CN103055875A - Preparation method of catalytic material mixed by copper and cerium oxide - Google Patents
Preparation method of catalytic material mixed by copper and cerium oxide Download PDFInfo
- Publication number
- CN103055875A CN103055875A CN2012104355333A CN201210435533A CN103055875A CN 103055875 A CN103055875 A CN 103055875A CN 2012104355333 A CN2012104355333 A CN 2012104355333A CN 201210435533 A CN201210435533 A CN 201210435533A CN 103055875 A CN103055875 A CN 103055875A
- Authority
- CN
- China
- Prior art keywords
- cerium oxide
- copper
- preparation
- cerium
- citric acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000010949 copper Substances 0.000 title claims abstract description 50
- 239000000463 material Substances 0.000 title claims abstract description 46
- 229910000420 cerium oxide Inorganic materials 0.000 title claims abstract description 33
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 title claims abstract description 33
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 230000003197 catalytic effect Effects 0.000 title abstract description 15
- 229910000431 copper oxide Inorganic materials 0.000 title abstract 2
- 238000003756 stirring Methods 0.000 claims abstract description 51
- 239000000843 powder Substances 0.000 claims abstract description 48
- 238000001035 drying Methods 0.000 claims abstract description 24
- 229910052802 copper Inorganic materials 0.000 claims abstract description 23
- 150000001879 copper Chemical class 0.000 claims abstract description 15
- 239000012266 salt solution Substances 0.000 claims abstract description 13
- 150000002500 ions Chemical class 0.000 claims abstract description 12
- 238000000227 grinding Methods 0.000 claims abstract description 11
- 239000011259 mixed solution Substances 0.000 claims abstract description 11
- 239000007787 solid Substances 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 150
- 229910052684 Cerium Inorganic materials 0.000 claims description 43
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 40
- 239000008367 deionised water Substances 0.000 claims description 36
- 229910021641 deionized water Inorganic materials 0.000 claims description 36
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 31
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 31
- 239000000243 solution Substances 0.000 claims description 30
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 27
- 238000006555 catalytic reaction Methods 0.000 claims description 27
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 20
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 20
- 150000000703 Cerium Chemical class 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical group [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 10
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 10
- 238000002425 crystallisation Methods 0.000 claims description 10
- 230000008025 crystallization Effects 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- -1 polytetrafluoroethylene Polymers 0.000 claims description 10
- 239000013049 sediment Substances 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 239000011148 porous material Substances 0.000 abstract description 14
- 238000007254 oxidation reaction Methods 0.000 abstract description 9
- 230000003647 oxidation Effects 0.000 abstract description 8
- 238000002474 experimental method Methods 0.000 abstract description 3
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract description 2
- 230000003287 optical effect Effects 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000001354 calcination Methods 0.000 abstract 1
- 238000004140 cleaning Methods 0.000 abstract 1
- 230000000694 effects Effects 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 238000000746 purification Methods 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 description 12
- 229910000906 Bronze Inorganic materials 0.000 description 5
- 239000010974 bronze Substances 0.000 description 5
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 5
- 238000000034 method Methods 0.000 description 4
- 125000004430 oxygen atom Chemical group O* 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 235000007849 Lepidium sativum Nutrition 0.000 description 1
- 244000211187 Lepidium sativum Species 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000035807 sensation Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Images
Landscapes
- Catalysts (AREA)
Abstract
The invention provides a preparation method of a catalytic material mixed by copper and cerium oxide. The preparation method comprises the following steps of: (a) dissolving copper salt in a solvent, and continuously mixing the copper salt for 0.5-1 hour, wherein the concentration of Cu ions is 0.00872-0.17492 mol/mL; (b) adding mesoporous cerium oxide powder into a copper salt solution obtained by the step (a) according to the liquid-to-solid ratio of 10:1 to 6:1, stilling the copper salt solution for 24-48 hours after the mesoporous cerium oxide powder is dissolved, and meanwhile, aperiodically stirring the copper salt solution; (c) drying the mixed solution obtained by the step (b) at 110-120 DEG C for 10-12 hours, grinding the dried resultant, and calcining the resultant at 200-300 DEG C for 2-3 hours, thus obtaining the catalytic material mixed by the copper and the cerium oxide. The preparation method has the advantages of simplicity in operation and experimental procedure, low cost of raw materials, and no environmental pollution, and the prepared catalytic material has the advantages of large specific surface area and pore volume, high low-temperature activity and favorable thermal stability. The prepared catalytic material can be widely applied to optical CO oxidation sensors, motor vehicle exhaust gas cleaning and purification systems and the like, and is prone to industrial production.
Description
Technical field
The present invention relates to a kind of CuO-CeO for low-temperature CO oxidation reaction
2Efficient catalytic material preparation method specifically belongs to cerium Base Metal material technology field.
