CN104645979B - 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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CN104645979B
CN104645979B CN201510055247.8A CN201510055247A CN104645979B CN 104645979 B CN104645979 B CN 104645979B CN 201510055247 A CN201510055247 A CN 201510055247A CN 104645979 B CN104645979 B CN 104645979B
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alkaline earth
catalyst
tio
metal oxide
earth metal
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CN104645979A (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

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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/TiO2- alkaline earth oxide microspherical catalyst and its preparation and application
Technical field
The invention belongs to CO catalytic oxidation removing field, and in particular to alkaline earth oxide（AEMO）In Au/TiO2Body Method of the effect of the electronic auxiliary and structural auxiliary agent that manifest in system to improve the oxidation CO removals of Au catalysts.
Background technology
CO is a kind of inflammable, explosive gas pollutant.Gas and family in imperfect combustion discharge gas, the mine of hydro carbons Discharge gas with gas range etc., containing a large amount of carbon monoxides.When CO contents are 2.0 × 10 in air-5 During mol/L, two is little When within people dizzy and vomiting phenomenon just occurs；When content reaches 1.2 %, meeting causing death in 1-3 min.For The removing of CO, has become one of main environmental problem, causes the common concern of people.
It is well known that Au nanometer particle loads are in reproducibility carrier TiO2（As active carrier）It is upper that there is excellent low temperature CO catalytic oxidation activity [J. Catal. 199 (2001) 48; Nature. 376 (1995) 238; J. Catal. 144 (1993) 175].Although its reaction mechanism is still controversial, generally believing the high electron density of golden nanometer particle has Promote the absorption and activation of CO to the antibonding orbital of CO beneficial to transfer electronics, and then beneficial to the catalysis oxidation of CO.Therefore, Hen Duofang Formula, takes such as N doping, sulfur doping on titania support, wraps up the facilitation of one layer of alumina flake and ferrum oxide, They think that it is considered as in Au/TiO to the interface on Au surfaces to set up the good electron transfer that promotes2What upper raising CO was aoxidized has Effect approach.And, our previous work also indicates that high-velocity electrons transfer and the high charge density of gold surface between gold and carrier It is advantageous for the catalysis oxidation of CO.The balance of electric charge is experienced between Au and carrier is improved the energy of whole system.Thus, The activation for being incorporated in Au catalyst the interfacial migration acceleration molecular oxygen for being possible to promote electronics of new pattern and specific carrying material And or even stable Au nano-particles size.
For this purpose, AEMO and Au nanoparticles are incorporated into TiO by this work by the method that hydro-thermal method combines precipitation deposition2It is micro- On balloon borne body, Au/TiO is prepared2- AEMO catalyst, and investigated its room temperature（25℃）Hydrogen-rich selective catalytic oxidation CO Energy.As a result find, the introducing of AEMO promotes the oxidation of CO really（Fig. 2）.Binding experiment and various phenetic analysis, AEMO pair Au/TiO2Facilitation be not to stablize the effect of golden nanometer particle size performance structure auxiliary agent, but by change dioxy Change the fermi level of titanium so as to change the electronic capability that it is transferred to Au nanoparticle surface, Au nanoparticles is rich in Absorption and activation of the high electric surface density beneficial to CO and molecular oxygen.
The content of the invention
The present invention is to be used as auxiliary agent to improve Au/TiO by alkaline earth oxide2The performance of CO catalytic oxidation, its mesh Be the low temperature active for improving such catalyst.The present invention is needed at relatively high temperatures just for conventional Au loaded catalysts The problem of energy CO catalytic oxidation, selects in Au/TiO2Load AEMO on catalyst to prepare Au/TiO2- AEMO supported catalysts Agent.AEMO not only acts as structural auxiliary agent, and is electronic auxiliary, so as to significantly improve the performance of its CO catalytic oxidation, greatly The use temperature of catalyst is reduced greatly, reduces energy consumption, and the method for preparing catalyst is simple, is conducive to promoting and answers With.
The present invention is implemented by following technical solution：
The support type Au/TiO of AEMO modifications is first obtained2Catalyst, then investigates it and is catalyzed in supported Au catalysts CO Effect in the reaction system of oxidation.
Above-mentioned reaction system is the continuous flow device of normal pressure, and the continuous flow device of the normal pressure is included with air inlet and outlet The quartz glass reactor of mouth, the inner chamber of the quartz glass reactor is filled with supported Au catalysts, the quartz glass Reactor the week side of boss is provided with follows bad condensate water device.
Above-mentioned supported Au catalysts are with TiO2It is active component for auxiliary agent and Au nanoparticles that microsphere is carrier, AEMO High-dispersion loading type catalyst, and in the supported Au catalysts active component A u content be 0.1-5wt%, remaining is Carrier.
