CN107008290B - Preparation method and catalytic application of monoatomic dispersion palladium-based catalyst - Google Patents
Preparation method and catalytic application of monoatomic dispersion palladium-based catalyst Download PDFInfo
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- CN107008290B CN107008290B CN201710354344.6A CN201710354344A CN107008290B CN 107008290 B CN107008290 B CN 107008290B CN 201710354344 A CN201710354344 A CN 201710354344A CN 107008290 B CN107008290 B CN 107008290B
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/652—Chromium, molybdenum or tungsten
- B01J23/6522—Chromium
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- C—CHEMISTRY; METALLURGY
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/10—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of aromatic six-membered rings
- C07C5/11—Partial hydrogenation
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- C—CHEMISTRY; METALLURGY
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
- C07C2523/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
- C07C2523/56—Platinum group metals
- C07C2523/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tatalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C07C2523/652—Chromium, molybdenum or tungsten
Abstract
The invention discloses a preparation method of a monoatomic dispersion palladium-based catalyst and a catalytic application thereof. The preparation method of the monoatomic dispersion palladium-based catalyst adopts a photo-deposition method, and adopts zinc-containing hydrotalcite as a carrier to prepare the monoatomic dispersion palladium-based catalyst. Adding alcohol solution and H into aqueous solution dissolved with hydrotalcite carrier2PdCl4Under the irradiation of ultraviolet light, electrons in the hydrotalcite semiconductor are transferred from a valence band to a conduction band, the electrons obtained from the conduction band reduce palladium ions into palladium atoms, and alcohol molecules in the solution are oxidized at a hole to generate hydroxyl radicals. Through research on the light deposition process, the addition of H through control is found2PdCl4The amount of the solution and the illumination time can prepare the monoatomic palladium catalyst. According to the invention, by carrying out reduction treatment on the catalyst sample at different temperatures, the monatomic palladium does not generate aggregation, and the monatomic dispersed palladium-based catalyst has excellent catalytic activity and selectivity for phenylacetylene hydrogenation reaction.
Description
Technical Field
The invention relates to the technical field of catalyst preparation, in particular to a monoatomic dispersion palladium-based catalyst prepared by a light deposition method and using a hydrotalcite semiconductor as a carrier, and an application of the catalyst in catalyzing selective hydrogenation reaction of alkyne.
Background
Polystyrene is generally prepared industrially using styrene polymerization. However, the styrene raw material contains a small amount of phenylacetylene, which easily poisons the catalyst. In order to increase the purity of styrene monomer, phenylacetylene in the feedstock is generally converted to styrene by selective hydrogenation of phenylacetylene. At present, the supported palladium-based catalyst is widely used in the reaction due to its high catalytic hydrogenation activity, but when the conversion rate of the phenylacetylene is higher than 95%, the selectivity of the styrene is greatly reduced. Palladium sites are currently modified to increase styrene selectivity, usually by poisoning and alloying, but this generally sacrifices the reactivity. Therefore, the research of the palladium-based catalyst with high selectivity and high activity is of great significance.
At present, the storage amount of the global noble metal palladium is extremely low, so that the waste of the palladium is avoided in the chemical industry, and the utilization rate of the palladium is improved. For catalytic hydrogenation reaction, the active sites of the supported nano palladium-based catalyst generally act as palladium atoms on the surface of palladium particles, and for monoatomic dispersed palladium-based catalyst, each palladium atom is an active center and can play a role in catalysis, the atom utilization efficiency can reach 100% theoretically, and further the catalytic reaction rate is improved. And the monatomic palladium does not have a subsurface and does not contain subsurface hydrogen, so that the selectivity of alkyne hydrogenation is improved. Therefore, the method for simply preparing the monoatomic dispersion palladium-based catalyst has important significance.
