CN103752317A - Preparation of Co3O4 / CeO2 composite oxide and catalytic application - Google Patents
Preparation of Co3O4 / CeO2 composite oxide and catalytic application Download PDFInfo
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- CN103752317A CN103752317A CN201310600448.2A CN201310600448A CN103752317A CN 103752317 A CN103752317 A CN 103752317A CN 201310600448 A CN201310600448 A CN 201310600448A CN 103752317 A CN103752317 A CN 103752317A
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- 239000002131 composite material Substances 0.000 title claims abstract description 21
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 title claims abstract description 8
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 title claims abstract description 6
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 title claims abstract description 6
- 239000003054 catalyst Substances 0.000 claims abstract description 23
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 18
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 230000003647 oxidation Effects 0.000 claims abstract description 13
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000012495 reaction gas Substances 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 229910052684 Cerium Inorganic materials 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 230000032683 aging Effects 0.000 claims description 6
- 238000011026 diafiltration Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 239000010453 quartz Substances 0.000 claims description 3
- 239000013049 sediment Substances 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 230000005587 bubbling Effects 0.000 claims description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 description 10
- 239000010941 cobalt Substances 0.000 description 10
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 229910000420 cerium oxide Inorganic materials 0.000 description 3
- 229910000428 cobalt oxide Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 3
- 230000010718 Oxidation Activity Effects 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- MNUSFSHFJMPRIV-UHFFFAOYSA-N [Co].[Ce] Chemical compound [Co].[Ce] MNUSFSHFJMPRIV-UHFFFAOYSA-N 0.000 description 1
- 210000002659 acromion Anatomy 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 150000001785 cerium compounds Chemical class 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000029058 respiratory gaseous exchange Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/20—Capture or disposal of greenhouse gases of methane
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Abstract
The invention discloses preparation of Co3O4 / CeO2 composite oxide and catalytic application in low-temperature oxidation of carbon monoxide. The atomic ratio of Co to Ce in the Co3O4 / CeO2 composite oxide is 19 / 1. The Co3O4 / CeO2 composite oxide has a strong oxidation function, at a lower temperature (196K), the conversion rate of the catalyst for CO oxidation is 99%, and can be continuously maintained for more than 480min, and when a reaction gas contains 3.1vol.% of moisture, and the temperature is 383K, the CO conversion rate still maintains at 81% after 2580min of reaction.
Description
Technical field
The present invention relates to a kind of Co
3o
4/ CeO
2the technology of preparing of composite oxides and the catalytic applications of this oxide in CO low temperature oxidation.
Background technology
CO low temperature oxidation is widely used in weather monitoring, breathing mask and the removal to trace carbon monoxide in the enclosed environments such as spaceship, submarine.Research discovery, part transition metal oxide also can be realized the low-temperature oxidation to carbon monoxide.Cunningham etc. [Catal. Lett. 25 (1994) 257] report Co
3o
4under drying condition, can realize the conversion completely to carbon monoxide in the low temperature of 197 K.Thorm hlen etc. [J.Catal.188 (1999) 300] report is by Co
3o
4support in Al
2o
3the upper temperature at 210 K can make the conversion ratio of carbon monoxide reach 50%.In practical application and unstripped gas, the existence of water is inevitable, due to Co
3o
4there is strong absorptive, cause the rapid deactivation [Appl.Catal.B 48 (2004) 267, Appl Catal, A 251 (2003) 143] of catalyst.Cerium oxide is as second component, add in cobalt oxide catalyst, can improve the ability of the water-fast vapour of catalyst, likely improve the ability of the storage/release oxygen of catalyst, the carrying out of accelerating oxidation reaction, meanwhile, having of cerium oxide may make cobalt oxide can disperse better [Appl.Catal.A 251 (2003) 143].M. Kang, waits [Appl. Catal. A 251 (2003) 143-156] to study period 4 transition metal oxide and supports in CeO
