CN108704666B - Au/ZnO-Alq3 catalyst, and preparation method and application thereof - Google Patents
Au/ZnO-Alq3 catalyst, and preparation method and application thereof Download PDFInfo
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- 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
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Abstract
The invention discloses an Au/ZnO-Alq3 catalyst and a preparation method and application thereof, wherein an organic semiconductor material Alq3 is added into a ZnO precursor to prepare an Alq3 modified ZnO carrier, and then active component Au nano particles are dispersed on the surface of the Alq3 modified ZnO carrier through a coprecipitation method to prepare a high-dispersion supported catalyst Au/ZnO-Alq 3. The introduction of Alq3 in the invention improves the activity of CO catalytic oxidation of the obtained catalyst under visible light, so that the catalyst is suitable for removing CO at normal temperature in air or other occasions, and the preparation method is simple and easy to implement and is beneficial to popularization and application.
Description
Technical Field
The invention belongs to the technical field of visible light catalytic oxidation CO, and particularly relates to an Au/ZnO-Alq3 catalyst, and a preparation method and application thereof.
Background
CO is typically a flammable, explosive, toxic gas that readily binds to hemoglobin (Hb) in blood. When the air contains ppm-level CO, the human body can be poisoned; when the CO content in the air reaches 400ppm, people can feel headache, tiredness, nausea and the like; when the content reaches 600ppm, the human has palpitation and hyperfunction accompanied by collapse symptom; when the content is more than 1000ppm, people can sleep and spasm, and suffocate when the content is serious. In the most studied hydrogen fuel cells at present, a trace amount of CO poisons a catalyst, an electrode, and the like, and most typically, a proton membrane exchange fuel cell (PEMFC). 0.5-1.0 vol% CO in the reformate gas poisons the PEMFC electrodes and the CO concentration in the fuel gas must be reduced to less than 100 ppm. Similarly, in industrial production, the presence of trace amounts of CO can cause catalyst poisoning in some synthesis reactions, which is extremely disadvantageous for industrial production, for example, when the raw material gas for ammonia synthesis industry contains trace amounts of CO, it must be purified and removed. Therefore, how to efficiently remove CO has become one of the current major environmental issues.
Currently, the most common methods for removing CO include physical methods and chemical removal methods, wherein the physical methods include cryogenic separation, pressure swing adsorption, membrane separation, solvent absorption, and the like; the chemical removal method comprises a low-temperature water gas shift method, a methanation method, a catalytic oxidation method and the like. But the CO purification equipment is required to have the characteristics of low temperature, light weight, small volume, convenient operation, simple process, continuous work and the like, so that the physical purification method is not easy to adopt; the low-temperature water gas shift reaction method is to convert CO into CO by the reaction of CO and water vapor2And simultaneously generate H2The catalyst is very suitable for a CO removal system, but the reaction rate is relatively slow under the low-temperature condition, the reaction is limited by thermodynamic equilibrium, and the requirement of reducing CO to ppm level is difficult to achieve, so the catalyst is only suitable for removing CO with high concentration; the methanation of CO is a relatively mature process, but consumes a large amount of hydrogen (3 moles of H are consumed for 1 mole of CO removal) during the reaction2) And reverse water-gas shift reaction may occur inside the system. Therefore, the low (normal) temperature (C) was investigated<The catalytic oxidation of CO under the condition of 100 ℃ has practical significance for eliminating CO pollution.
Currently, most researches on catalytic oxidation of CO are carried out by loading noble metals (Pd, Au, Ag, Rh, Pt, etc.) as active components on a certain carrier (Al)2O3、SiO2、TiO2Etc.) to produce a catalyst exhibiting a certain catalytic oxidation effect on CO. Research finds that for an Au/ZnO system, when gold nanoparticles are highly dispersed on the surface of a metal oxide carrier, the Au/ZnO composite material not only has excellent catalytic activity on CO oxidation, but also has good water resistance, stability and humidity enhancement effect; ZnO is popular among researchers in photocatalytic oxidation of CO because of its advantages such as proper forbidden bandwidth, high photoelectric conversion efficiency, low price, etc. The Au/ZnO system has better catalytic oxidation activity on COHowever, the method is limited by the disadvantages of poor stability, easy inactivation, low selectivity, etc. Therefore, how to realize the efficient and low-cost catalytic oxidation of CO by using an Au catalyst under normal temperature conditions is still one of the hot problems of research so far.
