CN107029705B - Preparation and application of supported metal catalysts - Google Patents

Preparation and application of supported metal catalysts Download PDF

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CN107029705B
CN107029705B CN201710351216.6A CN201710351216A CN107029705B CN 107029705 B CN107029705 B CN 107029705B CN 201710351216 A CN201710351216 A CN 201710351216A CN 107029705 B CN107029705 B CN 107029705B
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张庆红
王珊珊
邓卫平
李适
王野
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Xiamen University
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Abstract

kinds of supported metal catalyst preparation and its application, relate to glucaric acid, catalyst adopt the light semiconductor carrier, reduce and deposit the metal ion by the mere electron and make, wherein the supported metal catalyst includes the single metal or bimetallic component.

Description

Preparation and application of supported metal catalysts
Technical Field
The invention relates to glucaric acid, in particular to preparation and application of supported metal catalysts.
Background
Glucaric acid is nontoxic natural organic acids, is commonly found in fruits such as grapefruit, apple, orange and the like and cruciferous vegetables, glucaric acid is also important biomass conversion platform compounds, and can be used as an intermediate for preparing a plurality of derivatives, which are applied to industries such as food, medicine, chemical industry and the like wide, the commercial production of fortified milk powder and dairy products added with glucaric acid calcium is also in the development stage, and glucaric acid 1, 4-lactone which is a derivative thereof play a role in reducing cholesterol level, regulating human body hormone and the like, are emphasized by the medical field.
Currently, methods for preparing glucaric acid include biological and chemical methods. The biological method takes glucuronic acid as raw material, takes glucuronic acid enzyme as catalyst, and uses H2O2And Fe2+The existing method for producing glucaric acid by fermentation has low yield, long culture time, difficult separation and extraction and difficult promotion to utilization3The main products are glucaric acid and small molecular carboxylic acid, and the reaction is violent, the reaction process is difficult to control, the yield of the process is low, the benefit is not high, in addition, the nitric acid belongs to a strong corrosive chemical and seriously damages equipment, in addition, a multi-phase catalytic method is also used, the noble metal is used as a catalyst to catalyze the conversion of the glucose into the glucaric acid, the noble metal loading in the catalyst is high, the activity of the catalyst is limited, and the target glucaric acid product is easy to be oxidized by steps.
Chinese patent CN 103436910A discloses methods for preparing glucaric acid by an electrochemical method, which uses sulfuric acid or sulfate as electrolyte, uses electrocatalytic oxidation of glucose to generate glucaric acid, and uses a membrane separation technology to realize separation of products.
Jin X et al report the preparation of Pt by impregnation1Cu3/TiO2Supported catalyst with metal core-shell structure (empirical performance of bimetallic Pt)1Cu3/TiO2,nanocatalysts for oxidationof gluconic acid and glucose with O2,to glucaric acid[J]Journal of catalysis,2015,330:323-329), but the Cu shell of the catalyst is leached out due to complexation of gluconic acid in the product after reaction for a plurality of cycles, so that the catalytic performance of the catalyst is not stable enough. And has a large particle diameter of (>5nm) and high noble metal loading amount (>4 wt.%). Saha B et al reported the production of glucaric acid by catalyzing Glucose with a commercial 5 wt% Pt/C catalyst (Pt Catalysts for Efficient Aerobic Oxidation of Glucose to glucaric acid in Water [ J]Green Chemistry,2016,18, 3815-3822). However, the loading of noble metal in the catalyst is high, and the catalyst is poisoned and deactivated due to strong adsorption of the intermediate product gluconic acid at high conversion rate.
Disclosure of Invention
The th object of the present invention is to provide supported metal catalysts.
The second purpose of the invention is to provide a single metal catalyst for preparing glucarate by glucose selective oxidation, which is prepared by a photo-deposition method.
The third purpose of the invention is to provide a bimetallic catalyst for preparing glucarate by glucose selective oxidation, which is prepared by a coprecipitation method.
The fourth purpose of the invention is to provide a bimetallic catalyst for preparing glucarate by glucose selective oxidation, which is prepared by a distributed light deposition method.