Disclosure of Invention
In order to solve the problems, the invention provides a monoatomic dispersion palladium-based catalyst, a preparation method and a using method thereof, which aim to solve the problems of low selectivity and low activity of the existing palladium-based catalyst. The preparation method comprises adding appropriate amount of alcohol solution and H into aqueous solution dissolved with hydrotalcite carrier2PdCl4Under the irradiation of ultraviolet light, electrons in the hydrotalcite semiconductor are transferred from a valence band to a conduction band, the electrons obtained from the conduction band reduce palladium ions into palladium atoms, and alcohol molecules in the solution are oxidized at a hole to generate hydroxyl radicals. Through research on the light deposition process, the addition of H through control is found2PdCl4The amount of the solution and the illumination time can prepare the monoatomic palladium catalyst. By subjecting the catalyst sample to reduction treatment at various temperatures (200 ℃, 300 ℃, 500 ℃), the monatomic Pd does not aggregate.
A palladium-based catalyst, monatomic palladium is dispersed on the surface of a semiconductor hydrotalcite carrier.
Preferably, the zinc salt used in the semiconductor hydrotalcite is zinc nitrate or zinc chloride, and the trivalent salt used is aluminum nitrate, chromium nitrate, ferric nitrate, cobalt nitrate, gallium nitrate, or any one of aluminum chloride, chromium chloride, ferric chloride, cobalt chloride, or gallium chloride.
Preferably, the semiconductor hydrotalcite carrier is zinc-chromium hydrotalcite, the molar ratio of Zn to Cr is 2/1, and the loading amount of the palladium catalyst on the semiconductor hydrotalcite carrier is 0.1-0.3 wt%.
A preparation method of a palladium-based catalyst comprises the following steps:
(a) preparing semiconductor hydrotalcite by a double-drop method;
(b) electrons transferred from the valence band to the conduction band within the semiconductor hydrotalcite reduce palladium ions to palladium atoms using a photo-deposition method.
Preferably, in step (a), the divalent salt used is zinc nitrate or zinc chloride, and the trivalent salt used is aluminum nitrate, chromium nitrate, ferric nitrate, cobalt nitrate, gallium nitrate, or any one of aluminum chloride, chromium chloride, ferric chloride, cobalt chloride, or gallium chloride.
Preferably, the semiconductor hydrotalcite produced in step (a) is a zinc-chromium hydrotalcite with a Zn/Cr molar ratio of 2/1.
Preferably, the specific reaction conditions in step (b) are as follows: ultrasonically dispersing the semiconductor hydrotalcite obtained in the step (a) in deionized water, adding an alcohol solvent, ultrasonically dispersing uniformly, and then adding H2PdCl4And (2) irradiating the solution by ultraviolet rays under the stirring condition to ensure that electrons in the hydrotalcite semiconductor are transferred from a valence band to a conduction band, reducing palladium ions into palladium atoms by the electrons obtained by the conduction band, carrying out oxidation reaction on alcohol molecules in the solution at a cavity to generate hydroxyl free radicals, centrifugally washing a product, centrifugally washing the product by absolute ethyl alcohol, and drying in vacuum to obtain the monoatomic dispersed palladium-based catalyst.
Preferably, in the step (b), the hydrotalcite semiconductor is 1g of zinc-chromium hydrotalcite, the alcohol solvent is ethylene glycol, the dosage is 10-30mL, and a xenon lamp current-stabilized power lamp is used for ultraviolet irradiation for 10-30 min.
The monoatomic dispersion palladium-based catalyst prepared by the method is applied to the phenylacetylene hydrogenation reaction catalysis.
The monoatomic dispersion palladium-based catalyst prepared by the method is reduced at high temperature and then applied to phenylacetylene hydrogenation reaction; the high-temperature reduction conditions are as follows: reducing for 3-8h at 200-500 ℃ in hydrogen atmosphere, wherein the heating rate is 5-10 ℃/min.
The specific operation of applying the palladium-based catalyst prepared by the method to the phenylacetylene hydrogenation reaction is as follows: 1ml phenylacetylene substrate, 5-15ml ethanol as solvent, 0.005-0.1g of monoatomic dispersion palladium-based catalyst or its product after high temperature reduction, 20-50 ℃ of reaction temperature, H2The pressure is 0.1MPa-0.5 MPa.