2the research of upper CO reaction, finds CoO
x/ CeO
2cO is presented to optimum activity, and steam may be that the competitive Adsorption mechanism on adsorption activity position causes due to vapour molecule and reaction gas molecule to the inhibitory action of oxidation reaction.Co
3o
4comprise two kinds of cations, i.e. tetrahedral Co
2+and octahedral Co
3+ion, the atomic ratio of the two is 1:2, the Co of formation
2+/ Co
3+in to the oxidizing process of CO, can there is the catalytic action of redox cycle.By further research, find, the sintering temperature in catalyst preparation process affects consumingly it and resists moisture capacity, and the sintering temperature of thinking fit can obtain better crystalline form.F. Grillo etc. [Appl. Catal. B 48 (2004) 267] finds by XPS research, and with the increase of cobalt content, acromion is than reducing, and in meaning cerium oxide, partial oxygen enters in cobalt/cobalt oxide, forms the cobalt of high valence state, and this may be and CeO
2oxygen memory action relevant.Result shows, cerium, for cobalt provides oxygen, makes cobalt keep the state of high valence state, and has higher activity.Preparation method affects large [Appl. Catal. B 97 (2010) 28 – 35, Appl. Catal. B 119 – 120 (2012) 62 – 73] to the catalytic activity of catalyst.Shao Jianjun etc. [catalysis journal, 28 (2007) 163-169] have synthesized carbon monoxide are presented cobalt, the ce composite oxidation catalyst of excellent low-temperature oxidation activity and reported.Because cobalt cerium comparison catalyst is at large [Applied Catalysis B 66 (2006) 217 – 227 of catalytic activity impact, Appl. Catal. B 128 (2012) 21 – 30], the cobalt and cerium compound oxide catalyst of studying best proportioning is still a challenging problem to the low-temperature oxidation of carbon monoxide.
Summary of the invention
The object of the present invention is to provide a kind of Co
3o
4/ CeO
2under the preparation method of composite oxides and this composite oxide catalytic low-temp reaction condition, realize the Quick Oxidation to carbon monoxide.
A kind of Co
3o
4/ CeO
2composite oxides, is characterized in that: in composite oxides, the atomic ratio of Co and Ce is 19/1, can further improve the oxidation activity of composite oxide catalysts.
Co of the present invention
3o
4/ CeO
2its preparation method of composite oxides, is characterized in that: cobalt nitrate and the cerous nitrate mixed solution of metering ratio are slowly splashed into 0.2 mol/L Na in proportion
2cO
3in the aqueous solution, with 0.2 mol/L NaOH, regulate pH value to 10.0, and at this temperature after aging 4 h, diafiltration.Then, the sediment obtaining is again mixed by deionized water and stirred, and slowly splash into appropriate H
2o
2(30%).After aging 1 h, again use deionized water diafiltration, 383 K are dried 12 h, at 538 K roasting temperature 4 h.The method is characterized in that can make ceria and cobaltosic oxide mixing more evenly and obtain the Co of high valence state
3+.
Co of the present invention
3o
4/ CeO
2composite oxide catalysts can be used for equally changing carbon low-temperature oxidation, it is characterized in that: in the miniature fixed bed quartz tube reactor of normal pressure, carry out, HP-6890 type gas chromatograph on-line analysis for reactor outlet gas, and nickel converter is installed before fid detector, in hydrogen atmosphere respectively by CO and CO
2be converted into quantitatively CH
4.
Accompanying drawing explanation
Fig. 1 be catalyst under differential responses condition to the variation diagram of the stability time of CO oxidation reaction (GHSV=15000 ml/gh).
The specific embodiment
Below in conjunction with drawings and the embodiments, the present invention is further detailed explanation.
Embodiment 1
The Co that the atomic ratio of cobalt and cerium is 19 to 1
3o
4/ CeO
2the preparation of composite oxides.The Co that the atomic ratio that adopts precipitation oxidizing process to prepare cobalt and cerium is 19 to 1
3o
4/ CeO
2composite oxide catalysts.Under 333K and stirring condition, by the Co (NO of 1 mol/L
3)
26H
2ce (the NO of O and 1 mol/L
3)
36H
2the O aqueous solution slowly splashes in the aqueous sodium carbonate of 0.2 mol/L in proportion, regulates pH value to 10.0, and after aging 4 h, use deionized water diafiltration with 0.2 mol/L NaOH at this temperature.Then, the sediment obtaining is again mixed by deionized water and stirred, and slowly splash into appropriate H
2o
2(30%).After aging 1 h, again use deionized water diafiltration, 383 K are dried 12 h, at 538 K roasting temperature 4 h.
