vacuum drying chamber.Take out sample, grinding is sieved, and sample is placed in little porcelain boat, first at 5% H
2/ Ar(flow is: 80mL/min) under atmosphere reduction (with 5
oc/min is warming up to 300
oc, and keep 2 h), after under air (flow is: 100mL/min) atmosphere oxidation (with 5
oc/min is warming up to 500
oc, and keep 2 h), obtain the LaMnO of three-dimensional ordered mesoporous structure
3the 5%Ag/LaMnO of load
3catalyst, the temperature of CO conversion 90% is 200
oc.160
oduring C, CO conversion ratio is active in significant change in 66%, 12h.
Claims (8)
1. order mesoporous LaCoO
3and LaMnO
3the preparation method of loaded with nano Ag catalyst, is characterized in that, comprise the steps:
(1) order mesoporous LaCoO is prepared
3and LaMnO
3: get lanthanum nitrate hexahydrate and cobalt nitrate hexahydrate joins stirring and dissolving in absolute ethyl alcohol, wherein nitric hydrate lanthanum: cobalt nitrate hexahydrate: ethanol is 12.5mmol:12.5mmol:6mL or nitric hydrate lanthanum: manganese nitrate: ethanol is 12.5mmol:12.5mmol:5 mL, form precursor liquid A, for subsequent use;
(2) be respectively hard template with ordered mesoporous silica dioxide, be placed in the bottle,suction vacuumized, and keep vacuum state 1 hour, upper end uses the rubber stopper seal that dropping funel is housed;
(3) precursor liquid A is placed in dropping funel, under vacuum state slowly in instillation template, continues to be evacuated to dry after dripping off;
(4) step (3) gained sample is transferred in crystallising dish, is placed in 50
ocontinue dry in C vacuum drying chamber;
(5) grinding is sieved, and is placed in tubular type kiln roasting, in air atmosphere, with 1
oc/min is warming up to 650
oc, and keep 2 hours;
(6) product that step (5) obtains is placed in the beaker of the NaOH filling 2 moL/L, repeatedly stirs in a water bath, suction filtration, dry finally by vacuum drying oven, obtain the LaCoO of ordered mesopore structure
3and LaMnO
3;
(7) Ag/LaCoO is prepared
3, Ag/LaMnO
3catalyst: take silver nitrate and be dissolved in absolute ethyl alcohol, wherein silver nitrate: absolute ethyl alcohol is 0.46 mmol:10mL; Stirring and dissolving, forms precursor liquid B, for subsequent use; With the mesoporous LaCoO that step (6) is obtained
3and LaMnO
3be respectively carrier, be placed in the bottle,suction vacuumized, and keep vacuum 1 hour, upper end uses the rubber stopper seal that dropping funel is housed; Afterwards precursor liquid B is placed in dropping funel, under vacuum state, slowly instills carrier LaCoO
3or LaMnO
3in, drip off rear maintenance vacuum state 1 hour; The solution of transfer bottle,suction, in crystallising dish, is placed on 50
oin C vacuum drying chamber, after dry 12 hours, be placed in tubular type kiln roasting, first at 5% H
2/ Ar, flow is: 80mL/min, reduces, with 5 under atmosphere
oc/min is warming up to 300
oc, and keep 2 hours, after at air, flow is: 80mL/min, is oxidized, with 5 under atmosphere
oc/min is warming up to 500
oc, and keep 2 hours, obtain order mesoporous LaCoO
3and LaMnO
3the nanometer Ag catalyst of load.
2. order mesoporous LaCoO according to claim 1
3and LaMnO
3the preparation method of loaded with nano Ag catalyst, is characterized in that, step (1) described template is the silica with ordered mesopore structure.
3. order mesoporous LaCoO according to claim 1
3and LaMnO
3the preparation method of loaded with nano Ag catalyst, is characterized in that, step (4) described drying time is 12 hours.
4. order mesoporous LaCoO according to claim 1
3and LaMnO
3the preparation method of loaded with nano Ag catalyst, is characterized in that, step (5) described air velocity is 100 mL/min.
5. order mesoporous LaCoO according to claim 1
3and LaMnO
3the preparation method of loaded with nano Ag catalyst, is characterized in that, step (6) described bath temperature is 50 DEG C, and oven drying temperature is 50 DEG C.