Tris (8-hydroxyquinoline) aluminum (Alq 3) is a very stable fluorescent solid material, often used in multilayer thin film light emitting devices. Blue-green fluorescence can be subjected to blue shift or red shift by introducing a substituent group into an Alq3 molecule or adding an optically inactive spacer molecule into an Alq3 crystal form network. In addition, based on the fact that the organic semiconductor Alq3 has an aromatic ring structure and an energy band gap of 2.5eV (calculated by an ultraviolet and visible spectrum), the organic semiconductor Alq3 is also applied to the field of photocatalysis, such as catalytic degradation of methylene blue dye under visible light. According to the invention, the organic micromolecular functional material Alq3 is introduced into the metal oxide, the chemical property is stable, the electronic transmission capability is good, and the improvement of the electronic density on the surface of the Au nano particle is facilitated, so that the low-temperature catalytic oxidation of CO can be promoted.
Disclosure of Invention
The invention aims to provide an Au/ZnO-Alq3 catalyst, a preparation method and application thereof, aiming at the problem that the traditional Au supported catalyst can catalyze and oxidize CO only at a higher temperature, the carrier ZnO is modified by introducing an organic micromolecular functional material Alq3 which has stable chemical properties and good electron transmission capability, so that the electron density on the surface of an Au nanoparticle is improved, and the low-temperature catalytic oxidation of CO is promoted.
In order to achieve the purpose, the invention adopts the following technical scheme:
an Au/ZnO-Alq3 catalyst is characterized in that Au nanoparticles are used as active components and are uniformly dispersed on the surface of a ZnO carrier modified by an organic semiconductor material Alq3 to form a high-dispersion supported catalyst.
The content of Alq3 in the obtained catalyst is 1.0-20.0 wt%, and the content of Au is 0.1-5.0 wt%.
The preparation method of the Au/ZnO-Alq3 catalyst comprises the following steps:
a) adding Alq3 into the ZnO precursor, and preparing the modified ZnO carrier of Alq3 through hydrothermal reaction and high-temperature calcination;
b) loading Au nano particles on the surface of the Alq3 modified ZnO carrier prepared in the step a) by using a coprecipitation method to prepare the catalyst.
The method comprises the following specific steps: adding 0.5-2 g of PVP and 0.01-0.2 g of Alq3 into deionized water, performing ultrasonic dispersion uniformly, and then adding Zn (NO) with the molar ratio of 1:33)2·6H2Carrying out hydrothermal reaction on O and urea at 130-180 ℃ for 10-15 h, then centrifuging, washing, carrying out vacuum drying at 60-100 ℃, and calcining at 500 ℃ for 2h to obtain an Alq3 modified ZnO carrier; adding Alq3 modified ZnO carrier and HAuCl with Au concentration of 0.005-0.02 g/mL4And mixing the solutions, adjusting the pH value of the obtained mixed solution to 8-12 by using 0.1-0.25 mol/L NaOH solution, reacting for 12 hours, centrifuging, washing, drying at 60-100 ℃, and calcining at 300 ℃ for 1-3 hours to obtain the Au/ZnO-Alq3 catalyst.
The obtained Au/ZnO-Alq3 catalyst can be used for removing CO at normal temperature in air or other occasions under the catalysis of visible light.
The invention has the following remarkable advantages:
(1) according to the preparation method, an organic micromolecular functional material Alq3 is used as an auxiliary agent to modify ZnO as a carrier, so that the electron density on the surface of the Au nanoparticle is improved; meanwhile, because Alq3 has strong light absorption, the red shift of the absorption band edge of Au/ZnO in a visible light area can be caused, which is beneficial to improving the activity of the catalyst for photocatalytic oxidation of CO under visible light.
(2) The combination of Alq3 and ZnO realizes the combination of organic semiconductor materials and metal oxides, and is beneficial to developing the application of other organic semiconductor materials in the aspect of catalytic oxidation of CO.
