CN108704666A - A kind of Au/ZnO-Alq3 catalyst and the preparation method and application thereof - Google Patents
A kind of Au/ZnO-Alq3 catalyst and the preparation method and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 14
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/864—Removing carbon monoxide or hydrocarbons
-
- B01J35/39—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/10—Noble metals or compounds thereof
- B01D2255/106—Gold
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20792—Zinc
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/80—Type of catalytic reaction
- B01D2255/802—Photocatalytic
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/502—Carbon monoxide
-
- 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
Abstract
The invention discloses a kind of Au/ZnO-Alq3 catalyst and the preparation method and application thereof, it is that organic semiconducting materials Alq3 is added in the presoma of ZnO, the modified ZnO carriers of Alq3 are made, then pass through coprecipitation, active component A u nano-particles are dispersed in the modified ZnO carrier surfaces of Alq3, the loaded catalyst Au/ZnO-Alq3 of high dispersive is made.The introducing of Alq3 improves the activity of CO catalytic oxidation under gained catalyst visible light in the present invention, so that the catalyst is suitable for the room temperature removal of CO under air or other occasions, preparation method is simple and practicable, is conducive to promote and apply.
Description
Technical field
The invention belongs to visible light catalytic oxidation CO technical fields, and in particular to a kind of Au/ZnO-Alq3 catalyst and its
Preparation method and application.
Background technology
CO is typical inflammable, explosive, toxic gas, easily with the hemoglobin in blood（Hb）In conjunction with.When in air
When containing ppm grades of CO, human poisoning will be caused；Can be made one when CO contents reach 400ppm in air occur headache, it is tired,
The feelings such as nausea；When content reaches 600ppm, human hair life palpitaition is hyperfunction, and with collapse symptom；When content is more than 1000ppm
When, lethargic sleep, spasm will occur in people, will be choked to death when serious.In the most hydrogen fuel cell of current research, micro CO
It will make the poisonings such as catalyst and electrode, wherein most typical is exactly proton membrane exchange fuel cell（PEMFC）.In reforming gas
0.5-1.0 vol% CO will make PEMFC electrodes be poisoned, it is necessary to which the CO concentration in fuel gas is down to 100ppm or less.Equally,
In the industrial production, the presence of trace amounts of CO can cause the catalyst poisoning of some synthetic reactions, totally unfavorable to industrial production, such as
Removing must be just purified when containing trace amounts of CO in ammonia synthesizing industry unstripped gas.Therefore, how efficiently to remove CO and have become and work as
One of preceding main Environmental Problems.
Current most common CO minimizing technologies have physical method and chemical stripping method, and wherein physical method includes cryogenic separation
Method, pressure swing adsorption method, membrane separation process, solvent absorption etc.；Chemical stripping method include low-temperature water gas shift method, methanation and
Catalytic oxidation etc..But since the cleaning equipment of CO requires, temperature is low, light-weight, small, easy to operate, technique is simple
The features such as list, continuous work, therefore physical cleaning method is not easy to use；And low-temperature water gas shift reaction method is by CO and water vapour
Reaction is converted into CO2And H is generated simultaneously2, it is very suitable for the removing system of CO, but speed is reacted in the reaction under cryogenic
Rate is relatively slow, and reaction is also limited by thermodynamical equilibrium, it is difficult to reach and CO is dropped to ppm grades of requirement, so only
Suitable for removal of CO concentration when higher；CO methanations are the technique of a comparative maturity, but can be disappeared during the reaction
Consume a large amount of hydrogen（1 mole of CO of removal will consume 3 moles of H2）, system inside is it may also happen that Reversed Water-gas Shift is anti-
It answers.Therefore, it studies low（Often）Temperature（<100 ℃）Under the conditions of CO catalysis oxidations, to eliminate CO pollution more is of practical significance.
Currently, about CO catalytic oxidation most study it is exactly by active component noble metal（Pd, Au, Ag, Rh and Pt etc.）
It loads on certain carrier（Al2O3、SiO2、TiO2Deng）, to prepare the catalysis for showing certain catalytic oxidation effect to CO
Agent.The study found that for Au/ZnO systems, it is not only right when gold nano grain is highly dispersed at metal oxide carrier surface
The oxidation of CO has fabulous catalytic activity, and has good water-resistance, stability and humidity enhancement effect；And ZnO because
It is ground in photochemical catalytic oxidation CO by vast with the advantages such as suitable energy gap, high photoelectric conversion efficiency, inexpensive
The person's of studying carefully dotes on.It is poor since there are stability, easy although Au/ZnO systems show preferable catalytic oxidation activity to CO
Inactivation, selectivity the shortcomings of being not very high and be restricted.Therefore, how under normal temperature condition realize Au catalyst it is efficient, low
The CO catalytic oxidation of cost is still one of the hot issue of research so far.