Concrete preparation process is as follows：
（1）：4 ~ 6 mL tetra-n-butyl titanates are added in 100 ~ 200 mL ethylene glycol and are stirred 1 ~ 3 hour, then added The acetone of 200 ~ 400 mL obtains settled solution, then instills the water of 6 ~ 10 mL, and solution becomes at once white precipitate, stirring reaction 8 ~ 10 hours, centrifugation, deionized water was washed away after excess ions, was dried at 60～100 DEG C, and titanium dioxide microballoon sphere presoma is obtained.
（2）：By step（1）Obtained TiO2Presoma ultrasonic disperse in the water of 60 ~ 80 mL, according to TiO210 wt% The alkaline earth nitrate of respective amount is added, is then poured in the middle of politef hydro-thermal tank, 180 ~ 220 DEG C process 10 ~ 12 Hour.It is then centrifuged for, deionized water is washed away after excess ions, is dried at 60～100 DEG C, AEMO composite titanium dioxides is obtained micro- Ball.
（3）By step（2）Obtained 1～3 g carriers are added to the HAuCl containing 0.01～0.04 g4·3H2O solution In, the min of magnetic agitation 30～60, it is 8～12 to adjust its pH value with 0.5～1 mol/L NaOH solutions afterwards, centrifugation, deionized water After washing away excess ions, dry at 60～100 DEG C, obtain supported Au catalysts presoma.
（4）By step（3）Obtained Au catalyst precursors are placed in Muffle furnace 250 ~ 450 DEG C of roastings 2 ~ 5 hours, are obtained Supported Au catalysts.
Wherein, HAuCl4·3H2The mass concentration containing Au is 0.01～0.04 g/mL in O solution.
The AEMO of the present invention is as auxiliary agent to Au/TiO2The method of the facilitation of CO catalytic oxidation can be used for fuel cell CO in the removal of CO and air atmosphere under middle hydrogen-rich atmosphere2Conversion.
The present invention remarkable advantage be：（1）The present invention takes full advantage of carrier and turns with Au nanoparticles as active component Move to the transfer electronic capability of active component, when AEMO is carried on Au/TiO2On, due to the TiO that alkaline-earth metal causes2Quasiconductor The lifting of fermi level can strengthen the surface high electron density of active metal Au, so as to being conducive to the absorption and activation of CO and promoting The activation of oxygen, and then promote the catalysis oxidation of CO.（2）The preparation method and application operational approach of the present invention is simple, favorably In popularization and application.
Description of the drawings
Fig. 1 is Au/TiO2Au and TiO in-alkaline earth oxide microspherical catalyst2The effect schematic diagram of electron transfer.
Fig. 2 is the gained Au/TiO of embodiment 12And Au/TiO2The conversion ratio of-AEMO room temperature catalytic oxidation CO.Here, negate The result answered 6 hours calculates CO conversion ratios.
Fig. 3 is Au/TiO2And Au/TiO2The scanning electron microscope (SEM) photograph of-AEMO. a, Au/TiO2; b, Au/TiO2-MgO; c, Au/TiO2-CaO; d, Au/TiO2-SrO; e, Au/TiO2-BaO。
Fig. 4 is Au/TiO2And Au/TiO2The transmission electron microscope picture of-AEMO. a, Au/TiO2; b, Au/TiO2-MgO; c, Au/TiO2-CaO; d, Au/TiO2-SrO; e, Au/TiO2-BaO。
Fig. 5 is the gained Au/TiO of embodiment 12And Au/TiO2The XRD figure of-AEMO.
Fig. 6 is the gained Au/TiO of embodiment 12And Au/TiO2The Raman figure of-AEMO.
Specific embodiment
It is that the features described above and advantage of the present invention can be become apparent, special embodiment below, and coordinate accompanying drawing, make detailed Carefully it is described as follows, but the present invention is not limited to this.
Embodiment 1
Au/TiO2The preparation of-MgO catalyst
4mL tetra-n-butyl titanates are added in the middle of the ethylene glycol solution of 150 mL and are stirred 1 hour, then add 300 mL Acetone obtain settled solution, then instill the water of 8 mL, solution becomes at once white precipitate, and stirring reaction 8 hours, centrifugation is gone Ionized water is washed away after excess ions, is dried at 80 DEG C, and titanium dioxide microballoon sphere presoma is obtained.Titanium dioxide microballoon sphere presoma is surpassed Sound is scattered in the water of 80 mL, adds the magnesium nitrate of corresponding amount, is poured in the middle of politef hydro-thermal tank, and 180 DEG C process 10 Hour.It is then centrifuged for, deionized water is washed away after excess ions, is dried at 80 DEG C, the compound titanium dioxide microballoon spheres of MgO is obtained.Claim Take 2 g TiO2-MgO（Granular size is 60 ~ 80 mesh）To 100 mL water dispersed with stirring.The 2 mL concentration containing Au are then added to be The HAuCl of 0.01g/mL4Solution（1g HAuCl4 3H2The O HCl solution constant volumes of 100 mL 0.1mol/mL）.Contained with 20 mL It is 10 that the concentration of the NaOH of 0.1mol/L adjusts it, stir 3 hours, filter, washed away with distilled water be attached to precipitation on it is unnecessary from Son, after in 80 DEG C of oven for drying.Finally Au catalyst precursors obtained above are placed in in Muffle furnace 350 DEG C of roastings 3 hours, Prepared supported Au catalysts.