Background technology
Cerium has many advantages as rare earth element, such as: under oxygen enrichment (oxidizing condition), can be Ce
3+Be oxidized to Ce
4+Thereby, in material, store oxygen atom; And under oxygen deprivation (reducing condition), can the oxygen atom of its storage be discharged i.e. Ce
4+Be reduced to Ce
3+, make reducing substances obtain oxygen atom, reached the purpose that discharges oxygen atom.This is just so that cerium-this rare earth element becomes reasonable catalyst material.Mesoporous material has preferably specific area and plot ratio and has obtained widely research aspect catalyst, adopts chemical precipitation method to synthesize meso-pore Ce O such as (CN1837053A) such as Song Xiaolan
2, the advantage such as it is larger to have specific area, and distribution of particles is more even.
But simple cerium oxide is in some deficiencies of aspect such as catalytic oxidation, light sensation, temperature-sensitive and fuel cells, as: catalytic temperature is too high, and sensitivity is not enough, and catalytic effect and heat endurance are bad etc.A lot of scholars are to CeO
2Carried out the experiment of mixing, as: Zhao Wenguang etc. have studied the cerium oxide-doped yittrium oxide to zirconic thermal expansion character; The Fan Yang of U.S. Brookhaven National Laboratory has studied the research of Cu doped Ce O to oxidation CO performance.But domestic relevant for the doped meso-porous CeO of Cu
2Report still rare.
Summary of the invention
The object of the invention is to propose a kind of preparation method of copper doped cerium oxide catalysis material, this preparation method is simple, raw material obtains easily, cheap, and gained catalysis material low-temperature oxidation CO is active high.
The present invention realizes by following technical proposal: a kind of preparation method of copper doped cerium oxide catalysis material, and following each step of process:
(a) get mantoquita and be dissolved in the solvent, continuous stirring 0.5～1h; Wherein the concentration of Cu ion is 0.00872～0.17492mol/mL;
(b) be 10 ︰, 1～6 ︰ 1 by liquid-solid ratio, the mesoporous ceria powder added in step (a) the gained copper salt solution, after the dissolving, leave standstill 24～48h, during not timing stir;
(c) mixed solution with step (b) places thermostatic drying chamber with 110～120 ℃ of drying 10～12h, is placed in the Muffle furnace with 200～300 ℃ of roasting 2～3h through grinding again, namely obtains copper doped cerium oxide catalysis material.
The mantoquita of described step (a) is copper nitrate (Cu (NO
3)
23H
2O).
The mesoporous ceria powder of described step (b) makes through following each step:
(1) get 17.1852～52.240g cerium salt and 1.7～5.2964g citric acid is dissolved in the solvent, continuous stirring 0.5～1h obtains the citric acid presoma of cerium;
(2) get CTAB and be dissolved in the solvent, in 30～40 ℃ of lower continuous stirring 0.5～1h, obtaining concentration is the CTAB solution of 0.08～0.25mol/L;
(3) in 65～70 ℃ water-bath, be 5 ︰, 1～1 ︰ 1 by the citric acid presoma of cerium and the volume ratio of CTAB solution, step (2) gained solution is joined in the citric acid presoma of step (1) gained cerium slowly, continuous stirring 2～4h adds NH again
3H
2O to the pH value of mixed liquor be till 8.5～10;
(4) mixture that step (3) is obtained places the autoclave of polytetrafluoroethylene (PTFE), then carries out crystallization 8～12 hours with 100～120 ℃, is precipitated thing;
(5) respectively with the sediment of absolute ethyl alcohol and water wash step (4) gained each three times, in 100～120 ℃, dried 8～12 hours again, obtain powder;
(6) powder that step (5) is obtained namely obtains the mesoporous ceria powder with 300～500 ℃ of roastings.
Cerium salt is cerous nitrate (Ce (NO in the described step (1)
3)
36H
2O).
The concentration of cerium salt is 0.4～1.2mol/L in the citric acid presoma of the middle cerium of described step (1).
The water of described step (5) is deionized water.
Described solvent is deionized water.
The copper doped cerium oxide catalysis material that the present invention obtains is by adopting 1%CO, 10%O
2And 89%N
2Gaseous mixture detect the conversion ratio of CO as unstripped gas, at room temperature begin to pass into unstripped gas, begin to be converted into CO at 70～80 ℃ of CO
2, and all be converted into CO at 120～130 ℃ of CO
2Show that such as Fig. 6 this catalyst just can all be converted into CO to CO at low temperatures
2, solved the shortcoming that catalytic temperature is too high, sensitivity is not enough and catalytic effect is bad, be the design sketch of 100 ℃ of CO catalytic oxidations, show that the heat endurance of this catalyst is fine.
The present invention adopts homemade meso-pore Ce O
2Use infusion process to prepare copper doped cerium oxide material, the method is simple to operate, experimental procedure is terse, the prices of raw and semifnished materials are cheap, non-environmental-pollution makes catalyst material and has higher specific area and pore volume, low temperature active height and Heat stability is good, can be widely used at aspects such as CO oxidation, optical pickocff, motor-vehicle tail-gas Cress systems, and be easy to suitability for industrialized production.