Three（8-hydroxyquinoline）Aluminium（Alq3）It is frequently used for plural layers luminaire, is a kind of very stable fluorescent solid
Material.The nonactive spacer molecule of optics is either added in Alq3 crystal form networks by being introduced into substituent group in Alq3 molecules,
It can make its bluish-green fluorescence that blue shift either red shift occur.In addition, there is aromatic ring structure and 2.5eV based on organic semiconductor Alq3
Band gap（Uv-vis spectra is calculated）, it is also applied to photocatalysis field, such as catalytic degradation is sub- under visible light
Methyl blue dye.The present invention introduces organic molecule functional material Alq3 in metal oxide, and chemical property is stablized, had good
Good electron transport ability is conducive to the electron density for improving Au nanoparticle surfaces, so as to promote CO low-temperature catalytic oxidations.
Invention content
The purpose of the present invention is to provide a kind of Au/ZnO-Alq3 catalyst and the preparation method and application thereof, for biography
Au loaded catalysts of uniting need at relatively high temperatures could CO catalytic oxidation the problem of, by introducing, chemical property is stable, there have to be good
The organic molecule functional material Alq3 of good electron transport ability is modified carrier ZnO, to improve Au nanoparticle surfaces
Electron density, to promote CO low-temperature catalytic oxidations.
To achieve the above object, the present invention adopts the following technical scheme that：
A kind of Au/ZnO-Alq3 catalyst is to be dispersed in organic semiconductor using Au nano-particles as active component
ZnO carrier surfaces modified materials A lq3 form high-dispersion loading type catalyst.
The content of Alq3 is 1.0 ~ 20.0 wt% in gained catalyst, and the content of Au is 0.1 ~ 5.0 wt%.
The preparation method of the Au/ZnO-Alq3 catalyst includes the following steps：
a）Alq3 is added in ZnO precursor, by hydro-thermal reaction and high-temperature calcination, the modified ZnO carriers of Alq3 are made；
b）Using coprecipitation in step a）ZnO carrier surfaces modified Alq3 obtained load Au nano-particles, and institute is made
State catalyst.
Its specific steps includes：0.5 ~ 2g PVP and 0.01 ~ 0.2g Alq3 are add to deionized water, ultrasonic disperse
Uniformly, it is 1 molar ratio to be then added:3 Zn (NO3)2·6H2O and urea, 130 ~ 180 DEG C of 10 ~ 15h of hydro-thermal reaction, then from
The heart, washing calcine 2h in 500 DEG C after 60 ~ 100 DEG C of vacuum drying, obtain the modified ZnO carriers of Alq3；Alq3 is modified
ZnO carriers and a concentration of 0.005 ~ 0.02 g/mL of Au HAuCl4Solution mixes, and gained mixed solution is with 0.1 ~ 0.25
It is 8 ~ 12 that mol/L NaOH solutions, which adjust pH value, centrifugation, washing after reaction 12h, 60 ~ 100 DEG C of dryings, 300 DEG C of 1 ~ 3h of calcining, i.e.,
The Au/ZnO-Alq3 catalyst is made.
The room temperature that gained Au/ZnO-Alq3 catalyst can be used for CO in air or other occasions under visible light catalytic is gone
It removes.
The remarkable advantage of the present invention is：
（1）The present invention is modified carrier ZnO using organic molecule functional material Alq3 as auxiliary agent, is conducive to raising Au and receives
The electron density on rice corpuscles surface；Meanwhile because Alq3 has very strong light absorption, Au/ZnO can be made in the absorption of visible region
Red shift occurs for band edge, is conducive to improve the activity of catalyst photochemical catalytic oxidation CO under visible light.
（2）Alq3's and ZnO has been implemented in combination with organic semiconducting materials and oxide-metal combinations, is conducive to develop other
Application of the organic semiconducting materials in terms of CO catalytic oxidation.