The invention has the following beneficial effects:
the invention uses the light deposition method and uses the hydrotalcite with the property of semiconductor as the carrier to prepare the palladium-based catalyst with monoatomic dispersion. The catalyst shows excellent catalytic activity and selectivity for phenylacetylene selective hydrogenation reaction. The monoatomic dispersion palladium-based catalyst is roasted at the temperature of 500 ℃, the interaction force of the carrier and the active component is changed, and the catalyst is applied to the phenylacetylene hydrogenation reaction, so that the selectivity and the activity of the catalyst can be further improved. Through research on the photoreduction process, the invention also finds that the monatomic palladium-based catalyst can be prepared by controlling the amount of the catalyst and the ultraviolet illumination time. By carrying out heat treatment at 500 ℃ on a sample, palladium atoms do not generate aggregation, the catalyst has good stability, and has higher catalytic activity and selectivity for phenylacetylene hydrogenation reaction.
Drawings
FIG. 1 is a scanning electron micrograph of ZnCrLDH prepared in example 1.
FIG. 2 is a high resolution transmission electron micrograph of a high angle dark field image of the monoatomic dispersion Pd catalyst prepared in example 1, which is aberration corrected.
FIG. 3 is a high resolution transmission electron micrograph of a high angle dark field image corrected for aberrations of a catalyst sample obtained after reduction of the monoatomic dispersion Pd catalyst prepared in example 1 at 500 ℃.
FIG. 4 is a graph of the selectivity of the monatomic dispersed Pd catalyst and the supported nano Pd catalyst prepared in example 1 as a function of conversion.
Detailed Description
In order to make those skilled in the art better understand the technical scheme of the present invention, the following describes the preparation method of the monoatomic dispersion palladium-based catalyst provided by the present invention in detail with reference to the accompanying drawings.
Example 1
In this example, ZnCr-LDH was prepared by a double-drop method. The Zn/Cr molar ratio is 2/1; first, 0.66mol of Zn (NO) is obtained3)2·6H2O，0.33mol Cr(NO3)3·9H2And O, measuring 60ml of deionized water by using a measuring cylinder, fully mixing the deionized water with the metal salt, and placing the mixture into an ultrasonic cleaner for standing for 10min to achieve full dissolution. 0.30mol of NaOH and 0.25mol of Na are weighed out separately2CO3Putting into a cleaned beaker, stirring with 80ml deionized water to dissolve, and also putting into an ultrasonic cleaner to perform ultrasonic treatment for 10min to fully dissolve; 150ml of deionized water solution is firstly added into a three-neck flask; then adding the alkali solution and the salt solution which are well subjected to ultrasonic treatment into two constant-pressure dropping funnels respectively, adding 150ml of carbon dioxide-removed aqueous solution into a three-neck flask, dropwise adding the aqueous solution into the three-neck flask, controlling the pH value of the mixed solution to be stable at 10, stirring the obtained mixed solution in a water bath kettle at 60 ℃, and crystallizing for 36 hours. Centrifuging the obtained slurry for 5 minutes in a centrifugal machine with the speed of 4000 revolutions per minute, washing the slurry for several times by using deionized water, then centrifugally washing the slurry for one time by using absolute ethyl alcohol, putting the obtained paste product into an electric heating constant-temperature vacuum drying oven to dry the product at the temperature of 30 ℃, and grinding the product into fine powder by using an agate mortar to obtain the zinc-chromium hydrotalcite carrier which is marked as Zn2Cr-LDH。
Weighing 1g of zinc-chromium hydrotalcite carrier, adding the zinc-chromium hydrotalcite carrier into a 300ml quartz beaker, adding 200ml of deionized water into the quartz beaker, dispersing the mixture in an ultrasonic cleaner until the mixture is uniform, adding 10ml of sacrificial agent ethylene glycol, stirring and carrying out ultrasonic treatment for 5 min; under the condition of stirring, a liquid-transfering gun is used for transferring H with the theoretical loading of 0.1 wt%2PdCl4Adding the solution into a quartz beaker, and illuminating the quartz beaker for 10min by using a xenon lamp current-stabilizing power lamp; the reacted solution is washed with centrifugal water, finally washed with ethanol, dried in a vacuum oven at 30 ℃ and then ground for direct use.