Description of drawings
Fig. 1 is the XRD diffraction pattern of embodiment 4 mesoporous ceria powder;
Fig. 2 is the XRD diffraction pattern of embodiment 8 bronze medal doped cerium oxide catalysis materials;
Fig. 3 is the N of embodiment 1 bronze medal doped cerium oxide catalysis material
2Absorption and desorption curve;
Fig. 4 is the N of embodiment 6 bronze medal doped cerium oxide catalysis materials
2Absorption and desorption curve;
Fig. 5 is that the curve map of the CO conversion rate of oxidation of embodiment 5 bronze medal doped cerium oxide catalysis materials reaches the curve of stability in time;
Fig. 6 is that the CO low-temperature oxidation catalytic activity of embodiment 2 bronze medal doped cerium oxide catalysis materials is with the reaction time change curve;
Fig. 1 shows that this powder is pure CeO
2Fig. 2 is the meso-pore Ce O that Cu mixes
2The XRD collection of illustrative plates, show that Cu element or Cu ion enter meso-pore Ce O
2Lattice in, can improve its catalytic performance; Fig. 3,4 shows that adsorption curve is the isothermal curve of typical IV class absorption/desorption, is H2 type hysteresis loop, shows that this material has meso-hole structure; Fig. 5,6 shows that this catalyst has preferably catalytic performance and heat endurance.
The specific embodiment
The present invention will be further described below in conjunction with embodiment.
(a) get 0.06318g copper nitrate (Cu (NO
3)
23H
2O) be dissolved in the deionized water continuous stirring 0.5h; Wherein the concentration of Cu ion is 0.00872mol/mL;
(b) be 8 ︰ 1 by liquid-solid ratio, the mesoporous ceria powder added in step (a) the gained copper salt solution, after the dissolving, leave standstill 24h, during not timing stir;
(c) mixed solution with step (b) places thermostatic drying chamber with 110 ℃ of dry 10h, is placed in the Muffle furnace with 300 ℃ of roasting 2h through grinding again, namely obtains copper doped cerium oxide catalysis material, and its specific area is 154.289m
2/ g, pore volume are 0.975cm
3/ g.
Wherein, the mesoporous ceria powder makes through following each step:
(1) gets 52.240g cerous nitrate (Ce (NO
3)
36H
2O) and the 5.2510g citric acid be dissolved in the deionized water, continuous stirring 0.5h obtains the citric acid presoma of cerium, wherein the concentration of cerium salt is 1.2mol/L in the citric acid presoma of cerium;
(2) get the 8.9926gCTAB(softex kw) be dissolved in the deionized water, in 30 ℃ of lower continuous stirring 0.5h, obtaining concentration is the CTAB solution of 0.25mol/L;
(3) in 65 ℃ water-bath, be 3 ︰ 1 by the citric acid presoma of cerium and the volume ratio of CTAB solution, step (2) gained solution is joined in the citric acid presoma of step (1) gained cerium slowly, continuous stirring 2h adds NH again
3H
2O to the pH value of mixed liquor be till 8.5;
(4) mixture that step (3) is obtained places the autoclave of polytetrafluoroethylene (PTFE), then puts into thermostatic drying chamber and carries out crystallization 12 hours with 120 ℃, is precipitated thing;
(5) respectively with the sediment of absolute ethyl alcohol and deionized water washing step (4) gained each three times, place again thermostatic drying chamber with 120 ℃ of oven dry 12 hours, obtain powder;
(6) powder that step (5) is obtained places Muffle furnace with 300 ℃ of roasting 4h, namely obtains the mesoporous ceria catalyst material.
(a) get 0.1972g copper nitrate (Cu (NO
3)
23H
2O) be dissolved in the deionized water continuous stirring 0.8h; Wherein the concentration of Cu ion is 0.02616mol/mL;
(b) be 10 ︰ 1 by liquid-solid ratio, the mesoporous ceria powder added in step (a) the gained copper salt solution, after the dissolving, leave standstill 36h, during not timing stir;
(c) mixed solution with step (b) places thermostatic drying chamber with 120 ℃ of dry 12h, is placed in the Muffle furnace with 280 ℃ of roasting 3h through grinding again, namely obtains copper doped cerium oxide catalysis material, and its specific area is 150.976m
2/ g, pore volume are 0.879cm
3/ g.