A fifth object of the present invention is to provide a mono-or bimetallic catalyst for the selective oxidation of glucose to glucose di-acid salts.
The supported metal catalyst is composed of a semiconductor carrier loaded with single metal or double metals, wherein the carrier in the catalyst accounts for 92-99.7% by mass, the metal active component accounts for 0.3-8% by mass, the metal component is a single component or a double component, the single component is a metal element A, the double component is the metal element A and the metal element B, the mass ratio of the metal element A to the metal element B is (1-5): 1, the metal element A is selected from of Cr, Mn, Fe, Co, Nb, Ru, Rh, Pd, Ag, Re, Ir, Pt, Au, Bi and the like, the metal element B is selected from of Pt, Pd, Ag, Au, Bi and the like, the metal element A and the metal element B are not the same elements, and the semiconductor carrier is selected from TiO2、Cu2O、ZnO、CdS、SnO2、WO3Etc. of at least .
The single metal catalyst for preparing glucose diacid salt by glucose selective oxidation is prepared by adopting a light deposition method, and the preparation method comprises the following steps:
1) preparing a 0.01-0.5M aqueous solution I of metal salt of a metal element A as a precursor;
2) mixing a semiconductor carrier, a sacrificial agent and water, and stirring for 0.5h to prepare a suspension II;
3) adding the aqueous solution I into the suspension II, performing ultrasonic treatment for 20min, and mixing uniformly at 600mW/cm2Under the irradiation of a xenon lamp, carrying out photoreduction under the stirring of a magnetic stirrer at the speed of 200-500 r/min to obtain a supported single-metal catalyst suspension III;
4) and filtering the suspension III to obtain solid particles, washing with deionized water, and drying in vacuum to obtain the supported monometal catalyst.
The bimetallic catalyst for preparing glucose diacid salt by selective oxidation of glucose can be prepared by a coprecipitation method, and the preparation method comprises the following steps:
1) dissolving metal salts of a metal element A and a metal element B in water together to prepare an aqueous solution I with the total concentration of 0.01-0.5M as a precursor;
2) mixing a semiconductor carrier, a sacrificial agent and water, and stirring for 0.5h to prepare a suspension II;
3) adding the aqueous solution I into the suspension II, performing ultrasonic treatment for 20min, and mixing uniformly at 600mW/cm2Under the irradiation of a xenon lamp, carrying out photoreduction under the stirring of a magnetic stirrer at the speed of 200-500 r/min to obtain a supported single-metal catalyst suspension III;
4) and filtering the suspension III to obtain solid particles, washing with deionized water, and drying in vacuum to obtain the supported monometal catalyst.
The bimetallic catalyst for preparing glucose diacid salt by glucose selective oxidation can be prepared by a distributed light deposition method, and the preparation method comprises the following steps:
1) preparing a water-soluble metal salt of a metal element A into a 0.01-0.5M aqueous solution I, and preparing a water-soluble metal salt of a metal element B into a 0.01-0.5M solution II as a precursor;
2) mixing a semiconductor carrier, a sacrificial agent and water, and stirring for 0.5h to prepare a suspension III;
3) adding the aqueous solution I into the suspension III, performing ultrasonic treatment for 20min, and mixing uniformly at 600mW/cm2Under the irradiation of a xenon lamp, stirring by a magnetic stirrer at the speed of 200-500 r/min for photoreduction to obtain a suspension IV;
4) adding the aqueous solution II into the suspension IV, and stirring for 30min by a magnetic stirrer at 200-500 r/min at 600mW/cm2Stirring by a magnetic stirrer at 200-500 r/min under the irradiation of a xenon lamp for photoreduction to obtain an A-B bimetallic catalyst suspension V;
5) and filtering the suspension V to obtain solid particles, washing with deionized water, and drying in vacuum to obtain the supported bimetallic catalyst.
In the method for preparing the supported metal catalyst, the sacrificial agent can be at least of alcohols or aldehydes such as methanol, ethanol, ethylene glycol, propylene glycol, glycerol, formaldehyde, acetaldehyde, glucose, fructose and the like.
The mass ratio of the carrier, the water and the sacrificial agent can be 1: 10-200: 0.1-50.
The photoreduction time can be 0.5-10 h, and is different according to the reduced metal.