The ground catalyst is divided into 4 parts, one part is not treated, the other three parts are respectively put into a hydrogen atmosphere furnace to be reduced for 5 hours at 200 ℃, 300 ℃ and 500 ℃, and the heating rate is 5 ℃/min.
In order to compare the catalytic performance of the samples, a supported nano palladium-based catalyst was prepared for comparison, the carrier of the supported nano palladium-based catalyst is ZnCr-LDH, the theoretical loading capacity of palladium is 1 wt%, except that H was added2PdCl4The amount of the solution was 1 wt% of theoretical loading, and the rest of the preparation process was the same as the above-described process for preparing the monoatomic dispersion palladium-based catalyst.
The palladium-based catalyst prepared by the method is applied to phenylacetylene selective hydrogenation reaction, and the process conditions are as follows: weighing 0.01g of prepared monoatomic dispersion palladium-based catalyst or high-temperature reduction product thereof or supported nano palladium-based catalyst in a 50ml high-pressure reaction kettle, weighing 1ml of phenylacetylene substrate and 9ml of ethanol as solvent, sealing the reaction kettle, and filling N into the reaction kettle2After the air is removed and the reaction is repeatedly carried out for three times, H is filled into the reaction kettle2Three times and discharging, the process is carried out quickly so as not to influence the reaction result, and then H is introduced2The pressure is made to reach 0.5MPa, the reaction temperature is set to be 30 ℃, the stirring speed is 1000r/min, samples are taken at regular intervals, and qualitative and quantitative analysis is carried out on the product by utilizing a gas chromatography.
TOF (Time of Flight, TOF for short) values of the monoatomic dispersion palladium-based catalyst and the supported nano palladium-based catalyst prepared in example 1 were calculated to be 64.5s for 0.1% Pd/ZnCr-LDH (R500), 0.1% Pd/ZnCr-LDH and 1% Pd/ZnCr-LDH, respectively-1,31.2s-1And 6.6s-1(ii) a I.e. TOF values are compared as: 0.1% Pd/ZnCr-LDH (R500)>0.1％Pd/ZnCr-LDH>1％Pd/ZnCr-LDH。
FIG. 4 is a graph showing the selectivity of the monoatomic dispersion palladium-based catalyst and the supported nano palladium-based catalyst prepared in example 1 according to the conversion rate. From fig. 4, it can be seen that the selectivity is, in order from large to small: 0.1% R500> 0.1% > 1%. For the 0.1% R500 sample, the selectivity can be maintained at 92% when the conversion reaches 100%.
It will be understood that the above embodiments are merely exemplary embodiments taken to illustrate the principles of the present invention, which is not limited thereto. It will be apparent to those skilled in the art that various modifications and improvements can be made without departing from the spirit and substance of the invention, and these modifications and improvements are also considered to be within the scope of the invention.