Wherein, the mesoporous ceria powder makes through following each step:
(1) gets 17.3652g cerous nitrate (Ce (NO
3)
36H
2O) and the 1.72812g citric acid be dissolved in the deionized water, continuous stirring 0.5h obtains the citric acid presoma of cerium, wherein the concentration of cerium salt is 0.4mol/L in the citric acid presoma of cerium;
(2) get the 2.9885gCTAB(softex kw) be dissolved in the deionized water, in 30 ℃ of lower continuous stirring 0.5h, obtaining concentration is the CTAB solution of 0.08mol/L;
(3) in 70 ℃ water-bath, be 5 ︰ 1 by the citric acid presoma of cerium and the volume ratio of CTAB solution, step (2) gained solution is joined in the citric acid presoma of step (1) gained cerium slowly, continuous stirring 3h adds NH again
3H
2O to the pH value of mixed liquor be till 9.5;
(4) mixture that step (3) is obtained places the autoclave of polytetrafluoroethylene (PTFE), then puts into thermostatic drying chamber and carries out crystallization 12 hours with 120 ℃, is precipitated thing;
(5) respectively with the sediment of absolute ethyl alcohol and deionized water washing step (4) gained each three times, place again thermostatic drying chamber with 120 ℃ of oven dry 12 hours, obtain powder;
(6) powder that step (5) is obtained places Muffle furnace with 300 ℃ of roasting 4h, namely obtains the mesoporous ceria catalyst material.
Embodiment 3
(a) get 0.3235g copper nitrate (Cu (NO
3)
23H
2O) be dissolved in the deionized water continuous stirring 1h; Wherein the concentration of Cu ion is 0.0436mol/mL;
(b) be 6 ︰ 1 by liquid-solid ratio, the mesoporous ceria powder added in step (a) the gained copper salt solution, after the dissolving, leave standstill 48h, during not timing stir;
(c) mixed solution with step (b) places thermostatic drying chamber with 120 ℃ of dry 10h, is placed in the Muffle furnace with 200 ℃ of roasting 2.5h through grinding again, namely obtains copper doped cerium oxide catalysis material, and its specific area is 147.630m
2/ g, pore volume are 0.859cm
3/ g.
Wherein, the mesoporous ceria powder makes through following each step:
(1) gets 30.8873g cerous nitrate (Ce (NO
3)
36H
2O) and the 3.1002g citric acid be dissolved in the deionized water, continuous stirring 0.8h obtains the citric acid presoma of cerium, wherein the concentration of cerium salt is 0.71mol/L in the citric acid presoma of cerium;
(2) get the 5.39658gCTAB(softex kw) be dissolved in the deionized water, in 35 ℃ of lower continuous stirring 0.8h, obtaining concentration is the CTAB solution of 0.15mol/L;
(3) in 65 ℃ water-bath, be 1 ︰ 1 by the citric acid presoma of cerium and the volume ratio of CTAB solution, step (2) gained solution is joined in the citric acid presoma of step (1) gained cerium slowly, continuous stirring 4h adds NH again
3H
2O to the pH value of mixed liquor be till 10;
(4) mixture that step (3) is obtained places the autoclave of polytetrafluoroethylene (PTFE), then puts into thermostatic drying chamber and carries out crystallization 10 hours with 110 ℃, is precipitated thing;
(5) respectively with the sediment of absolute ethyl alcohol and deionized water washing step (4) gained each three times, place again thermostatic drying chamber with 110 ℃ of oven dry 10 hours, obtain powder;
(6) powder that step (5) is obtained places Muffle furnace with 300 ℃ of roasting 4h, namely obtains the mesoporous ceria catalyst material.
Embodiment 4
(a) get 0.4455g copper nitrate (Cu (NO
3)
23H
2O) be dissolved in the deionized water continuous stirring 1h; Wherein the concentration of Cu ion is 0.06104mol/mL;
(b) be 10 ︰, 1～6 ︰ 1 by liquid-solid ratio, the mesoporous ceria powder added in step (a) the gained copper salt solution, after the dissolving, leave standstill 24h, during not timing stir;
(c) mixed solution with step (b) places thermostatic drying chamber with 115 ℃ of dry 12h, is placed in the Muffle furnace with 300 ℃ of roasting 3h through grinding again, namely obtains copper doped cerium oxide catalysis material, and its specific area is 140.286m
2/ g, pore volume are 0.801cm
3/ g.
Wherein, the mesoporous ceria powder makes through following each step:
(1) gets 51.5283g cerous nitrate (Ce (NO
3)
36H
2O) and the 5.2964g citric acid be dissolved in the deionized water, continuous stirring 1h obtains the citric acid presoma of cerium, wherein the concentration of cerium salt is 1.19mol/L in the citric acid presoma of cerium;
(2) get the CTAB(softex kw) be dissolved in the deionized water, in 40 ℃ of lower continuous stirring 1h, obtaining concentration is the CTAB solution of 0.25mol/L;
(3) in 68 ℃ water-bath, be 2 ︰ 1 by the citric acid presoma of cerium and the volume ratio of CTAB solution, step (2) gained solution is joined in the citric acid presoma of step (1) gained cerium slowly, continuous stirring 2h adds NH again
3H
2O to the pH value of mixed liquor be till 8.5;
(4) mixture that step (3) is obtained places the autoclave of polytetrafluoroethylene (PTFE), then puts into thermostatic drying chamber and carries out crystallization 8 hours with 100 ℃, is precipitated thing;
(5) respectively with the sediment of absolute ethyl alcohol and deionized water washing step (4) gained each three times, place again thermostatic drying chamber with 100 ℃ of oven dry 8 hours, obtain powder;
(6) powder that step (5) is obtained places Muffle furnace with 500 ℃ of roasting 4h, namely obtains the mesoporous ceria catalyst material.