A mono-or bimetallic catalyst for the selective oxidation of glucose to glucose diacid salts.
The supported metal or bimetallic catalyst is prepared by using a semiconductor as a carrier and using a light deposition method, and has the characteristic of high dispersion degree of active components. The prepared catalyst is applied to the reaction of preparing the glucarate by selectively oxidizing glucose, and can obtain higher yield of the glucarate.
The invention uses the photocatalysis principle to load metal active components on a semiconductor, and uses the surface of a semiconductor carrier to reduce and prepare the metal catalyst with high dispersibility and small grain size (less than 5nm), and has the advantages that the prepared metal active component is high in dispersion and small grain size, the use amount of noble metal is reduced, the performance of the catalyst is adjusted by using a second active metal component, the defect that a single metal component is easy to be poisoned in reaction is improved, and the activity of the catalyst is improved.
The invention takes a semiconductor as a carrier to prepare a load type single metal or double metal catalyst, and the catalyst is prepared by adopting a method that metal ions receive photo-generated electron reduction deposition on the semiconductor carrier. The catalyst prepared by the method has small particle size and high dispersion degree of active components, and can realize high catalytic activity under low metal loading. The invention reports that the catalyst prepared by the method is used for preparing glucose diacid salt by selectively oxidizing glucose.
The prepared catalyst is applied to the reaction of preparing glucose diacid salt by oxidizing glucose. The reaction is carried out in a high-pressure reaction kettle. Adding 20ml of water, 0.1g of catalyst and 0.5g of glucose into a reaction kettle with a polytetrafluoroethylene lining, taking 2.5mmol of sodium hydroxide or sodium bicarbonate as an auxiliary agent, controlling the oxidation reaction temperature at 40-80 ℃, controlling the oxygen pressure at 0.1-3 MPa, and reacting for 1-20 h. Glucose can produce gluconic acid, glucuronic acid, glucaric acid and other oxidation products. The acid generated in the reaction process can be neutralized with the alkali in the solution to generate a salt.
The invention has the following outstanding advantages:
1) the preparation method of the catalyst is simple, the raw materials for preparation are nontoxic, the cost is low, and the prepared heterogeneous catalyst is easy to separate;
2) the catalyst has stable performance and high catalytic activity under the condition of low metal loading;
3) the prepared heterogeneous catalyst is applied to preparing glucose diacid salt by oxidizing glucose, and the raw material glucose is low in cost and easy to obtain. The yield of the product glucarate is high.
Drawings
FIG. 1 shows the stepwise photo-deposition of 0.25 wt% Pt to 0.25 wt% Au/TiO2Transmission electron micrographs.
Detailed Description
The invention is further illustrated with reference to the following examples, which include but are not limited to the following.
Example 1:
to a 100ml quartz flask was added 1g TiO2Carrier, 20ml water and 2ml methanol to obtain a mixed solution I. Mix vigorously at room temperature for 0.5 h. 3.320ml of 0.0386M H was added dropwise to the mixture I under vigorous stirring2PtCl6And (5) ultrasonically mixing the aqueous solution uniformly to obtain a mixed solution II. Vigorously stirring the obtained mixed solution II at 600mW/cm2And (5) irradiating and reducing for 1h under a xenon lamp. Filtering the reduced mixed solution to obtain a solid catalyst, washing the catalyst for multiple times by using deionized water until AgNO is contained in the filtrate3Detecting no Cl ions, and vacuum drying for 6h to obtain Pt/TiO2Adding 20ml of water, 0.1g of catalyst, 0.5g of glucose, 2.5mmol of sodium hydroxide and magnetons into a reaction kettle with a polytetrafluoroethylene lining, sealing the kettle body, discharging air in the kettle body by using oxygen, repeating the steps for 6 times, filling 1MPa of oxygen, heating the reaction kettle to 60 ℃, reacting for 4 hours, filtering the product by a microporous filter membrane, and analyzing the conversion rate of the glucose in the product by using High Performance Liquid Chromatography (HPLC) to be 99 percent and the yield of the sodium glucarate to be 52 percent.
