CN104645979A - Au/TiO2-alkaline earth metal oxide microsphere catalyst as well as preparation and application thereof - Google Patents

Au/TiO2-alkaline earth metal oxide microsphere catalyst as well as preparation and application thereof Download PDF

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CN104645979A
CN104645979A CN201510055247.8A CN201510055247A CN104645979A CN 104645979 A CN104645979 A CN 104645979A CN 201510055247 A CN201510055247 A CN 201510055247A CN 104645979 A CN104645979 A CN 104645979A
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alkaline earth
tio
catalyst
earth oxide
metal oxide
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CN104645979B (en
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戴文新
杨凯
陈旬
王绪绪
刘平
付贤智
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Fuzhou University
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Fuzhou University
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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
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

The invention discloses an Au/TiO2-alkaline earth metal oxide microsphere catalyst as well as preparation and application thereof. The Au/TiO2-alkaline earth metal oxide microsphere catalyst is prepared by the following steps: preparing a TiO2 microsphere precursor by virtue of a precipitation method firstly, and then hydrothermally preparing an alkaline earth metal oxide composite TiO2 microsphere carrier; precipitating and depositing active components loading Au nano-particles on the alkaline earth metal oxide composite TiO2 microsphere carrier; and finally, evaluating in a CO catalytic oxidation reaction system. According to the Au/TiO2-alkaline earth metal oxide microsphere catalyst as well as the preparation and the application disclosed by the invention, after being compounded in an Au/TiO2 microsphere system, alkaline earth metal oxide is capable of promoting the performance of an Au supported type heat catalyst of catalyzing CO oxidation; the alkaline earth metal oxide promoter is simple and feasible in introduction method and is beneficial for being applied to removing of CO in air and conversion of the CO in CO2.

