CN107029705A - The preparation and its application of a kind of load type metal catalyst - Google Patents
The preparation and its application of a kind of load type metal catalyst Download PDFInfo
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- CN107029705A CN107029705A CN201710351216.6A CN201710351216A CN107029705A CN 107029705 A CN107029705 A CN 107029705A CN 201710351216 A CN201710351216 A CN 201710351216A CN 107029705 A CN107029705 A CN 107029705A
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- 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
- 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
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
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- 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
- 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
- B01J23/48—Silver or gold
- B01J23/50—Silver
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- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/23—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups
- C07C51/235—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups of —CHO groups or primary alcohol groups
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Abstract
The preparation and its application of a kind of load type metal catalyst, are related to glucaric acid.Catalyst uses illumination semiconductor carrier, is made by light induced electron reduction metal ions.Load type metal catalyst therein includes monometallic or bimetallic component.Obtained supported nano-gold metal catalyst has metal component particle diameter small, and decentralization is high, the characteristics of being evenly distributed.The method for preparing catalyst technique is simple, environmental protection.When obtained catalyst is applied to grape glycoxidative glucaric acid reactant salt processed, glucarate high income, catalyst can recycled for multiple times.
Description
Technical field
The present invention relates to glucaric acid, more particularly, to the preparation and its application of a kind of load type metal catalyst.
Background technology
Glucaric acid is a kind of nontoxic natural organic acids, is common in the fruit such as grape fruit, apple, orange and cruciate flower
In section vegetables.Glucaric acid or a kind of important biomass transformation platform compound, can be prepared a variety of as intermediate
Derivative.It is extensive in sector applications such as food, medicine, chemical industry.Add the strengthening model and dairy products of antacidin
Commercially produce, pharmaceutical preparation is also for the development phase.And glucaric acid and its derivative glucaric acid 1,4- lactone by
Play a role and paid attention to by medical field in terms of reduction cholesterol levels, regulation and control human hormone in it.In addition, glucose
Diacid also has actual application value in chemical field.It can as polymer monomer synthesizing amide class, hydroxylating nylon and
Dimethyl silicone polymer polyamide, synthesising biological degradable polymer, slow release fertilizer etc., also it can produce household washing as raw material
Agent, preservative and concrete admixture.Glucaric acid can also be used as the chelating agent of anti-corrosion of metal in electroplating technology.
In 2004, glucaric acid was defined as one of " 12 kinds of most valuable biomass platform chemicals " by USDOE.
It as a variety of emerging biomass energies synthesis material, with huge potential age deduction.Using renewable resource, from Portugal
Grape sugar sets out, and to prepare glucaric acid particularly significant.
At present, the preparation method of glucaric acid includes bioanalysis and chemical method.Bioanalysis using glucuronic acid as raw material,
Using glycuronidase as catalyst, in H2O2And Fe2+In the presence of be made glucaric acid.And because metabolic pathway is long,
The reaction for preparing glucaric acid by biofermentation reaction by raw material of glucose is difficult to.Produced currently with fermentation method
The method of glucaric acid yields poorly, and incubation time is long, and separation and Extraction is difficult, it is difficult to utilization and extention.Chemical method is main with grape
Sugar is raw material, with HNO3As strong oxidizer, by controlling reaction process, the selectivity of regulation generation product.Primary product is
Glucaric acid and small carboxylic acid molecules.Because reaction is violent, reaction process control is difficult, and the process yield is low, and benefit is not high.
In addition, nitric acid belongs to severe corrosive chemicals, it is serious to damage of facilities.In addition, also have using heterogeneous catalysis method, using noble metal as
Catalyst glucose is converted into glucaric acid.Noble metal carrying capacity in usual catalyst is high, and catalyst activity is limited,
Target product glucaric acid is easily further aoxidized.