Example 2:
into a 100ml quartz flask1g of ZnO carrier, 20ml of water and 2ml of methanol, and the resulting mixture I is mixed at room temperature with vigorous stirring for 0.5 h. 0.261ml of 0.0486M HAu (NO) was added dropwise to the mixture I under vigorous stirring3)4And (5) ultrasonically mixing the aqueous solution uniformly to obtain a mixed solution II. Vigorously stirring the obtained mixed solution II at 600mW/cm2The method comprises the steps of irradiating and reducing for 1h under a xenon lamp, filtering reduced mixed liquid to obtain a solid catalyst, washing the catalyst for multiple times by using deionized water, and drying for 6h in vacuum to obtain an Au/ZnO catalyst, adding 20ml of water, 0.1g of the catalyst, 0.5g of glucose, 2.5mmol of sodium hydroxide and magnetons into a reaction kettle with a polytetrafluoroethylene lining, sealing the kettle body, discharging air in the kettle body by using oxygen, repeating for 6 times, filling 1MPa of oxygen, heating the reaction kettle to 60 ℃, reacting for 4h, filtering the product by using a microporous filter membrane, and analyzing the conversion rate of glucose in the product by using High Performance Liquid Chromatography (HPLC) to be 99% and the yield of sodium glucarate to be 36%.
Example 3:
to a 100ml quartz flask was added 1g TiO2Carrier, 20ml water and 2ml methanol to obtain a mixed solution I. Mix vigorously at room temperature for 0.5 h. 0.261ml 0.0486M HAuCl was added dropwise to the mixture I under vigorous stirring4And (5) ultrasonically mixing the aqueous solution uniformly to obtain a mixed solution II. Vigorously stirring the obtained mixed solution II at 600mW/cm2And (5) irradiating and reducing for 1h under a xenon lamp. 0.332ml of 0.0386M H were subsequently added dropwise2PtCl6Aqueous solution at 600mW/cm2And (5) irradiating and reducing for 1h under a xenon lamp. Filtering the reduced mixed solution to obtain a solid catalyst, washing the catalyst for multiple times by using deionized water until AgNO is contained in the filtrate3Detecting no Cl ions, and drying for 6h in vacuum to obtain Au @ Pt/TiO2Adding 20ml of water, 0.1g of catalyst, 0.5g of glucose, 2.5mmol of sodium hydroxide and magnetons into a reaction kettle with a polytetrafluoroethylene lining, sealing the kettle body, discharging air in the kettle body by using oxygen, repeating the steps for 6 times, filling 1MPa of oxygen, heating the reaction kettle to 60 ℃, reacting for 4 hours, filtering the product by a microporous filter membrane, and analyzing the conversion rate of the glucose in the product by using High Performance Liquid Chromatography (HPLC) to be 99 percent and the yield of the sodium glucarate to be 71 percent (see table 1)。
Example 4:
1g of ZnO carrier, 20ml of water and 2ml of methanol are added into a 100ml quartz flask to obtain a mixed solution I. Mix vigorously at room temperature for 0.5 h. 0.332ml of 0.0386M H was added dropwise to the mixture I under vigorous stirring2PtCl6And (5) ultrasonically mixing the aqueous solution uniformly to obtain a mixed solution II. Vigorously stirring the obtained mixed solution II at 600mW/cm2And (5) irradiating and reducing for 1h under a xenon lamp. 0.261ml of 0.0486M HAuCl was then added dropwise4Aqueous solution at 600mW/cm2And (5) irradiating and reducing for 1h under a xenon lamp. Filtering the reduced mixed solution to obtain a solid catalyst, washing the catalyst for multiple times by using deionized water until AgNO is contained in the filtrate3Detecting no Cl ions, drying in vacuum for 6h to obtain a Pt @ Au/ZnO catalyst, adding 20ml of water, 0.1g of catalyst, 0.5g of glucose, 2.5mmol of sodium hydroxide and magnetons into a reaction kettle with a polytetrafluoroethylene lining, sealing the kettle body, discharging air in the kettle body by using oxygen, repeating the steps for 6 times, filling 1MPa of oxygen, heating the reaction kettle to 60 ℃, reacting for 4h, filtering the product by a microporous filter membrane, and analyzing the glucose conversion rate in the product by using High Performance Liquid Chromatography (HPLC) to be 99% and the yield of the sodium glucarate to be 58%.