Description

A kind of Au/TiO 2-alkaline earth oxide microspherical catalyst and Synthesis and applications thereof
Technical field
The invention belongs to CO catalytic oxidation and remove field, be specifically related to alkaline earth oxide (AEMO) at Au/TiO 2being used for of the electronic auxiliary manifested in system and structural auxiliary agent improves the method that Au catalyst oxidation CO removes.
Background technology
CO is a kind of inflammable, explosive gas pollutant.The discharge gas etc. of the imperfect combustion discharge gas of hydro carbons, the gas in mine and household gas cooker, all containing a large amount of carbon monoxide.When CO content in air is 2.0 × 10 -5during mol/L, within two hours, people just there will be dizzy and vomiting phenomenon; When content reaches 1.2 %, meeting causing death in 1-3 min.Removing for CO, has now become one of main environmental problem, has caused the common concern of people.
As everyone knows, Au nanometer particle load is at reproducibility carrier TiO 2(as active carrier) has excellent CO catalytic oxidation under low temperature activity [J. Catal. 199 (2001) 48; Nature. 376 (1995) 238; J. Catal. 144 (1993) 175].Although its reaction mechanism is still controversial, generally believes that the high electron density of golden nanometer particle is conducive to metastatic electron promotes CO absorption and activation to the antibonding orbital of CO, and then be beneficial to the catalytic oxidation of CO.Therefore, a lot of mode, titania support is taked as N doping, sulfur doping, and the facilitation of parcel one deck alumina flake and iron oxide, they think that setting up good promotion electro transfer is considered to be in Au/TiO to the interface on Au surface 2the effective way of upper raising CO oxidation.And our previous work also shows that high-velocity electrons transfer between gold and carrier and the high charge density of gold surface are the catalytic oxidations being conducive to CO.The balance experiencing electric charge between Au and carrier makes the energy of whole system be improved.Thus, new pattern and being incorporated into of certain band material likely promote the activation of the interfacial migration acceleration molecular oxygen of electronics and even stablize Au nano-particles size in Au catalyst.
For this reason, AEMO and Au nano particle is incorporated into TiO by the method that this work combines precipitation deposition by hydro-thermal method 2on microsphere supported, prepare Au/TiO 2– AEMO catalyst, and investigated its room temperature (25 DEG C) rich hydrogen selective catalytic oxidation CO performance.Found that, the introducing of AEMO facilitates the oxidation (Fig. 2) of CO really.Binding experiment and various phenetic analysis, AEMO is to Au/TiO 2facilitation be not the effect that stable golden nanometer particle size shows structural auxiliary agent, but change the electronic capability that it is transferred to Au nanoparticle surface by the fermi level that changes titanium dioxide, finally make Au nano particle be rich in absorption and activation that high electric surface density is beneficial to CO and molecular oxygen.
Summary of the invention
The present invention improves Au/TiO by alkaline earth oxide as auxiliary agent 2the performance of CO catalytic oxidation, its object is to the low temperature active improving this type of catalyst.The present invention is directed to that conventional Au loaded catalyst needs at relatively high temperatures could the problem of CO catalytic oxidation, selects at Au/TiO 2on catalyst, load AEMO prepares Au/TiO 2-AEMO loaded catalyst.AEMO not just as structural auxiliary agent, and is electronic auxiliary, thus significantly improves the performance of its CO catalytic oxidation, greatly reduce the serviceability temperature of catalyst, reduce energy consumption, and this method for preparing catalyst is simple, be conducive to applying.
The present invention implements by following technical solution:
The first support type Au/TiO of obtained AEMO modification 2catalyst, then investigates its effect in the reaction system of supported Au catalysts CO catalytic oxidation.
Above-mentioned reaction system is normal pressure continuous-flow device, this normal pressure continuous-flow device comprises the quartz glass reactor with air inlet and gas outlet, the inner chamber of described quartz glass reactor is filled with supported Au catalysts, and all sides of described quartz glass reactor are provided with follows bad condensate water device.
Above-mentioned supported Au catalysts is with TiO 2microballoon is carrier, AEMO is auxiliary agent and Au nano particle is the high-dispersion loading type catalyst of active component, and in described supported Au catalysts, the content of active component A u is 0.1-5wt%, and all the other are carrier.Concrete preparation process is as follows:
(1): 4 ~ 6 mL tetra-n-butyl titanates are joined in 100 ~ 200 mL ethylene glycol and stir 1 ~ 3 hour, the acetone then adding 200 ~ 400 mL obtains settled solution, then the water of 6 ~ 10 mL is instilled, solution becomes white precipitate at once, stirring reaction 8 ~ 10 hours, centrifugal, after deionized water washes away excess ions, dry at 60 ~ 100 DEG C, obtained titanium dioxide microballoon sphere presoma.
(2): the TiO obtained by step (1) 2presoma ultrasonic disperse in the water of 60 ~ 80 mL, according to TiO 210 wt% add the alkaline earth nitrate of respective amount, be then poured in the middle of polytetrafluoroethylene (PTFE) hydro-thermal tank, 180 ~ 220 DEG C of process 10 ~ 12 hours.Then centrifugal, after deionized water washes away excess ions, dry at 60 ~ 100 DEG C, obtained AEMO composite titanium dioxide microballoon.
(3) 1 ~ 3 g carrier that step (2) is obtained is added to HAuCl containing 0.01 ~ 0.04 g 43H 2in O solution, magnetic agitation 30 ~ 60 min, rear use 0.5 ~ 1 mol/L NaOH solution adjusts its pH value to be 8 ~ 12, after centrifugal, deionized water washes away excess ions, dries, obtain supported Au catalysts presoma at 60 ~ 100 DEG C.
