CN103752310A - Preparation and catalytic application of Au/ZnO/TiO2 catalyst - Google Patents

Preparation and catalytic application of Au/ZnO/TiO2 catalyst Download PDF

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CN103752310A
CN103752310A CN201310600449.7A CN201310600449A CN103752310A CN 103752310 A CN103752310 A CN 103752310A CN 201310600449 A CN201310600449 A CN 201310600449A CN 103752310 A CN103752310 A CN 103752310A
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tio
catalyst
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邵建军
鞠晓春
李家波
周学滨
张永坤
陈高杰
赵鹏远
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Abstract

The invention discloses preparation of Au / ZnO / TiO2 catalyst and catalytic application in low-temperature oxidation of carbon monoxide. The Au mass is 2% of the ZnO / TiO2 catalyst mass, and the atomic ratio of Zn to Ti in the ZnO / TiO2 composite oxide is 12 / 1. The CO low-temperature catalytic oxidation activity of the Au / ZnO / TiO2 catalyst is improved compared with that of Au / ZnO catalyst, and CO full conversion can be realized at 248K.

Description

Au/ZnO/TiO 2catalyst preparation and catalytic applications
Technical field
The present invention relates to a kind of Au/ ZnO/TiO 2the technology of preparing of catalyst, and the catalytic applications of this oxide in carbon monoxide under low temperature environmental oxidation.
Background technology
CO low temperature oxidation is widely used in environmental pollution control, breathing mask and the removal to trace carbon monoxide in the enclosed environments such as spaceship, submarine.In numerous catalyst systems, the Au catalyst supporting on suitable oxide presents good CO low temperature oxidation active [J. Mol. Catal. A 200 (2003) 229, J. Catal. 216 (2003) 425].Research shows, different sintering temperatures, Pretreatment atmosphere will directly affect the physical and chemical performance such as particle diameter, valence state of golden species, thereby Oxidation of Carbon Monoxide activity is also had to impact [Appl. Catal. A 226 (2002) 1.] in various degree.In the oxide carrier of golden load, on relevant ZnO carrier, the research of supported gold species is seldom reported.Wang etc. studied precipitating reagent and sintering temperature on the Au/ZnO catalyst of preparation under normal temperature moisture condition on the impact of Oxidation of Carbon Monoxide performance [Appl. Catal. A 239 (2003) 1].Au particle size and chemical state thereof are that [J. Catal. 144 (1993) 175 for the key factor that affects the redox property of catalyst, J. Catal. 240 (2006) 222], Wolf etc. [Appl. Catal. A. 226 (2002) 1-13] system research the catalytic performance of the Au catalyst that supports of different carriers, the oxidation activity that draws Au catalyst is not only relevant with the particle diameter of golden species, affected by gold and the strong interaction of support oxide.Kolov etc. have reported and have adopted compound and the settled metal hydroxides of phosphatization gold to make presoma, the precipitation of Au compound and the phase transformation of carrier are carried out simultaneously, can make to occur between Au and carrier more effective interaction, and then formed the Au catalyst [Appl. Catal. A. 182 (1999) 9-28, J. Catal. 181 (1999) 37-48] simultaneously with high activity and high stability.The adding to be of value to of auxiliary agent obtain the golden species of small particle diameter [J. Phys. Chem. B 109 (2005) 9678-9683].
Japanese Fujishima in 1972 and Honda are at n-type semiconductor TiO 2after upper discovery Single Crystalline Electrodes light decomposition water, photocatalysis oxidation method has caused numerous scientific research personnel's great attention, and effective application [Powd. Tech. 217 (2012) 585 – 590 progressively aspect curbing environmental pollution, have been obtained, Appl. Catal. B 144 (2014) 498 – 506, J. Photochem. Photobio. A 271 (2013) 45 – 55].Wolf etc. [Aplli.Catal.A 226 (2002) 1-13] to the catalytic activity of several carriers relatively in, be carried on TiO 2on Au catalyst higher to catalyzing carbon monoxide oxidation activity, think in load type gold catalyst, not only TiO2 as carrier be of value to obtain high dispersive, compared with the golden species of granule crystalline substance, the conspiracy relation of carrier and golden species is brought into play catalytic action equally.Zinc titanium presents good Oxidation of Carbon Monoxide active [I n t. j. Hydr. Energy. 37 (2012) 15140-15155] as the Au catalyst of carrier, and, because carrier also has considerable influence to load gold catalyst activity, the golden zinc titanium 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 Au/ZnO/TiO 2under the preparation method of catalyst and this catalyst low-temp reaction condition, realize the Quick Oxidation to carbon monoxide.