Example 5:
to a 100ml quartz flask was added 1g TiO2Carrier, 20ml water and 2ml methanol to obtain a mixed solution I. Mix vigorously at room temperature for 0.5 h. 0.664ml of 0.0386M Pt (NO) was added dropwise to the mixture I under vigorous stirring3)2And (5) ultrasonically mixing the aqueous solution uniformly to obtain a mixed solution II. Vigorously stirring the obtained mixed solution II at 600mW/cm2And (5) irradiating and reducing for 1h under a xenon lamp. 0.349ml of 0.0663M AgNO was subsequently added dropwise3Aqueous solution at 600mW/cm2And (5) irradiating and reducing for 1h under a xenon lamp. Filtering the reduced mixed solution to obtain a solid catalyst, washing the catalyst for multiple times by using deionized water, and drying for 6 hours in vacuum to obtain Pt @ Ag/TiO2Adding 20ml of water, 0.1g of catalyst, 0.5g of glucose, 2.5mmol of sodium hydroxide and magnetons into a reaction kettle with a polytetrafluoroethylene lining, sealing the kettle body, discharging air in the kettle body by using oxygen, and repeating the stepsAfter 6 times, 1MPa oxygen gas is filled. The reaction kettle is heated to 60 ℃ and the reaction time is 4 h. After the product was filtered through a microporous membrane, the product was analyzed for glucose conversion of 99% and yield of sodium glucarate of 67% using High Performance Liquid Chromatography (HPLC).
Example 6:
to a 100ml quartz flask, 1g of ZnO carrier, 20ml of water, and 2ml of formaldehyde were added, and the resulting mixture I was vigorously stirred and mixed at room temperature for 0.5 h. 0.664ml of 0.0386M H was added dropwise to the mixture I under vigorous stirring2PtCl6And (5) ultrasonically mixing the aqueous solution uniformly to obtain a mixed solution II. Vigorously stirring the obtained mixed solution II at 600mW/cm2And (5) irradiating and reducing for 1h under a xenon lamp. 0.261ml of 0.0486M HAuCl was then added dropwise4Aqueous solution at 600mW/cm2And (5) irradiating and reducing for 1h under a xenon lamp. Filtering the reduced mixed solution to obtain a solid catalyst, washing the catalyst for multiple times by using deionized water until AgNO is contained in the filtrate3Detecting no Cl ions, drying in vacuum for 6h to obtain a Pt @ Au/ZnO catalyst, adding 20ml of water, 0.1g of catalyst, 0.5g of glucose, 2.5mmol of sodium hydroxide and magnetons into a reaction kettle with a polytetrafluoroethylene lining, sealing the kettle body, discharging air in the kettle body by using oxygen, repeating the steps for 6 times, filling 1MPa of oxygen, heating the reaction kettle to 60 ℃, reacting for 4h, filtering the product by a microporous filter membrane, and analyzing the glucose conversion rate in the product by using High Performance Liquid Chromatography (HPLC) to be 87% and the yield of the sodium glucarate to be 60%.
Example 7:
to a 100ml quartz flask was added 1g TiO2Carrier, 20ml water and 2ml methanol to obtain a mixed solution I. Mix vigorously at room temperature for 0.5 h. 0.332ml of 0.0386M H was added dropwise to the mixture I under vigorous stirring2PtCl6Aqueous solution and 0.261ml 0.0486M HAuCl4And (5) ultrasonically mixing the aqueous solution uniformly to obtain a mixed solution II. Vigorously stirring the obtained mixed solution II at 600mW/cm2And (5) irradiating and reducing for 1h under a xenon lamp. Filtering the reduced mixed solution to obtain a solid catalyst, washing the catalyst for multiple times by using deionized water until AgNO is contained in the filtrate3Detecting no Cl ions, and vacuum drying for 6h to obtain PtAu/TiO2Adding 20ml of water, 0.1g of catalyst, 0.5g of glucose, 2.5mmol of sodium hydroxide and magnetons into a reaction kettle with a polytetrafluoroethylene lining, sealing the kettle body, discharging air in the kettle body by using oxygen, repeating the steps for 6 times, filling 1MPa of oxygen, heating the reaction kettle to 60 ℃, reacting for 4 hours, filtering the product by a microporous filter membrane, and analyzing the conversion rate of the glucose in the product by using High Performance Liquid Chromatography (HPLC) to be 99% and the yield of the sodium glucarate to be 62% (see table 1).