Embodiment 2
The Co that the atomic ratio of cobalt and cerium is 19 to 1
3o
4/ CeO
2the test of composite oxide catalysts catalyzing carbon monoxide oxidation reaction performance.The active testing of catalyst is to carry out in the miniature fixed bed quartz tube reactor of normal pressure.By composite oxide power compression molding, and fragmentation is screened to 40-60 order, and 200 mg are contained in the crystal reaction tube of Ф=6 mm.Reaction gas CO/O
2/ He=1 %/21 %/He, gas overall flow rate is 50 ml/min.Low-temp reaction is that U-shaped reactor is immersed in liquid nitrogen container, by regulating the distance of catalyst and liquid nitrogen liquid level to control reaction temperature.Moisture condition is that reaction gas is realized to (moisture content is 3.1 vol%) by 298 K constant water bath box bubblings.Before reaction, catalyst is air pretreatment 1 h under 538 K first.HP-6890 type gas chromatograph on-line analysis for reactor outlet gas, and nickel converter is installed before fid detector, in hydrogen atmosphere respectively by CO and CO
2be converted into quantitatively CH
4.Fig. 1 is the stability test result of catalyst to CO low temperature oxidation reaction.At dried feed gas and 196 K temperature, catalyst surpasses 480 min to the reaction time of the conversion of 99 % of CO.In reaction gas, containing 3.1 % volume ratio steam, temperature, be to react after 2580 min under the condition of 383 K, catalyst maintains 81% to the conversion ratio of carbon monoxide.
Claims (3)
1. a Co
3o
4/ CeO
2composite oxides, have catalytic oxidation function, it is characterized in that: in composite oxides, the atomic ratio of Co and Ce is 19/1, shows good performance aspect catalytic oxidation of carbon monoxide under low temperature.
2. a Co claimed in claim 1
3o
4/ CeO
2the preparation method of composite oxides, is characterized in that: cobalt nitrate and the cerous nitrate mixed solution of metering ratio are slowly splashed into 0.2 mol/L Na in proportion
2cO
3in the aqueous solution, with 0.2 mol/L NaOH, regulate pH value to 10.0, and at this temperature after aging 4 h, diafiltration; Then, the sediment obtaining is again mixed by deionized water and stirred, and slowly splash into appropriate H
2o
2(30%), after aging 1 h, again use deionized water diafiltration, 383 K are dried 12 h, at 538 K roasting temperature 4 h; The method is characterized in that can make ceria and cobaltosic oxide mixing more evenly and obtain the Co of high valence state
3+.
3. a Co claimed in claim 1
3o
4/ CeO
2composite oxide catalysts can be used for CO low temperature oxidation, it is characterized in that: in the miniature fixed bed quartz tube reactor of normal pressure, carry out; Low-temp reaction is that U-shaped reactor is immersed in liquid nitrogen container, by regulating the distance of catalyst and liquid nitrogen liquid level to control reaction temperature; Moisture condition is that reaction gas is realized to (moisture content is 3.1 vol%) by 298 K constant water bath box bubblings; HP-6890 type gas chromatograph on-line analysis for reactor outlet gas, and nickel converter is installed before fid detector, in hydrogen atmosphere respectively by CO and CO
2be converted into quantitatively CH
4.