(3) The preparation method is simple and easy to implement and is beneficial to popularization and application.
Drawings
FIG. 1 is an X-ray powder diffraction pattern of ZnO, Alq3 and ZnO-Alq3, Au/ZnO-Alq3 and Au/ZnO prepared in examples and comparative examples.
FIG. 2 is a graph showing the diffuse reflection spectra of ZnO and ZnO-Alq3, Au/ZnO-Alq3 and Au/ZnO prepared in examples and comparative examples, wherein a is ZnO, b is Au/ZnO, c is ZnO-Alq3 and d is Au/ZnO-Alq 3.
FIG. 3 is a photo-electric diagram of ZnO and ZnO-Alq3, Au/ZnO-Alq3 and Au/ZnO prepared in examples and comparative examples, wherein a is ZnO, b is Au/ZnO, c is Au/ZnO-Alq3 and d is ZnO-Alq 3.
FIG. 4 is a graph comparing the performance of Au/ZnO and Au/ZnO-Alq3 in catalytic oxidation of CO before and after light irradiation.
Detailed Description
In order to make the present invention more comprehensible, the technical solutions of the present invention are further described below with reference to specific embodiments, but the present invention is not limited thereto.
EXAMPLES preparation of Au/ZnO-Alq3 catalyst
(1) 0.05g of Alq3 was added to 240mL of an aqueous solution containing 1g of PVP, dispersed with ultrasound for 30min and then stirred vigorously for 6h, after which 4.76g of Zn (NO) was added3)2·6H2Adding O and 2.88g of urea into the solution, carrying out hydrothermal reaction for 12h at 150 ℃, then centrifuging, washing, carrying out vacuum drying for 12h at 80 ℃, and then putting into a muffle furnace for calcining for 2h at 500 ℃ to obtain a ZnO-Alq3 carrier;
(2) mixing the carrier prepared in step (1) with 2 mL HAuCl containing 0.01g/mL Au4Solution (1.0 g HAuCl)4·3H2Dissolving O with deionized water, and fixing the volume to 100 mL), adding the solution into 100mL of water, adjusting the pH value of the solution to 10 with 0.1 mol/L NaOH solution, stirring the solution for reaction for 12 hours, centrifuging and washing the solution, drying the obtained precipitate at 80 ℃, and calcining the dried precipitate at 300 ℃ for 2 hours to obtain the Au/ZnO-Alq3 catalyst with the Au load of 1.0 wt%.
Comparative example preparation of Au/ZnO catalyst
(1) 1g PVP is added into 240mL deionized water, the mixture is stirred vigorously for 6h after 30min of ultrasonic dispersion, and then 4.76g Zn (NO) is added3)2·6H2And adding O and 2.88g of urea into the solution, carrying out hydrothermal reaction for 12h at 150 ℃, then centrifuging, washing, carrying out vacuum drying for 12h at 80 ℃, and then putting into a muffle furnace to calcine for 2h at 500 ℃ to obtain the ZnO carrier.
(2) Mixing the carrier prepared in step (1) with 2 mL HAuCl containing 0.01g/mL Au4Solution (1.0 g HAuCl)4·3H2Dissolving O in deionized waterAnd fixing the volume to 100 mL), adjusting the pH value to 10 by using 0.1 mol/L NaOH solution, stirring for reaction for 12 hours, centrifuging and washing, drying the obtained precipitate at 80 ℃, and calcining the precipitate at 300 ℃ for 2 hours to obtain the Au/ZnO catalyst with the Au loading of 1.0 wt%.
FIG. 1 is an X-ray powder diffraction pattern of ZnO, Alq3 and ZnO-Alq3, Au/ZnO-Alq3 and Au/ZnO prepared in examples and comparative examples. As can be seen from the comparison of FIG. 1, the addition of Alq3 and the loading of Au do not change the crystal structure of ZnO.
FIG. 2 is a graph showing diffuse reflection spectra of ZnO (a) and ZnO-Alq3 (c), Au/ZnO-Alq3 (d), and Au/ZnO (b) obtained in examples and comparative examples. As can be seen from FIG. 2, the introduction of Alq3 makes the absorption band edge of the ZnO carrier red-shifted, and improves the absorption of visible light, thereby enhancing the promotion effect of visible light on the catalytic oxidation of CO by Au/ZnO-Alq 3.