A kind of Au/ZnO/TiO 2catalyst, is characterized in that: in catalyst, the quality percentage composition of Au is ZnO/TiO 22%, ZnO/TiO 2in composite oxides, the atomic ratio of Zn and Ti is 12/1.Described Au/ ZnO/TiO 2catalyst, the Oxidation of Carbon Monoxide can further improve under catalyst low temperature environment is active.
Au/ZnO/TiO of the present invention 2its ZnO/TiO used of catalyst 2its preparation method of composite oxides, is characterized in that: the ZnO/TiO that the atomic ratio that adopts sluggish precipitation to prepare zinc and titanium is 12 to 1 2composite oxide catalysts.Under stirring condition, by the Zn (NO of 1 mol/L 3) 26H 2ti (the SO of O and 1 mol/L 4) 2the aqueous solution slowly splashes in the boiling urea liquid of debita spissitudo in proportion, aging, diafiltration, dry, roasting.
Au/ZnO/TiO provided by the present invention 2the preparation method of catalyst, is characterized in that: by gold loading, be ZnO/TiO 2the rate of charge of combined oxidation amount 2% measures HAuCl 44H 2o solution is also adjusted to debita spissitudo.Na with 0.1 mol/L 2cO 3solution is respectively by HAuCl 44H 2o solution and ZnO/TiO 2composite oxides suspension regulates pH to appropriate value, then at the temperature and high-speed stirred of 343 K, by HAuCl 44H 2o solution slowly splashes into ZnO/TiO 2in composite oxides suspension, aging, dry.
Au/ZnO/TiO provided by the present invention 2the preparation method of catalyst, is characterized in that: dried presoma under moving air through 533K roasting.
Au/ZnO/TiO of the present invention 2catalyst agent 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.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 condition of different temperatures to the conversion ratio variation diagram of CO oxidation reaction (GHSV=24000 ml/gh).
The specific embodiment
Below in conjunction with drawings and the embodiments, the present invention is further detailed explanation.
Embodiment 1
The ZnO/TiO that the atomic ratio of zinc and titanium is 12 to 1 2the preparation of composite oxides.The ZnO/TiO that the atomic ratio that adopts sluggish precipitation to prepare zinc and cerium is 12 to 1 2composite oxide catalysts.Under stirring condition, by the Zn (NO of 1 mol/L 3) 26H 2ti (the SO of O and 1 mol/L 4) 2the aqueous solution slowly splashes in the boiling urea liquid of debita spissitudo in proportion, after aging 10 h, uses deionized water diafiltration, then uses absolute ethanol washing, and 383 K are dried 20 h, 573 K roasting 4 h.
Embodiment 2
2%Au/ZnO/TiO 2the preparation of catalyst.The ZnO/TiO of choosing preparation 2composite oxides are carrier, take gold as active component, adopt deposition-precipitation method.By gold loading, be ZnO/TiO 2the rate of charge of combined oxidation amount 2% measures HAuCl 44H 2o solution is also adjusted to debita spissitudo.Na with 0.1 mol/L 2cO 3solution is respectively by HAuCl 44H 2o solution and ZnO/TiO 2composite oxides suspension regulates pH to appropriate value, then at the temperature and high-speed stirred of 343 K, by HAuCl 44H 2o solution slowly splashes into ZnO/TiO 2in composite oxides suspension.At this temperature, after aging 4 h, use deionized water diafiltration, after the dry 24h of 353 K temperature, under moving air through 533 k roasting 4h.
Embodiment 3
2%Au/ZnO/TiO 2the test of catalyst agent 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 catalyst fines 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 80 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.Before reaction, catalyst is air pretreatment 1 h under 533K 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 test result of catalyst to CO low temperature oxidation reaction.In temperature, be at the temperature of 248 K, catalyst is realized the conversion completely to carbon monoxide.