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|---|---|---|---|
| CN201310600448.2A CN103752317A (en) | 2013-11-25 | 2013-11-25 | Preparation of Co3O4 / CeO2 composite oxide and catalytic application |
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|---|---|---|---|
| CN201310600448.2A CN103752317A (en) | 2013-11-25 | 2013-11-25 | Preparation of Co3O4 / CeO2 composite oxide and catalytic application |
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| Publication Number | Publication Date |
|---|---|
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104338533A (en) * | 2014-09-09 | 2015-02-11 | 上海纳米技术及应用国家工程研究中心有限公司 | Cobaltosic oxide catalyst subjected to hydrogen peroxide surface treatment and preparation and application of cobaltosic oxide catalyst |
| CN105148934A (en) * | 2014-06-06 | 2015-12-16 | 邵建军 | Preparation and catalytic application of PtMnO2/Co3O4/CeO2 |
| 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 |
| CN105854887A (en) * | 2016-03-25 | 2016-08-17 | 武汉工程大学 | Cobalt-cerium double-metal oxide nanosphere and preparation method thereof |
| CN106378142A (en) * | 2016-08-30 | 2017-02-08 | 上海化工研究院 | Catalyst for removing alkene material flow impurity through deep purification at room temperature, preparation method and application thereof |
| CN106807392A (en) * | 2017-03-07 | 2017-06-09 | 北京工业大学 | A kind of MoCeCoO for low temperature CO catalysisXThe preparation and application of catalyst |
| CN107362804A (en) * | 2017-07-14 | 2017-11-21 | 重庆交通大学 | Flower-shaped Co3O4‑CeO2The preparation method of composite oxide catalysts |
| CN109546001A (en) * | 2018-11-22 | 2019-03-29 | 京东方科技集团股份有限公司 | A kind of display panel and preparation method thereof, display device |
| CN109647403A (en) * | 2018-12-13 | 2019-04-19 | 西北大学 | A kind of controllable method for preparing of cobaltosic oxide catalyst and its application in CO methanation |
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2013
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Non-Patent Citations (4)
| Title |
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Cited By (15)
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|---|---|---|---|---|
| CN105148934A (en) * | 2014-06-06 | 2015-12-16 | 邵建军 | Preparation and catalytic application of PtMnO2/Co3O4/CeO2 |
| CN104338533B (en) * | 2014-09-09 | 2016-04-27 | 上海纳米技术及应用国家工程研究中心有限公司 | Hydrogen peroxide surface-treated cobaltosic oxide catalyst and Synthesis and applications thereof |
| CN104338533A (en) * | 2014-09-09 | 2015-02-11 | 上海纳米技术及应用国家工程研究中心有限公司 | Cobaltosic oxide catalyst subjected to hydrogen peroxide surface treatment and preparation and application of cobaltosic oxide catalyst |
| CN105327706B (en) * | 2015-09-23 | 2018-07-03 | 上海交通大学 | A kind of catalyst of low-temperature catalyzed removal environmental contaminants and preparation method thereof |
| 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 |
| CN105854887A (en) * | 2016-03-25 | 2016-08-17 | 武汉工程大学 | Cobalt-cerium double-metal oxide nanosphere and preparation method thereof |
| CN105854887B (en) * | 2016-03-25 | 2018-06-08 | 武汉工程大学 | A kind of cobalt cerium bimetallic oxide nanosphere and preparation method thereof |
| CN106378142A (en) * | 2016-08-30 | 2017-02-08 | 上海化工研究院 | Catalyst for removing alkene material flow impurity through deep purification at room temperature, preparation method and application thereof |
| CN106378142B (en) * | 2016-08-30 | 2019-09-27 | 上海化工研究院有限公司 | Catalyst for deep purification and removal of impurities in olefin stream at room temperature and its preparation and application |
| CN106807392A (en) * | 2017-03-07 | 2017-06-09 | 北京工业大学 | A kind of MoCeCoO for low temperature CO catalysisXThe preparation and application of catalyst |
| CN107362804A (en) * | 2017-07-14 | 2017-11-21 | 重庆交通大学 | Flower-shaped Co3O4‑CeO2The preparation method of composite oxide catalysts |
| CN107362804B (en) * | 2017-07-14 | 2020-04-28 | 重庆交通大学 | Preparation method of flower-like Co3O4-CeO2 composite oxide catalyst |
| CN109546001A (en) * | 2018-11-22 | 2019-03-29 | 京东方科技集团股份有限公司 | A kind of display panel and preparation method thereof, display device |
| CN109647403A (en) * | 2018-12-13 | 2019-04-19 | 西北大学 | A kind of controllable method for preparing of cobaltosic oxide catalyst and its application in CO methanation |
| CN109647403B (en) * | 2018-12-13 | 2021-12-03 | 西北大学 | Controllable preparation method of cobaltosic oxide catalyst and application of cobaltosic oxide catalyst in CO methanation |
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