（3）Preparation method is simple by the present invention, is conducive to promote and apply.
Description of the drawings
Fig. 1 is that the X of ZnO-Alq3, Au/ZnO-Alq3 and Au/ZnO made from ZnO, Alq3 and embodiment and comparative example are penetrated
Line powder diagram.
Fig. 2 is diffusing for ZnO and ZnO-Alq3, Au/ZnO-Alq3 and Au/ZnO made from embodiment and comparative example
Spectrogram, wherein a ZnO, b Au/ZnO, c ZnO-Alq3, d Au/ZnO-Alq3.
Fig. 3 is the photoelectricity flow graph of ZnO and ZnO-Alq3, Au/ZnO-Alq3 and Au/ZnO made from embodiment and comparative example,
Wherein, a ZnO, b Au/ZnO, c Au/ZnO-Alq3, d ZnO-Alq3.
Fig. 4 is the comparative situation figure of Au/ZnO and Au/ZnO-Alq3 CO catalytic oxidation performances before and after illumination.
Specific implementation mode
In order to make content of the present invention easily facilitate understanding, With reference to embodiment to of the present invention
Technical solution is described further, but the present invention is not limited only to this.
The preparation of embodiment Au/ZnO-Alq3 catalyst
（1）0.05g Alq3 are added in the 240mL aqueous solutions of the PVP containing 1g, 6h are vigorously stirred after ultrasonic disperse 30min, so
Afterwards by 4.76g Zn (NO3)2·6H2O and 2.88g urea is added in above-mentioned solution, 150 DEG C of hydro-thermal reaction 12h, be then centrifuged for,
Washing, 80 DEG C of vacuum drying 12h are subsequently placed into 500 DEG C of calcining 2h in Muffle furnace, obtain ZnO-Alq3 carriers；
（2）By step（1）The HAuCl of carrier obtained and 2 mL 0.01g/mL containing Au4Solution（1.0g HAuCl4·3H2O is used
Deionized water dissolving is settled to 100mL）It is added in 100 mL water, is 10 with 0.1 its pH value of mol/L NaOH solutions tune, stirs
Centrifugation after reacting 12h, washing are mixed, gained is deposited in 80 DEG C of drying, and it is 1.0 wt%'s that 2h is calcined at 300 DEG C to get Au load capacity
Au/ZnO-Alq3 catalyst.
The preparation of comparative example A's u/ZnO catalyst
（1）1g PVP are added in 240mL deionized waters, 6h is vigorously stirred after ultrasonic disperse 30min, then by 4.76g Zn
(NO3)2·6H2O and 2.88g urea is added in above-mentioned solution, and 150 DEG C of hydro-thermal reaction 12h are then centrifuged for, wash, and 80 DEG C true
The dry 12h of sky is subsequently placed into 500 DEG C of calcining 2h in Muffle furnace, obtains ZnO carriers.
（2）By step（1）The HAuCl of carrier obtained and 2 mL 0.01g/mL containing Au4Solution（1.0g HAuCl4·
3H2O deionized water dissolvings are settled to 100mL）It is added in 100 mL water, with 0.1 mol/L NaOH solutions tune its pH value
It is 10, is stirred to react centrifugation, washing after 12h, gained is deposited in 80 DEG C of drying, and calcining 2h is to get Au load capacity at 300 DEG C
The Au/ZnO catalyst of 1.0 wt%.
Fig. 1 is that the X of ZnO-Alq3, Au/ZnO-Alq3 and Au/ZnO made from ZnO, Alq3 and embodiment and comparative example are penetrated
Line powder diagram.There is no the crystalline structures for changing ZnO for the addition of Alq3 and the load of Au it can be seen from Fig. 1 comparisons.
Fig. 2 is ZnO（a）With ZnO-Alq3 made from embodiment and comparative example（c）,Au/ZnO-Alq3（d）And Au/ZnO
（b）The spectrogram that diffuses.As seen from Figure 2, the introducing of Alq3 makes the absorption band edge of ZnO carriers that red shift have occurred, and improves
Absorption to visible light, to enhancing facilitation of the visible light to Au/ZnO-Alq3 CO catalytic oxidations.