Example 8:
1g of ZnO carrier, 20ml of water and 2ml of ethanol are added into a 100ml quartz flask to obtain a mixed solution I. Mix vigorously at room temperature for 0.5 h. 0.664ml of 0.0386M Pt (NO) was added dropwise to the mixture I under vigorous stirring3)2Aqueous solution and 0.349ml of 0.0663M AgNO3And (5) ultrasonically mixing the aqueous solution uniformly to obtain a mixed solution II. Vigorously stirring the obtained mixed solution II at 600mW/cm2And (5) irradiating and reducing for 4h under a xenon lamp. Filtering the reduced mixed solution to obtain a solid catalyst, washing the catalyst for multiple times by using deionized water, and drying for 6 hours in vacuum to obtain PtAg/ZnO2Adding 20ml of water, 0.1g of catalyst, 0.5g of glucose, 2.5mmol of sodium hydroxide and magnetons into a reaction kettle with a polytetrafluoroethylene lining, sealing the kettle body, discharging air in the kettle body by using oxygen, repeating the steps for 6 times, filling 1MPa of oxygen, heating the reaction kettle to 60 ℃, reacting for 4 hours, filtering the product by a microporous filter membrane, and analyzing the conversion rate of the glucose in the product by using High Performance Liquid Chromatography (HPLC) to be 99 percent and the yield of the sodium glucarate to be 58 percent.
Example 9:
to a 100ml quartz flask was added 1g TiO2Carrier, 20ml water and 2ml methanol to obtain a mixed solution I. Mix vigorously at room temperature for 0.5 h. 0.349ml of 0.0663M AgNO is dropwise added into the mixed solution I under vigorous stirring3Aqueous solution and 0.261ml 0.0486M of HAu (NO)3)4And (5) ultrasonically mixing the aqueous solution uniformly to obtain a mixed solution II. Vigorously stirring the obtained mixed solution II at 600mW/cm2And (5) irradiating and reducing for 1h under a xenon lamp. Filtering the reduced mixed solution to obtain a solid catalyst, and repeatedly washing the solid catalyst with deionized waterThe mixture is processed by chemical agent and vacuum drying for 6 hours to obtain AgAu/TiO2Adding 20ml of water, 0.1g of catalyst, 0.5g of glucose, 2.5mmol of sodium hydroxide and magnetons into a reaction kettle with a polytetrafluoroethylene lining, sealing the kettle body, discharging air in the kettle body by using oxygen, repeating the steps for 6 times, filling 1MPa of oxygen, heating the reaction kettle to 60 ℃, reacting for 4 hours, filtering the product by a microporous filter membrane, and analyzing the conversion rate of the glucose in the product by using High Performance Liquid Chromatography (HPLC) to be 78% and the yield of the sodium glucarate to be 34%.
Example 10:
1g of ZnO carrier, 20ml of water and 2ml of methanol are added into a 100ml quartz flask to obtain a mixed solution I. Mix vigorously at room temperature for 0.5 h. 1.320ml of 0.0386M H was added dropwise to the mixture I under vigorous stirring2PtCl6Aqueous solution and 0.417ml of 0.0287M Bi (NO)3)3And (5) ultrasonically mixing the aqueous solution uniformly to obtain a mixed solution II. Vigorously stirring the obtained mixed solution II at 600mW/cm2And (5) irradiating and reducing for 1h under a xenon lamp. Filtering the reduced mixed solution to obtain a solid catalyst, washing the catalyst for multiple times by using deionized water until AgNO is contained in the filtrate3Detecting no Cl ions, and vacuum drying for 6h to obtain PtBi/ZnO2Adding 20ml of water, 0.1g of catalyst, 0.5g of glucose, 2.5mmol of sodium hydroxide and magnetons into a reaction kettle with a polytetrafluoroethylene lining, sealing the kettle body, discharging air in the kettle body by using oxygen, repeating the steps for 6 times, filling 1MPa of oxygen, heating the reaction kettle to 60 ℃, reacting for 4 hours, filtering the product by a microporous filter membrane, and analyzing the conversion rate of the glucose in the product by using High Performance Liquid Chromatography (HPLC) to be 99 percent and the yield of the sodium glucarate to be 57 percent.