Embodiment 5
(a) get 0.6324g copper nitrate (Cu (NO
3)
23H
2O) be dissolved in the deionized water continuous stirring 1h; Wherein the concentration of Cu ion is 0.00872mol/mL;
(b) be 8 ︰ 1 by liquid-solid ratio, the mesoporous ceria powder added in step (a) the gained copper salt solution, after the dissolving, leave standstill 24h, during not timing stir;
(c) mixed solution with step (b) places thermostatic drying chamber with 120 ℃ of dry 10h, is placed in the Muffle furnace with 200 ℃ of roasting 3h through grinding again, namely obtains copper doped cerium oxide catalysis material, and its specific area is 134.639m
2/ g, pore volume are 0.752cm
3/ g.
Wherein, the mesoporous ceria powder makes through following each step:
(1) gets 17.1852g cerous nitrate (Ce (NO
3)
36H
2O) and the 1.7196g citric acid be dissolved in the deionized water, continuous stirring 0.5h obtains the citric acid presoma of cerium, wherein the concentration of cerium salt is 0.4mol/L in the citric acid presoma of cerium;
(2) get the CTAB(softex kw) be dissolved in the deionized water, in 30 ℃ of lower continuous stirring 0.5h, obtaining concentration is the CTAB solution of 0.08mol/L;
(3) in 65 ℃ water-bath, be 4 ︰ 1 by the citric acid presoma of cerium and the volume ratio of CTAB solution, step (2) gained solution is joined in the citric acid presoma of step (1) gained cerium slowly, continuous stirring 2h adds NH again
3H
2O to the pH value of mixed liquor be till 9.5;
(4) mixture that step (c) is obtained places the autoclave of polytetrafluoroethylene (PTFE), then puts into thermostatic drying chamber and carries out crystallization 12 hours with 120 ℃, is precipitated thing;
(5) respectively with the sediment of absolute ethyl alcohol and deionized water washing step (4) gained each three times, place again thermostatic drying chamber with 120 ℃ of oven dry 12 hours, obtain powder;
(6) powder that step (5) is obtained places Muffle furnace with 400 ℃ of roasting 4h, namely obtains the mesoporous ceria catalyst material.
Embodiment 6
(a) get 0.8319g copper nitrate (Cu (NO
3)
23H
2O) be dissolved in the deionized water continuous stirring 0.5h; Wherein the concentration of Cu ion is 0.11478mol/mL;
(b) be 9 ︰ 1 by liquid-solid ratio, the mesoporous ceria powder added in step (a) the gained copper salt solution, after the dissolving, leave standstill 48h, during not timing stir;
(c) mixed solution with step (b) places thermostatic drying chamber with 120 ℃ of dry 12h, is placed in the Muffle furnace with 200 ℃ of roasting 3h through grinding again, namely obtains copper doped cerium oxide catalysis material, and its specific area is 130.112m
2/ g, pore volume are 0.719cm
3/ g.
Wherein, the mesoporous ceria powder makes through following each step:
(1) gets 31.9726g cerous nitrate (Ce (NO
3)
36H
2O) and the 3.1452g citric acid be dissolved in the deionized water, continuous stirring 0.5h obtains the citric acid presoma of cerium, wherein the concentration of cerium salt is 0.74mol/L in the citric acid presoma of cerium;
(2) get the CTAB(softex kw) be dissolved in the deionized water, in 30 ℃ of lower continuous stirring 0.5h, obtaining concentration is the CTAB solution of 0.14mol/L;
(3) in 70 ℃ water-bath, be 5 ︰ 1 by the citric acid presoma of cerium and the volume ratio of CTAB solution, step (2) gained solution is joined in the citric acid presoma of step (1) gained cerium slowly, continuous stirring 2h adds NH again
3H
2O to the pH value of mixed liquor be till 10;
(4) mixture that step (3) is obtained places the autoclave of polytetrafluoroethylene (PTFE), then puts into thermostatic drying chamber and carries out crystallization 12 hours with 100 ℃, is precipitated thing;
(5) respectively with the sediment of absolute ethyl alcohol and deionized water washing step (4) gained each three times, place again thermostatic drying chamber with 100 ℃ of oven dry 12 hours, obtain powder;
(6) powder that step (5) is obtained places Muffle furnace with 500 ℃ of roasting 4h, namely obtains the mesoporous ceria catalyst material.
Embodiment 7
(a) get 0.9509g copper nitrate (Cu (NO
3)
23H
2O) be dissolved in the deionized water continuous stirring 1h; Wherein the concentration of Cu ion is 0.13120mol/mL;
(b) be 7 ︰ 1 by liquid-solid ratio, the mesoporous ceria powder added in step (a) the gained copper salt solution, after the dissolving, leave standstill 30h, during not timing stir;
(c) mixed solution with step (b) places thermostatic drying chamber with 110 ℃ of dry 12h, is placed in the Muffle furnace with 300 ℃ of roasting 2h through grinding again, namely obtains copper doped cerium oxide catalysis material, and its specific area is 114.753m
2/ g, pore volume are 0.652cm
3/ g.