(4) the Au catalyst precursor that step (3) is obtained is placed in Muffle furnace 250 ~ 450 DEG C of roastings 2 ~ 5 hours, obtained supported Au catalysts.
Wherein, HAuCl 43H 2mass concentration containing Au in O solution is 0.01 ~ 0.04 g/mL.
AEMO of the present invention as auxiliary agent to Au/TiO 2the method of the facilitation of CO catalytic oxidation can be used for CO in the removal of CO under hydrogen rich gas atmosphere in fuel cell and air atmosphere 2conversion.
Remarkable advantage of the present invention is: (1) the present invention for active component, takes full advantage of the metastatic electron ability that carrier is transferred to active component, when AEMO is carried on Au/TiO with Au nano particle 2on, due to the TiO that alkaline-earth metal causes 2the surperficial high electron density of the lifting meeting enhanced activity metal A u of semiconductor fermi, thus be conducive to the absorption of CO and the activation of activation and promotion oxygen, and then promote the catalytic oxidation of CO.(2) preparation method of the present invention and application operating method simple, be conducive to applying.
Accompanying drawing explanation
Fig. 1 is Au/TiO 2au and TiO in-alkaline earth oxide microspherical catalyst 2the effect schematic diagram of electro transfer.
Fig. 2 is embodiment 1 gained Au/TiO 2and Au/TiO 2the conversion ratio of-AEMO room temperature catalytic oxidation CO.Here, the result that negate is answered 6 hours calculates CO conversion ratio.
Fig. 3 is Au/TiO 2and Au/TiO 2the scanning electron microscope (SEM) photograph of-AEMO. a, Au/TiO 2; B, Au/TiO 2-MgO; C, Au/TiO 2-CaO; D, Au/TiO 2-SrO; E, Au/TiO 2-BaO.
Fig. 4 is Au/TiO 2and Au/TiO 2the transmission electron microscope picture of-AEMO. a, Au/TiO 2; B, Au/TiO 2-MgO; C, Au/TiO 2-CaO; D, Au/TiO 2-SrO; E, Au/TiO 2-BaO.
Fig. 5 is for being embodiment 1 gained Au/TiO 2and Au/TiO 2the XRD figure of-AEMO.
Fig. 6 is for being embodiment 1 gained Au/TiO 2and Au/TiO 2-AEMO Raman figure.
Detailed description of the invention
For above-mentioned feature and advantage of the present invention can be become apparent, special embodiment below, and coordinate accompanying drawing, be described in detail below, but the present invention is not limited to this.
Embodiment 1
Au/TiO 2the preparation of-MgO catalyst
Stir 1 hour in the middle of ethylene glycol solution 4mL tetra-n-butyl titanate being joined 150 mL, the acetone then adding 300 mL obtains settled solution, then the water of 8 mL is instilled, solution becomes white precipitate at once, stirring reaction 8 hours, centrifugal, after deionized water washes away excess ions, dry at 80 DEG C, obtained titanium dioxide microballoon sphere presoma.By titanium dioxide microballoon sphere presoma ultrasonic disperse in the water of 80 mL, add the magnesium nitrate of corresponding amount, be poured in the middle of polytetrafluoroethylene (PTFE) hydro-thermal tank, 180 DEG C process 10 hours.Then centrifugal, after deionized water washes away excess ions, dry at 80 DEG C, the titanium dioxide microballoon sphere of obtained MgO compound.Take 2 g TiO 2-MgO(granular size is 60 ~ 80 orders) to 100 mL water dispersed with stirring.Then adding 2 mL containing Au concentration is the HAuCl of 0.01g/mL 4solution (1g HAuCl 43H 2the O HCl solution constant volume of 100 mL 0.1mol/mL).Adjust it to be 10 with 20 mL containing the concentration of NaOH of 0.1mol/L, stirs 3 hours, filtration, washes away the excess ions be attached in precipitation with distilled water, after 80 DEG C of oven for drying.Finally above-mentioned obtained Au catalyst precursor is placed in Muffle furnace 350 DEG C of roastings 3 hours, obtained supported Au catalysts.
Embodiment 2
The performance evaluation of catalyst
Catalyst oxidation CO performance evaluation obtained by embodiment 1 is carried out on the normal pressure continuous-flow reaction unit of the band circulating condensing water of designed, designed.About 0.5 g Catalyst packing is in quartzy stacked rectangular capsules (long 30mm* wide 15mm* height 1mm), and catalyst particle size is about 0.2 ~ 0.3 mm(60 ~ 80 order), CO and O in reaction gas 2content be fixed as 0.3 V% and 0.3 V%, He gas respectively and supplement gas as balance, reaction gas overall flow rate about 100 mL/min.Reaction temperature regulates and controls 25 by being with circulating condensing water oc (joining thermocouple to detect).Adopt CO, O in Agilent 7890D type gas chromatograph timing on-line analysis atmosphere 2and CO 2concentration, detector is TCD, and packed column is TDX-01, and the result that negate is answered 6 hours calculates CO conversion ratio.
The following formulae discovery of CO conversion ratio: C=(V inCO-V outCO)/V inCO× 100%
In formula, C is the conversion ratio of CO; V inCOand V outCObe respectively air inlet and the CO content (V%) in giving vent to anger.
In this way, the performance that the catalysis CO that have rated various catalyst is respectively oxidized, its result as shown in Figure 2.
Shown by result in Fig. 2, for each catalyst, Au/TiO 2au/TiO is compared in the catalyst display of-AEMO compound 2have higher CO oxidation activity, namely AEMO as auxiliary agent to Au/TiO 2significant CO catalytic performance is had to improve; As can be seen from Fig. 3 and Fig. 4, carrier has chondritic, is conducive to mass transfer and the heat transfer of catalyst, and along with the increase in alkaline-earth metal cycle, TiO 2the radius of microballoon is also along with increase, and active component has close domain size distribution; As can be seen from Figure 5, because Au content is low, in the XRD spectra of catalyst, only there is TiO 2with the diffraction cutting edge of a knife or a sword of AEMO, this also illustrates being uniformly dispersed of Au particle in catalyst; As can be seen from Figure 6, there is Au, AEMO and TiO in this catalyst 2interaction is there is between three.
The foregoing is only preferred embodiment of the present invention, all equalizations done according to the present patent application the scope of the claims change and modify, and all should belong to covering scope of the present invention.