Claims (5)

1. an Au/ZnO/TiO 2catalyst, has catalytic oxidation function, it is characterized in that: in catalyst, the quality percentage composition of Au is ZnO/TiO 22%; ZnO//TiO 2in composite oxides, Zn is 12/1 with the atomic ratio of/Ti; Described Au/ZnO/TiO 2catalyst, the Oxidation of Carbon Monoxide can further improve under catalyst low temperature environment is active.
2. an Au/ZnO/TiO claimed in claim 1 2catalyst, its ZnO/TiO used 2its preparation method of composite oxides, is characterised in that: the ZnO/TiO that the atomic ratio that adopts sluggish precipitation to prepare zinc and cerium is 12 to 1 2composite oxide catalysts; Under stirring condition, by the Zn (NO of 1 mol/L 3) 26H 2ti (the SO of O and 1mol/L 4) 2the aqueous solution slowly splashes in the boiling urea liquid of debita spissitudo in proportion, after aging 10 h, uses deionized water diafiltration, then uses absolute ethanol washing, and 383 K are dried 20 h, 573 K roasting 4 h.
3. an Au/ZnO/TiO claimed in claim 1 2the preparation method of catalyst, is characterized in that: the ZnO/TiO of choosing preparation 2composite oxides are carrier, take gold as active component, adopt deposition-precipitation method; By gold loading, be ZnO/TiO 2the rate of charge of combined oxidation amount 2% measures HAuCl 44H 2o solution is also adjusted to debita spissitudo, with the Na of 0.1 mol/L 2cO 3solution is respectively by HAuCl 44H 2o solution and ZnO/TiO 2composite oxides suspension regulates pH to appropriate value, then at the temperature and high-speed stirred of 343 K, by HAuCl 44H 2o solution slowly splashes into ZnO/TiO 2in composite oxides suspension, at this temperature, after aging 4 h, use deionized water diafiltration, after the dry 24h of 353 K temperature, under moving air through 533 k roasting 4h.
4. an Au/ZnO/TiO claimed in claim 1 2the preparation method of catalyst, is characterized in that: dried presoma under moving air through 533 K roastings.
5. an Au/ZnO/TiO claimed in claim 1 2catalyst agent 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; 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.
CN201310600449.7A 2013-11-25 2013-11-25 Preparation and catalytic application of Au/ZnO/TiO2 catalyst Pending CN103752310A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105126838A (en) * 2015-08-04 2015-12-09 上海应用技术学院 Zinc oxide doped titanium dioxide-nano gold catalyst, preparation method and applications thereof
CN105289605A (en) * 2014-06-06 2016-02-03 邵建军 Au-Pt MnO2/ZnO/TiO2 catalyst
CN108704666A (en) * 2018-05-28 2018-10-26 福州大学 A kind of Au/ZnO-Alq3 catalyst and the preparation method and application thereof
CN115521275A (en) * 2022-09-28 2022-12-27 中国科学院兰州化学物理研究所 Method for preparing oxamide compound by using gold-based catalyst

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CN101722009A (en) * 2008-10-24 2010-06-09 中国石油化工股份有限公司 Nano-gold catalyst for deeply removing carbon monoxide, preparing method and application thereof

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EP0787679A1 (en) * 1996-01-30 1997-08-06 Daimler-Benz Aktiengesellschaft Process and apparatus for the recovery of a gas rich in hydrogen and poor in carbon monoxide
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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105289605A (en) * 2014-06-06 2016-02-03 邵建军 Au-Pt MnO2/ZnO/TiO2 catalyst
CN105126838A (en) * 2015-08-04 2015-12-09 上海应用技术学院 Zinc oxide doped titanium dioxide-nano gold catalyst, preparation method and applications thereof
CN108704666A (en) * 2018-05-28 2018-10-26 福州大学 A kind of Au/ZnO-Alq3 catalyst and the preparation method and application thereof
CN108704666B (en) * 2018-05-28 2021-01-29 福州大学 Au/ZnO-Alq3 catalyst, and preparation method and application thereof
CN115521275A (en) * 2022-09-28 2022-12-27 中国科学院兰州化学物理研究所 Method for preparing oxamide compound by using gold-based catalyst
CN115521275B (en) * 2022-09-28 2024-01-05 中国科学院兰州化学物理研究所 Method for preparing oxamide compounds by using gold-based catalyst

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Application publication date: 20140430