Wherein, the mesoporous ceria powder makes through following each step:
(1) gets 17.1852g cerous nitrate (Ce (NO
3)
36H
2O) and the 5.2964g citric acid be dissolved in the deionized water, continuous stirring 1h obtains the citric acid presoma of cerium, wherein the concentration of cerium salt is 1.2mol/L in the citric acid presoma of cerium;
(2) get CTAB and be dissolved in the deionized water, in 30 ℃ of lower continuous stirring 1h, obtaining concentration is the CTAB solution of 0.25mol/L;
(3) in 65 ℃ water-bath, be 1 ︰ 1 by the citric acid presoma of cerium and the volume ratio of CTAB solution, step (2) gained solution is joined in the citric acid presoma of step (1) gained cerium slowly, continuous stirring 2h adds NH again
3H
2O to the pH value of mixed liquor be till 10;
(4) mixture that step (3) is obtained places the autoclave of polytetrafluoroethylene (PTFE), then carries out crystallization 12 hours with 120 ℃, is precipitated thing;
(5) respectively with the sediment of absolute ethyl alcohol and deionized water washing step (4) gained each three times, with oven dry in 100 ℃ 8 hours, obtain powder again;
(6) powder that step (5) is obtained namely obtains the mesoporous ceria powder with 300 ℃ of roasting 4h.
Embodiment 8
(a) get 1.2678g copper nitrate (Cu (NO
3)
23H
2O) be dissolved in the deionized water continuous stirring 1h; Wherein the concentration of Cu ion is 0.17492mol/mL;
(b) be 6 ︰ 1 by liquid-solid ratio, the mesoporous ceria powder added in step (a) the gained copper salt solution, after the dissolving, leave standstill 48h, during not timing stir;
(c) mixed solution with step (b) places thermostatic drying chamber with 110 ℃ of dry 10h, is placed in the Muffle furnace with 200 ℃ of roasting 3h through grinding again, namely obtains copper doped cerium oxide catalysis material, and its specific area is 102.572m
2/ g, pore volume are 0.495cm
3/ g.
Wherein, the mesoporous ceria powder makes through following each step:
(1) gets 52.240g cerous nitrate (Ce (NO
3)
36H
2O) and the 5.2964g citric acid be dissolved in the deionized water, continuous stirring 0.5h obtains the citric acid presoma of cerium, wherein the concentration of cerium salt is 0.4mol/L in the citric acid presoma of cerium;
(2) get CTAB and be dissolved in the deionized water, in 40 ℃ of lower continuous stirring 1h, obtaining concentration is the CTAB solution of 0.08mol/L;
(3) in 70 ℃ water-bath, be 5 ︰ 1 by the citric acid presoma of cerium and the volume ratio of CTAB solution, step (2) gained solution is joined in the citric acid presoma of step (1) gained cerium slowly, continuous stirring 2h adds NH again
3H
2O to the pH value of mixed liquor be till 10;
(4) mixture that step (3) is obtained places the autoclave of polytetrafluoroethylene (PTFE), then carries out crystallization 12 hours with 100 ℃, is precipitated thing;
(5) respectively with the sediment of absolute ethyl alcohol and deionized water washing step (4) gained each three times, with oven dry in 120 ℃ 8 hours, obtain powder again;
(6) powder that step (5) is obtained namely obtains the mesoporous ceria powder with 500 ℃ of roasting 4h.
Claims (7)
1. the preparation method of a copper doped cerium oxide catalysis material is characterized in that through following each step:
(a) get mantoquita and be dissolved in the solvent, continuous stirring 0.5～1h; Wherein the concentration of Cu ion is 0.00872～0.17492mol/mL;
(b) be 10 ︰, 1～6 ︰ 1 by liquid-solid ratio, the mesoporous ceria powder added in step (a) the gained copper salt solution, after the dissolving, leave standstill 24～48h, during not timing stir;
(c) with the mixed solution of step (b) with 110～120 ℃ of drying 10～12h, again after grinding with 200～300 ℃ of roasting 2～3h, namely obtain copper doped cerium oxide catalysis material.
2. the preparation method of copper doped cerium oxide catalysis material according to claim 1, it is characterized in that: the mantoquita of described step (a) is copper nitrate.