Claims (5)

1. an Au/TiO 2-alkaline earth oxide microspherical catalyst, is characterized in that: with alkaline earth oxide composite Ti O 2the high-dispersion loading type catalyst that microballoon is carrier, Au nano particle is active component, wherein alkaline earth oxide as electronq donor again as structural auxiliary agent.
2. Au/TiO according to claim 1 2-alkaline earth oxide microspherical catalyst, is characterized in that: in catalyst, the content of active component A u is 0.1 ~ 5 wt.%.
3. prepare Au/TiO as claimed in claim 1 for one kind 2the method of-alkaline earth oxide microspherical catalyst, is characterized in that: comprise the following steps:
(1) hydro-thermal method is utilized to prepare alkaline earth oxide composite Ti O 2microsphere supported;
(2) in the upper gold chloride of microsphere supported upper use 0.1 ~ 1 M NaOH solution precipitation deposition of step (1);
(3) presoma 250 ~ 450 DEG C of roastings step (2) obtained 2 ~ 5 hours, obtained described Au/TiO 2-alkaline earth oxide microspherical catalyst.
4. method according to claim 3, is characterized in that: be microsphere supportedly placed in 0.005 ~ 0.02g/mL HAuCl by shaping 43H 2in O solution, under then constantly stirring, add 0.1 ~ 0.25 mol/LNaOH solution wherein, regulate pH to be 8 ~ 12, stirred at ambient temperature 2 ~ 7 h, centrifugal, wash away excess ions by deionized water after, 60 ~ 100 DEG C of vacuum drying, last 250 ~ 450 DEG C of roastings 2 ~ 5 hours, obtained described Au/TiO 2-alkaline earth oxide microspherical catalyst.
5. an Au/TiO as claimed in claim 1 2the application of-alkaline earth oxide microspherical catalyst, is characterized in that: described Au/TiO 2-alkaline earth oxide microspherical catalyst is used for CO in the removal of CO under hydrogen rich gas atmosphere in fuel cell, air atmosphere 2conversion and air in the removing of CO.
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Cited By (1)

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Publication number Priority date Publication date Assignee Title
CN106881086A (en) * 2015-12-12 2017-06-23 中国科学院大连化学物理研究所 The preparation of gallate spinel supported nanometer gold catalyst and catalyst and application

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CN101204655A (en) * 2006-12-21 2008-06-25 中国人民解放军63971部队 Process for preparing nanometer gold catalyst

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Publication number Priority date Publication date Assignee Title
CN106881086A (en) * 2015-12-12 2017-06-23 中国科学院大连化学物理研究所 The preparation of gallate spinel supported nanometer gold catalyst and catalyst and application
CN106881086B (en) * 2015-12-12 2019-08-02 中国科学院大连化学物理研究所 The preparation of gallate spinel supported nanometer gold catalyst and catalyst and application

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