FIG. 3 is a graph showing photocurrents of Au/ZnO (b), Au/ZnO-Alq3 (c) and ZnO-Alq3 (d) produced by ZnO (a) and examples and comparative examples. As can be seen from FIG. 3, the introduction of Alq3 makes ZnO carriers obviously cause the increase of photocurrent, which shows that the introduction of Alq3 is favorable for improving the electron density of the surface of Au nanoparticles, thereby promoting the catalytic oxidation of Au/ZnO-Alq3 on CO.
Evaluation of catalyst Performance
The performance evaluation of the catalytic oxidation of CO by the catalyst is measured by a normal-pressure continuous flow device. The normal-pressure continuous flow device comprises a quartz glass reactor (with the length of 30mm, the width of 15mm and the height of 1 mm) with an air inlet and an air outlet, wherein a catalyst is filled in the inner cavity of the quartz glass reactor, a circulating condensate water device (thermocouple detection) and an optical filter (490 nm-760 nm) for exciting Au to generate a plasma resonance effect band and a xenon lamp device are arranged on the peripheral side of the quartz glass reactor, and light emitted by the xenon lamp device can penetrate through the quartz glass reactor to reach the surface of the catalyst.
The determination method comprises the following steps: filling 0.25 g of catalyst into a quartz glass reactor, wherein the particle size of the catalyst is 0.2-0.3 mm (60-80 meshes), and CO and O in reaction gas2The contents of the components are respectively 0.3V% and 0.3V%, helium is used as balance supplementary gas, and the total flow rate of the reaction gas is 100 mL/min. Inverse directionThe temperature is regulated and controlled at 25 ℃ by circulating condensed water. CO and O in atmosphere are analyzed on line at regular time by Agilent 7890D type gas chromatograph2And CO2The detector is TCD, the packed column is TDX-01, the CO conversion rate is calculated according to the result after 6 hours of reaction,
the CO conversion is calculated as: c = (V)inCO-VoutCO）/VinCO×100％，
In the formula, C is the conversion rate of CO; vinCOAnd VoutCOCO content (V%) in the inlet and outlet gases, respectively.
FIG. 4 is a graph comparing the performance of Au/ZnO and Au/ZnO-Alq3 in catalytic oxidation of CO before and after light irradiation. The results in FIG. 4 show that the introduction of Alq3 effectively improves the activity of Au/ZnO in photocatalytic oxidation of CO.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (3)
1. An Au/ZnO-Alq3 visible light catalyst for removing CO at normal temperature is characterized in that: au nano particles are used as an active component and are dispersed on the surface of a ZnO carrier modified by an organic semiconductor material Alq3 to form a high-dispersion supported catalyst; the preparation method comprises the following steps:
a) adding Alq3 into the ZnO precursor, and preparing the modified ZnO carrier of Alq3 through hydrothermal reaction and high-temperature calcination;
b) loading Au nano particles on the surface of the Alq3 modified ZnO carrier prepared in the step a) by using a coprecipitation method to prepare the catalyst;
the hydrothermal reaction in the step a) is carried out for 10-15 h at 130-180 ℃, and then centrifugation, washing and vacuum drying at 60-100 ℃ are carried out;
the coprecipitation method in the step b) is to mix the ZnO carrier modified by Alq3 and HAuCl4Mixing the solutions, then adjusting the pH value of the solution to 8-12 by using NaOH solution, reacting for 12 hours, centrifuging, washing, drying at 60-100 ℃, and then calcining for 1-3 hours at 300 ℃.
2. The Au/ZnO-Alq3 visible light photocatalyst of claim 1, wherein: the content of Alq3 in the obtained catalyst is 1.0-20.0 wt%, and the content of Au is 0.1-5.0 wt%.
3. The Au/ZnO-Alq3 visible light photocatalyst of claim 1, wherein: the HAuCl4The concentration of Au in the solution is 0.005-0.02 g/mL; the concentration of the NaOH solution is 0.1-0.25 mol/L.
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