3. the preparation method of copper doped cerium oxide catalysis material according to claim 1 and 2, it is characterized in that: the mesoporous ceria powder of described step (b) makes through following each step:
(1) get 17.1852～52.240g cerium salt and 1.7～5.2964g citric acid is dissolved in the solvent, continuous stirring 0.5～1h obtains the citric acid presoma of cerium;
(2) get CTAB and be dissolved in the solvent, in 30～40 ℃ of lower continuous stirring 0.5～1h, obtaining concentration is the CTAB solution of 0.08～0.25mol/L;
(3) in 65～70 ℃ water-bath, be 5 ︰, 1～1 ︰ 1 by the citric acid presoma of cerium and the volume ratio of CTAB solution, step (2) gained solution is joined in the citric acid presoma of step (1) gained cerium slowly, continuous stirring 2～4h adds NH again
3H
2O to the pH value of mixed liquor be till 8.5～10;
(4) mixture that step (3) is obtained places the autoclave of polytetrafluoroethylene (PTFE), then carries out crystallization 8～12 hours with 100～120 ℃, is precipitated thing;
(5) respectively with the sediment of absolute ethyl alcohol and water wash step (4) gained each three times, in 100～120 ℃, dried 8～12 hours again, obtain powder;
(6) powder that step (5) is obtained namely obtains the mesoporous ceria powder with 300～500 ℃ of roastings.
4. the preparation method of copper doped cerium oxide catalysis material according to claim 3 is characterized in that: cerium salt is cerous nitrate in the described step (1).
5. the preparation method of copper doped cerium oxide catalysis material according to claim 3 is characterized in that: in the described step (1) in the citric acid presoma of cerium the concentration of cerium salt be 0.4～1.2mol/L.
6. the preparation method of copper doped cerium oxide catalysis material according to claim 3, it is characterized in that: the water of described step (5) is deionized water.
7. the preparation method of copper doped cerium oxide catalysis material according to claim 3, it is characterized in that: described solvent is deionized water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012104355333A CN103055875A (en) | 2012-11-05 | 2012-11-05 | Preparation method of catalytic material mixed by copper and cerium oxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012104355333A CN103055875A (en) | 2012-11-05 | 2012-11-05 | Preparation method of catalytic material mixed by copper and cerium oxide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103055875A true CN103055875A (en) | 2013-04-24 |
Family
ID=48098942
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012104355333A Pending CN103055875A (en) | 2012-11-05 | 2012-11-05 | Preparation method of catalytic material mixed by copper and cerium oxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103055875A (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103920486A (en) * | 2014-03-10 | 2014-07-16 | 苏州科技学院相城研究院 | Method for preparing multi-component cerium oxide based nanometer slice material |
| CN106732326A (en) * | 2016-11-18 | 2017-05-31 | 湖南稀土金属材料研究院 | Gettering material and preparation method thereof and getter |
| CN107287643A (en) * | 2017-07-07 | 2017-10-24 | 上海应用技术大学 | A kind of rare earth, nickel and copper codope ceria/ceria film and preparation method thereof |
| CN108607565A (en) * | 2018-04-19 | 2018-10-02 | 上海理工大学 | A kind of CuO/CeO2Catalyst and its preparation method and application |
| CN110433814A (en) * | 2019-08-01 | 2019-11-12 | 南昌大学 | The copper cerium catalyst preparation method of active specy high dispersive |
| CN110508288A (en) * | 2019-09-24 | 2019-11-29 | 福州大学 | A kind of preparation and its application of the rodlike Copper-cladding Aluminum Bar ceria with porous structure |
| CN111732121A (en) * | 2020-07-13 | 2020-10-02 | 济南大学 | CuInS2@CuCo-CeO2Composite nano probe and preparation method thereof |
| US10807071B2 (en) * | 2016-05-05 | 2020-10-20 | University Of Connecticut | Mesoporous metal doped cerium oxide catalyst |
| CN112063236A (en) * | 2020-09-09 | 2020-12-11 | 深圳九星印刷包装集团有限公司 | Carbon monoxide indicating ink and preparation method thereof |
| CN112657501A (en) * | 2020-12-23 | 2021-04-16 | 上海应用技术大学 | CO oxidation catalyst and preparation method and application thereof |
| CN114181068A (en) * | 2021-11-25 | 2022-03-15 | 江西省科学院能源研究所 | Cerium-doped copper oxalate nano material and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102309960A (en) * | 2011-06-03 | 2012-01-11 | 中南大学 | Preparation method of CeO2-ZrO2 material with highly ordered mesoporous pore canal |
-
2012
- 2012-11-05 CN CN2012104355333A patent/CN103055875A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102309960A (en) * | 2011-06-03 | 2012-01-11 | 中南大学 | Preparation method of CeO2-ZrO2 material with highly ordered mesoporous pore canal |
Non-Patent Citations (1)
| Title |
|---|
| 郑修成等: "Cu/CeO2催化剂的制备、表征及催化性能研究", 《石油化工》 * |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103920486A (en) * | 2014-03-10 | 2014-07-16 | 苏州科技学院相城研究院 | Method for preparing multi-component cerium oxide based nanometer slice material |