Claims (5)
1. The preparation method of the monoatomic dispersion palladium-based catalyst is characterized in that the monoatomic dispersion palladium-based catalyst is obtained by dispersing monoatomic palladium on the surface of a semiconductor hydrotalcite carrier, and the load capacity of the palladium catalyst on the semiconductor hydrotalcite carrier is 0.1-0.3 wt%;
the preparation method comprises the following steps:
(a) preparing semiconductor hydrotalcite by a double-drop method;
(b) reducing palladium ions into palladium atoms by adopting a photo-deposition method through electrons transferred from a valence band to a conduction band in the semiconductor hydrotalcite;
step (a), the divalent salt is zinc nitrate or zinc chloride, and the trivalent salt is any one of aluminum nitrate, chromium nitrate, ferric nitrate, cobalt nitrate and gallium nitrate, or aluminum chloride, chromium chloride, ferric chloride, cobalt chloride and gallium chloride;
the specific reaction conditions of the step (b) are as follows: ultrasonically dispersing the semiconductor hydrotalcite obtained in the step (a) in deionized water, adding an alcohol solvent, ultrasonically dispersing uniformly, and then adding H2PdCl4And (2) irradiating the solution by ultraviolet rays under the stirring condition to ensure that electrons in the hydrotalcite semiconductor are transferred from a valence band to a conduction band, reducing palladium ions into palladium atoms by the electrons obtained by the conduction band, carrying out oxidation reaction on alcohol molecules in the solution at a cavity to generate hydroxyl free radicals, centrifugally washing a product, centrifugally washing the product by absolute ethyl alcohol, and drying in vacuum to obtain the monoatomic dispersed palladium-based catalyst.
2. The method of preparing a monoatomic dispersion palladium-based catalyst according to claim 1, wherein the semiconductor hydrotalcite prepared in the step (a) is zinc-chromium hydrotalcite, and the molar ratio of Zn/Cr is 2/1.
3. The method of claim 1, wherein the hydrotalcite semiconductor is 1g of zinc-chromium hydrotalcite, the alcohol solvent is ethylene glycol, the amount is 10-30mL, and the UV irradiation is performed for 10-30min using a xenon lamp stabilized power supply.
4. Use of a monoatomic palladium-based catalyst prepared by the method of any one of claims 1 to 3 for catalyzing the hydrogenation of phenylacetylene.
5. Reducing the monoatomic dispersion palladium-based catalyst prepared by the method of any one of claims 1 to 3 at a high temperature, and applying the reduced monoatomic dispersion palladium-based catalyst to phenylacetylene hydrogenation reaction; the high-temperature reduction conditions are as follows: reducing for 3-8h at 200-500 ℃ in hydrogen atmosphere, wherein the heating rate is 5-10 ℃/min.
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| CN107715876B (en) * | 2017-10-27 | 2020-06-09 | 天津理工大学 | Preparation method and application of catalyst for removing trace phenylacetylene in styrene |
| CN108777309A (en) * | 2018-05-15 | 2018-11-09 | 北京化工大学 | A kind of monatomic Pd catalyst of support type and preparation method thereof and catalytic applications |
| CN109012694B (en) * | 2018-08-09 | 2020-07-10 | 厦门大学 | Core-shell structure palladium-copper catalyst, preparation method and catalytic application thereof |
| CN109225253B (en) * | 2018-08-09 | 2020-07-17 | 厦门大学 | Atomic-level dispersed palladium-copper catalyst, and preparation method and catalytic application thereof |
| CN110947428B (en) * | 2018-09-26 | 2022-12-02 | 国家纳米科学中心 | UiO @ Pd @ UiO catalyst and preparation method and application thereof |
| CN109201048B (en) * | 2018-10-19 | 2021-02-09 | 清华大学深圳研究生院 | Monoatomic catalyst and its preparing process |
| CN110449176B (en) * | 2019-08-16 | 2021-01-29 | 江南大学 | Preparation method and application of non-noble metal monatomic catalyst |
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| CN111054333B (en) * | 2020-02-14 | 2022-11-01 | 郑州轻工业大学 | Hydrotalcite supported palladium catalyst for preparing styrene by selective hydrogenation of phenylacetylene, and preparation method and application thereof |
| CN113996312B (en) * | 2020-07-27 | 2023-02-28 | 中国科学院大连化学物理研究所 | Iron-doped magnesium aluminate spinel supported noble metal catalyst, preparation and application thereof |
| CN115724435A (en) * | 2022-12-15 | 2023-03-03 | 深圳先进电子材料国际创新研究院 | Silicon dioxide powder and preparation method and application thereof |
| CN115845840A (en) * | 2022-12-23 | 2023-03-28 | 辽宁大学 | Graphene-loaded atomic-level dispersed palladium-based catalyst and preparation method and application thereof |
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