6. order mesoporous LaCoO according to claim 1
3and LaMnO
3the preparation method of loaded with nano Ag catalyst, is characterized in that, in step (7), Ag load factor is 5%.
7. an order mesoporous LaCoO
3and LaMnO
3loaded with nano Ag catalyst, is characterized in that, according to above-mentioned arbitrary claim, method prepares.
8. order mesoporous LaCoO according to claim 8
3and LaMnO
3the application that loaded with nano Ag catalyst is oxidized at catalyzing carbon monoxide, is placed on above-mentioned catalyst the gaseous mixture passing into carbon monoxide and air in continuous-flow fixed bed device and reacts; Reaction pressure is normal pressure ~ 1 atm, and reaction velocity is 30000 mL/ (gh), and in air and carbon mono oxide mixture, the concentration of carbon monoxide is 1%.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410785849.4A CN104607201B (en) | 2014-12-18 | 2014-12-18 | Ordered mesoporous LaCoO3 and LaMnO3 supported nano Ag catalyst and preparation and application thereof |
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| CN201410785849.4A CN104607201B (en) | 2014-12-18 | 2014-12-18 | Ordered mesoporous LaCoO3 and LaMnO3 supported nano Ag catalyst and preparation and application thereof |
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| CN104607201A true CN104607201A (en) | 2015-05-13 |
| CN104607201B CN104607201B (en) | 2017-01-11 |
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| CN105327706A (en) * | 2015-09-23 | 2016-02-17 | 上海交通大学 | Catalyst for low temperature catalytic removal of environment pollutants, and preparation method thereof |
| CN110292935A (en) * | 2019-04-24 | 2019-10-01 | 武汉理工大学 | A kind of doped meso-porous LaCoO of Mn3Perovskite type catalyst and preparation method thereof |
| CN110773194A (en) * | 2019-10-17 | 2020-02-11 | 厦门大学 | CO (carbon monoxide) 2Catalyst for preparing methane by hydrogenation and preparation method thereof |
| CN111389393A (en) * | 2020-04-30 | 2020-07-10 | 武汉理工大学 | Preparation of porous L aMnO with ordered mesoporous carbon as hard template3Method for preparing catalyst, catalyst obtained by method and application of catalyst |
| CN112110497A (en) * | 2020-09-28 | 2020-12-22 | 中国科学技术大学 | Lanthanide metal-doped lanthanum cobaltate type nanotube material, preparation method thereof and method for producing hydrogen by electrolyzing water |
| WO2022089669A1 (en) * | 2020-10-26 | 2022-05-05 | 苏州大学 | Composite material of strontium-doped ordered mesoporous lanthanum manganite loaded with precious metal palladium, and preparation method therefor and use thereof in catalytic oxidation of toluene |
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| CN105327706A (en) * | 2015-09-23 | 2016-02-17 | 上海交通大学 | Catalyst for low temperature catalytic removal of environment pollutants, and preparation method thereof |
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| CN110292935A (en) * | 2019-04-24 | 2019-10-01 | 武汉理工大学 | A kind of doped meso-porous LaCoO of Mn3Perovskite type catalyst and preparation method thereof |
| CN110773194A (en) * | 2019-10-17 | 2020-02-11 | 厦门大学 | CO (carbon monoxide) 2Catalyst for preparing methane by hydrogenation and preparation method thereof |
| CN111389393A (en) * | 2020-04-30 | 2020-07-10 | 武汉理工大学 | Preparation of porous L aMnO with ordered mesoporous carbon as hard template3Method for preparing catalyst, catalyst obtained by method and application of catalyst |
| CN112110497A (en) * | 2020-09-28 | 2020-12-22 | 中国科学技术大学 | Lanthanide metal-doped lanthanum cobaltate type nanotube material, preparation method thereof and method for producing hydrogen by electrolyzing water |
| CN112110497B (en) * | 2020-09-28 | 2022-04-19 | 中国科学技术大学 | Lanthanide metal-doped lanthanum cobaltate type nanotube material, preparation method thereof and method for producing hydrogen by electrolyzing water |
| WO2022089669A1 (en) * | 2020-10-26 | 2022-05-05 | 苏州大学 | Composite material of strontium-doped ordered mesoporous lanthanum manganite loaded with precious metal palladium, and preparation method therefor and use thereof in catalytic oxidation of toluene |
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