Fig. 3 is ZnO（a）With Au/ZnO made from embodiment and comparative example（b）,Au/ZnO-Alq3（c）And ZnO-Alq3
（d）Photoelectricity flow graph.As seen from Figure 3, the introducing of Alq3 makes ZnO carriers obviously cause the increase of photoelectric current, illustrates Alq3
Introducing be conducive to improve Au nanoparticle surfaces electron density, to promote Au/ZnO-Alq3 to CO catalysis oxidations.
The performance evaluation of catalyst
The performance evaluation of catalyst oxidation CO is measured using the continuous flow device of normal pressure.The continuous flow device of the normal pressure
It include the quartz glass reactor with air inlet and gas outlet（Long 30mm × wide 15mm × high 1mm）, quartz glass reactor
Inner cavity be filled with catalyst, quartz glass reactor side, which is provided with, follows bad condensate water device（It is detected with thermocouple）And it is used for
Excitation Au generates the optical filter (490 nm-760 nm) of plasma resonance effect band and xenon lamp device, the xenon lamp device are sent out
Light can penetrate quartz glass reactor reach catalyst surface.
Assay method is：Take 0.25 g Catalyst packings in quartz glass reactor, catalyst particle size is 0.2 ~ 0.3
mm（60 ~ 80 mesh）, CO and O in reaction gas2Content be respectively 0.3 V% and 0.3 V%, helium is as balance supplement gas, reaction
Gas overall flow rate is 100 mL/min.Reaction temperature is regulated and controled by band circulating condensing water at 25 DEG C.Using Agilent 7890D type gas phases
CO, O in chromatograph timing on-line analysis atmosphere2And CO2Concentration, detector TCD, packed column TDX-01, negate answer it is 6 small
When after result calculate CO conversion ratios,
The calculation formula of CO conversion ratios is：C=（VinCO-VoutCO）/VinCO× 100%,
In formula, C is the conversion ratio of CO；VinCOAnd VoutCOCO contents respectively in air inlet and outlet（V%）.
Fig. 4 is the comparative situation figure of Au/ZnO and Au/ZnO-Alq3 CO catalytic oxidation performances before and after illumination.By Fig. 4 results
It has been shown that, the introducing of Alq3 effectively increase the activity of Au/ZnO photochemical catalytic oxidations CO.
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with
Modification should all belong to the covering scope of the present invention.
Claims (7)
1. a kind of Au/ZnO-Alq3 catalyst, it is characterised in that：Using Au nano-particles as active component, it is dispersed in organic
ZnO carrier surfaces modified semi-conducting material Alq3 form high-dispersion loading type catalyst.
2. Au/ZnO-Alq3 catalyst according to claim 1, it is characterised in that：The content of Alq3 in gained catalyst
Content for 1.0 ~ 20.0 wt%, Au is 0.1 ~ 5.0 wt%.
3. a kind of preparation method of Au/ZnO-Alq3 catalyst as described in claim 1, it is characterised in that：Including following step
Suddenly：
a）Alq3 is added in ZnO precursor, by hydro-thermal reaction and high-temperature calcination, the modified ZnO carriers of Alq3 are made；
b）Using coprecipitation in step a）ZnO carrier surfaces modified Alq3 obtained load Au nano-particles, and institute is made
State catalyst.
4. the preparation method of Au/ZnO-Alq3 catalyst according to claim 3, it is characterised in that：Step a）The water
Thermal response is 10 ~ 15h of reaction at 130 ~ 180 DEG C, then centrifuges, washs, 60 ~ 100 DEG C of vacuum drying.
5. the preparation method of Au/ZnO-Alq3 catalyst according to claim 3, it is characterised in that：Step b）It is described total
The precipitation method are by modified Alq3 ZnO carriers and HAuCl4Solution mixes, and it is 8 ~ 12 then to adjust its pH value with NaOH solution,
It is centrifuged after reaction 12h, washing, it is dry at 60 ~ 100 DEG C, 1 ~ 3h is then calcined at 300 DEG C.
6. the preparation method of Au/ZnO-Alq3 catalyst according to claim 5, it is characterised in that：The HAuCl4It is molten
A concentration of 0.005 ~ 0.02 g/mL of Au in liquid；A concentration of 0.1 ~ 0.25 mol/L of the NaOH solution.
7. a kind of application of Au/ZnO-Alq3 catalyst as described in claim 1, it is characterised in that：Under visible light catalytic,
Room temperature for CO removes.
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