| US10807071B2 (en) * | 2016-05-05 | 2020-10-20 | University Of Connecticut | Mesoporous metal doped cerium oxide catalyst |
| CN106732326A (en) * | 2016-11-18 | 2017-05-31 | 湖南稀土金属材料研究院 | Gettering material and preparation method thereof and getter |
| CN106732326B (en) * | 2016-11-18 | 2019-02-26 | 湖南稀土金属材料研究院 | Gettering material and preparation method thereof and getter |
| CN107287643A (en) * | 2017-07-07 | 2017-10-24 | 上海应用技术大学 | A kind of rare earth, nickel and copper codope ceria/ceria film and preparation method thereof |
| CN108607565A (en) * | 2018-04-19 | 2018-10-02 | 上海理工大学 | A kind of CuO/CeO2Catalyst and its preparation method and application |
| CN108607565B (en) * | 2018-04-19 | 2021-02-26 | 上海理工大学 | CuO/CeO2Catalyst, preparation method and application thereof |
| CN110433814A (en) * | 2019-08-01 | 2019-11-12 | 南昌大学 | The copper cerium catalyst preparation method of active specy high dispersive |
| CN110508288A (en) * | 2019-09-24 | 2019-11-29 | 福州大学 | A kind of preparation and its application of the rodlike Copper-cladding Aluminum Bar ceria with porous structure |
| CN111732121A (en) * | 2020-07-13 | 2020-10-02 | 济南大学 | CuInS2@CuCo-CeO2Composite nano probe and preparation method thereof |
| CN112063236A (en) * | 2020-09-09 | 2020-12-11 | 深圳九星印刷包装集团有限公司 | Carbon monoxide indicating ink and preparation method thereof |
| CN112063236B (en) * | 2020-09-09 | 2022-04-15 | 深圳九星印刷包装集团有限公司 | Carbon monoxide indicating ink and preparation method thereof |
| CN112657501A (en) * | 2020-12-23 | 2021-04-16 | 上海应用技术大学 | CO oxidation catalyst and preparation method and application thereof |
| CN114181068A (en) * | 2021-11-25 | 2022-03-15 | 江西省科学院能源研究所 | Cerium-doped copper oxalate nano material and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103055875A (en) | Preparation method of catalytic material mixed by copper and cerium oxide | |
| CN102441396B (en) | The application of double perovskite type oxide oxygen carrier in hydrogen production of chemical chain and preparation method | |
| CN111545192B (en) | MOFs-derived perovskite catalyst, preparation method thereof and application of MOFs-derived perovskite catalyst in catalytic degradation of organic pollutants | |
| CN102951940A (en) | Mesoporous cerium dioxide material preparation method | |
| CN107456964A (en) | For the extra specific surface area perovskite type composite oxide catalyst of hydrocarbon low-temperature oxidation and its preparation | |
| Da et al. | Catalytic oxidation of diesel soot particulates over Pt substituted LaMn1-xPtxO3 perovskite oxides | |
| CN112592474B (en) | Benzotriazole covalent organic framework material and preparation method and application thereof | |
| CN101584981A (en) | Low-temperature preparation method of ceria nano-crystalline microsphere of graduation structure | |
| Phadtare et al. | Crystalline LaCoO3 perovskite as a novel catalyst for glycerol transesterification | |
| CN106025178B (en) | It is a kind of to prepare the method for metal oxide and its application in lithium cell cathode material by template of MOF | |
| CN101134574B (en) | Method for preparing manganese octahedron molecular sieve by employing formwork agent modified backflow process | |
| CN111389411A (en) | Perovskite electrocatalyst and preparation method and application thereof | |
| CN103374430B (en) | High-stability oxygen carrier, preparation method and applications | |
| Du et al. | ZIF-67/CoOOH cocatalyst modified g-C3N4 for promoting photocatalytic deep oxidation of NO | |
| CN103055841A (en) | Preparation method of cerium-tin composite oxide nano-catalyst, and prepared catalyst and application thereof | |
| CN102443453A (en) | Composite oxide oxygen carrier for chemical chain combustion as well as preparation method and application thereof | |
| WO2012091168A1 (en) | Catalyst for Decomposition of Sulfur Trioxide and Hydrogen Production Process | |
| CN103464165A (en) | Honeycomb cerium-copper composite multibasic oxide catalyst, and preparation method and application of catalyst | |
| CN103599790A (en) | Cobalt rare earth composite oxide catalyst for efficiently catalyzing complete oxidation of methane at low temperature | |
| Liu et al. | Investigation on different valence B-site ions doped Pr0. 6Sr0. 4FeO3-δ ceramic membrane for hydrogen production from water splitting | |
| CN102441397A (en) | Chemical looping combustion double perovskite type oxide oxygen carrier and preparation method and application thereof | |
| CN111135834A (en) | LaNixCo1-xO3Photo-thermal synergistic degradation toluene of La perovskite | |
| CN101269832A (en) | Process for producing nano-cerium dioxide with high-specific surface area and high hole capacity | |
| CN102500386A (en) | Preparation method for cerium nickel composite oxide catalytic material | |
| CN103464134B (en) | Carbon dioxide decomposition prepares the catalyst of carbon monoxide and method for making and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20130424 |