Embodiment 2
The performance evaluation of catalyst
Normal pressure with circulating condensing water of the catalyst oxidation CO performance evaluations obtained by embodiment 1 in designed, designed Carry out on continuous flow reactor.About 0.5 g Catalyst packings are in quartzy stacked rectangular capsules（Long 30mm* width 15mm* is high 1mm）In, catalyst particle size is about 0.2 ~ 0.3 mm（60 ~ 80 mesh）, CO and O in reaction gas2Content be fixed to 0.3 V% And 0.3 V%, He gas supplements gas, the mL/min of reaction gas overall flow rate about 100 as balance.Reaction temperature is adjusted by band circulating condensing water Control is 25oC (with thermocouple detection).Using CO, O in Agilent 7890D type gas chromatograph timing on-line analyses atmosphere2 And CO2Concentration, detector is TCD, and packed column is TDX-01, negate answer 6 hours result calculate CO conversion ratios.
CO conversion ratios are calculated with following equation：C = ( VinCO-VoutCO ) / V inCO× 100%
In formula, C is the conversion ratio of CO；VinCOAnd VoutCOCO contents respectively in air inlet and outlet（V%）.
In this way, the performance of the catalysis CO oxidations of various catalyst is have rated respectively, and its result is as shown in Figure 2.
Shown by result in Fig. 2, for each catalyst, Au/TiO2The catalyst of-AEMO complex shows and compares Au/TiO2Have Higher CO oxidation activities, i.e. AEMO is as auxiliary agent to Au/TiO2There are significant CO catalytic performances to improve；Can from Fig. 3 and Fig. 4 To find out, carrier has chondritic, is conducive to mass transfer and the heat transfer of catalyst, and with the increase in alkaline-earth metal cycle, TiO2Also with increase, active component has close particle diameter distribution to the radius of microsphere；From figure 5 it can be seen that because Au contains Amount is low, and TiO is only occurred in that in the XRD spectra of catalyst2With the diffraction cutting edge of a knife or a sword of AEMO, this also illustrates Au particles in catalyst point Dissipate uniform；From fig. 6 it can be seen that there is Au, AEMO and TiO in this catalyst2Interaction is there is between three.
The foregoing is only presently preferred embodiments of the present invention, all impartial changes done according to scope of the present invention patent with Modification, should all belong to the covering scope of the present invention.

Claims (3)

1. a kind of Au/TiO2- alkaline earth oxide microspherical catalyst, it is characterised in that：With alkaline earth oxide composite Ti O2 The high-dispersion loading type catalyst that microsphere is carrier, Au nanoparticles are active component, wherein alkaline earth oxide is used as electricity Sub- donor is again as structural auxiliary agent；
Its concrete preparation process is as follows：
（1）4 ~ 6 mL tetra-n-butyl titanates are added in 100 ~ 200 mL ethylene glycol and are stirred 1 ~ 3 hour, then addition 200 ~ The acetone of 400 mL obtains settled solution, then instills the water of 6 ~ 10 mL, and solution becomes at once white precipitate, stirring reaction 8 ~ 10 Hour, centrifugation, deionized water is washed away after excess ions, is dried at 60～100 DEG C, and titanium dioxide microballoon sphere presoma is obtained；
（2）By step（1）Obtained titanium dioxide microballoon sphere presoma ultrasonic disperse in the water of 60 ~ 80 mL, according to TiO210 Wt% add respective amount alkaline earth nitrate, be then poured in the middle of politef hydro-thermal tank, 180 ~ 220 DEG C process 10 ~ 12 hours；It is then centrifuged for, deionized water is washed away after excess ions, is dried at 60～100 DEG C, alkaline earth oxide is obtained and is combined Titanium dioxide microballoon sphere carrier；
（3）By step（2）Obtained 1～3 g carriers are added to the HAuCl that mass concentration containing Au is 0.01～0.04 g/mL4· 3H2In O solution, the min of magnetic agitation 30～60, it is 8～12 to adjust its pH value with 0.5～1 mol/L NaOH solutions afterwards, centrifugation, Deionized water is washed away after excess ions, is dried at 60～100 DEG C, obtains supported Au catalysts presoma；
（4）By step（3）Obtained Au catalyst precursors are placed in Muffle furnace 250 ~ 450 DEG C of roastings 2 ~ 5 hours, and load is obtained Type Au catalyst.
2. Au/TiO according to claim 12- alkaline earth oxide microspherical catalyst, it is characterised in that：In catalyst The content of active component A u is 0.1～5 wt.%.
3. a kind of Au/TiO as claimed in claim 12The application of-alkaline earth oxide microspherical catalyst, it is characterised in that： Described Au/TiO2- alkaline earth oxide microspherical catalyst is used for removal, the air gas of CO under hydrogen-rich atmosphere in fuel cell CO in atmosphere2Conversion and air in CO removing.
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