Comparative example 1:
to a 100ml quartz flask was added 1g TiO2Carrier, 3ml water, 0.261ml 0.0486M HAuCl4Aqueous solution and 0.332ml 0.0386M H2PtCl6The aqueous solution was stirred at 80 ℃ to dry the solvent to obtain a solid powder I. Solid powder I was used H at 350 ℃2Roasting for 4h to obtain PtAu/TiO2(im) a catalyst. Adding 20ml of water and 0ml of water into a reaction kettle with a polytetrafluoroethylene lining1g of catalyst, 0.5g of glucose, 2.5mmol of sodium hydroxide and magnetons, sealing the kettle body, discharging air in the kettle body by using oxygen, repeating the steps for 6 times, filling 1MPa of oxygen, heating the reaction kettle to 60 ℃, reacting for 4 hours, filtering the product by a microporous filter membrane, and analyzing the conversion rate of the glucose in the product by using High Performance Liquid Chromatography (HPLC) to be 45% and the yield of the sodium glucarate to be 9% (see table 1).
TABLE 1
Figure BDA0001297844930000081
0.25 wt% Pt-0.25 wt% Au/TiO prepared by step-by-step light deposition method2See FIG. 1 for a transmission electron micrograph.
The invention adopts an illumination semiconductor carrier, and is prepared by reducing and depositing metal ions by photo-generated electrons. Wherein the supported metal catalyst comprises a single metal or a bimetallic component. The prepared supported nano metal catalyst has the characteristics of small metal component particle size, high dispersity and uniform distribution. The preparation method of the catalyst is simple in process and environment-friendly. The prepared catalyst is applied to the reaction of preparing glucarate by oxidizing glucose, the yield of the glucarate is high, and the catalyst can be recycled for multiple times.

Claims (5)

  1. The kinds of supported metal catalyst is characterized by that it is formed from semiconductor carrier supported single metal, and its mass percentage is that the carrier in the catalyst is 92% -99.7%, and the metal active component is 0.3% -8%, the described metal component is single component, and its single component is metal element A, and the described metal element A is selected from kinds of Cr, Mn, Fe, Co, Nb, Ru, Rh, Pd, Ag, Re, Ir, Pt, Au and Bi, and the described semiconductor carrier is selected from TiO, Pd, Ag, Re, Ir, Pt and Au, and Bi2、Cu2O、ZnO、CdS、SnO2、WO3At least ;
    the preparation method of the single metal catalyst for preparing the glucarate by the selective oxidation of the glucose by the light deposition comprises the following steps:
    1) preparing a 0.01-0.5M aqueous solution I of metal salt of a metal element A as a precursor;
    2) mixing a semiconductor carrier, a sacrificial agent and water, and stirring for 0.5h to prepare a suspension II;
    3) adding the aqueous solution I into the suspension II, performing ultrasonic treatment for 20min, and mixing uniformly at 600mW/cm2Under the irradiation of a xenon lamp, carrying out photoreduction under the stirring of a magnetic stirrer at the speed of 200-500 r/min to obtain a supported single-metal catalyst suspension III;
    4) and filtering the suspension III to obtain solid particles, washing with deionized water, and drying in vacuum to obtain the supported monometal catalyst.
  2. 2, supported metal catalysts, which are characterized by comprising a semiconductor carrier supported bimetal, wherein the carrier accounts for 92-99.7% of the catalyst, the metal active component accounts for 0.3-8%, the metal component is a double component, the double component comprises a metal element A and a metal element B, the mass ratio of the metal element A to the metal element B is (1-5): 1, the metal element A is selected from Cr, Mn, Fe, Co, Nb, Ru, Rh, Pd, Ag, Re, Ir, Pt, Au and Bi is , the metal element B is selected from Pt, Pd, Ag, Au and Bi is , the metal element A and the metal element B are not the same , and the semiconductor carrier is selected from TiO2、Cu2O、ZnO、CdS、SnO2、WO3At least ;
    the preparation method of the bimetallic catalyst for preparing glucose diacid salt by selective oxidation of glucose through light deposition comprises the following steps:
    1) preparing a water-soluble metal salt of a metal element A into a 0.01-0.5M aqueous solution I, and preparing a water-soluble metal salt of a metal element B into a 0.01-0.5M solution II as a precursor;
    2) mixing a semiconductor carrier, a sacrificial agent and water, and stirring for 0.5h to prepare a suspension III;
    3) adding the aqueous solution I into the suspension III, performing ultrasonic treatment for 20min, and mixing uniformly at 600mW/cm2Under the irradiation of a xenon lamp, stirring by a magnetic stirrer at the speed of 200-500 r/min for photoreduction to obtain a suspension IV;
    4) adding aqueous solution II, 20 to the suspension IVStirring for 30min by a magnetic stirrer at a speed of 0-500 r/min under 600mW/cm2Stirring by a magnetic stirrer at 200-500 r/min under the irradiation of a xenon lamp for photoreduction to obtain an A-B bimetallic catalyst suspension V;
    5) and filtering the suspension V to obtain solid particles, washing with deionized water, and drying in vacuum to obtain the supported bimetallic catalyst.
  3. 3. Supported metal catalysts according to claim 1 or 2 wherein the sacrificial agent is selected from at least of methanol, ethanol, ethylene glycol, propylene glycol, glycerol, formaldehyde, acetaldehyde, glucose, fructose.
  4. 4. The supported metal catalyst of claim 1 or claim 2, wherein the mass ratio of the carrier, water and sacrificial agent is 1: 10-200: 0.1-50.
  5. 5. The supported metal catalysts of claim 1 or 2, wherein the photoreduction time is 0.5-10 hours.
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CN107537479B (en) * 2017-08-15 2020-08-25 武汉理工大学 Catalyst for degrading volatile organic pollutants and preparation method thereof
CN109759057A (en) * 2019-01-23 2019-05-17 常州市龙星工业自动化系统有限公司 A kind of preparation method and its catalyst of noble metal-oxide composite catalyst
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CN112642469B (en) * 2019-10-10 2023-06-06 中国石油化工股份有限公司 Catalyst for preparing ethylene glycol by oxalate hydrogenation, preparation method and application thereof, and method for preparing ethylene glycol
CN112675843A (en) * 2021-01-11 2021-04-20 西部金属材料股份有限公司 Silver quantum dot composite photocatalyst and preparation method thereof
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CN113786831A (en) * 2021-09-10 2021-12-14 上海电力大学 Amorphous TiO2Ag/composite nano-particle and preparation method and application thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101773827A (en) * 2009-05-27 2010-07-14 南京理工大学 Preparation method of high-activity platinum-loaded TiO2 nanotube photocatalyst
CN102603515A (en) * 2012-02-21 2012-07-25 厦门大学 Method for preparing gluconic acid by direct oxidization of cellulose
CN104923278A (en) * 2015-05-22 2015-09-23 宁夏大学 Novel graphene-based Mo2N-Mo2C/CdS composite photocatalyst, and preparation and application thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101773827A (en) * 2009-05-27 2010-07-14 南京理工大学 Preparation method of high-activity platinum-loaded TiO2 nanotube photocatalyst
CN102603515A (en) * 2012-02-21 2012-07-25 厦门大学 Method for preparing gluconic acid by direct oxidization of cellulose
CN104923278A (en) * 2015-05-22 2015-09-23 宁夏大学 Novel graphene-based Mo2N-Mo2C/CdS composite photocatalyst, and preparation and application thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
"Using the hydrogen and oxygen in water directly for hydrogenation reactions and glucose oxidation by photocatalysis";Baowen Zhou et al.;《Chemical Science》;20151009;第7卷;第463-468页 *
"葡萄糖催化氧化制备葡萄糖酸(盐)催化剂研究进展";王素芳等;《工业催化》;20071015;第15卷(第10期);第5-11页 *

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