Chinese patent CN 103436910A disclose a kind of method that utilization electrochemical process prepares glucaric acid.This method
Using sulfuric acid or sulfate as electrolyte, glucaric acid is generated using electrocatalytic oxidation glucose, and utilize membrane separation technique
Realize the separation of product.But this method has the problem of reaction raw materials concentration is relatively low, accessory substance is more.Additionally due to needing to use sulphur
, there is etching apparatus and problem of environmental pollution in acid or Sulfates electrolyte.
Jin X etc. report infusion process and prepare Pt1Cu3/TiO2The loaded catalyst of metal core shell structure
(Exceptional performance of bimetallic Pt1Cu3/TiO2,nanocatalysts for oxidation
of gluconic acid and glucose with O2,to glucaric acid[J].Journal of
Catalysis,2015,330:323-329), but its Cu shell can due to the grape in product after reaction is recycled for multiple times
The complexing of saccharic acid is leached, and causes catalyst catalytic performance to be not sufficiently stable.And exist particle diameter it is larger (>5nm), noble-metal-supported
Amount height (>4wt%) the problem of.Saha B etc. are reported prepares grape using the 5wt%Pt/C catalyst glucose of business
Saccharic acid (Pt Catalysts for Efficient Aerobic Oxidation of Glucose to Glucaric
Acid in Water[J].Green Chemistry,2016,18,3815-3822).But deposit the negative of noble metal in the catalyst
Carrying capacity is high, the problem of causing to have catalyst poisoning inactivation due to the strong absorption of intermediate product gluconic acid in high conversion.
The content of the invention
The first object of the present invention is to provide a kind of load type metal catalyst.
The second object of the present invention is that providing the monometallic for preparing glucarate for glucose selective oxidation urges
Agent is prepared using light deposition method.
The third object of the present invention is that providing the bimetallic for preparing glucarate for glucose selective oxidation urges
Agent is prepared using coprecipitated method.
The fourth object of the present invention is that providing the bimetallic for preparing glucarate for glucose selective oxidation urges
Agent is prepared using distribution light deposition method.
The fifth object of the present invention be provide be used for glucose selective oxidation prepare glucarate monometallic or
Bimetallic catalyst.
The load type metal catalyst loads monometallic by semiconductor carrier or bimetallic is constituted, with the percentage of quality
Carrier accounts for 92%~99.7% in meter, catalyst, and metal active constituent accounts for 0.3%~8%；The metal component be one pack system or
Two-component, single group is divided into metal element A, and two-component is metal element A and metallic element B, and metal element A is with metallic element B's
Mass ratio is (1~5) ︰ 1, the metal element A is selected from Cr, Mn, Fe, Co, Nb, Ru, Rh, Pd, Ag, Re, Ir, Pt, Au, Bi etc.
In one kind；The one kind of metallic element B in Pt, Pd, Ag, Au, Bi etc.；The metal element A and metallic element B are not same
A kind of element, the semiconductor carrier is selected from TiO2、Cu2O、ZnO、CdS、SnO2、WO3At least one of Deng.
The single-metal reforming catalyst for preparing glucarate for glucose selective oxidation is prepared using light deposition method, its
Preparation method comprises the following steps：
1) aqueous solution I that the metal salt of metal element A is configured to 0.01~0.5M is used as presoma；
2) semiconductor carrier, sacrifice agent and water are mixed, suspension II is made in stirring 0.5h；
3) aqueous solution I is added in suspension II, ultrasonic 20min, be well mixed, in 600mW/cm2Under xenon lamp irradiation,
Photo-reduction is carried out under 200~500r/min magnetic stirrers, load single-metal reforming catalyst suspension III is obtained；
4) suspension III is filtered, solid particle is obtained, makes to be washed with deionized, is dried in vacuo, obtains support type Dan Jin
Metal catalyst.
The bimetallic catalyst for preparing glucarate for glucose selective oxidation can be prepared using coprecipitated method,
Its preparation method comprises the following steps：
1) by the common total concentration soluble in water that is configured to of metal element A and metallic element B metal salt for 0.01~0.5M
Aqueous solution I be used as presoma；
2) semiconductor carrier, sacrifice agent and water are mixed, suspension II is made in stirring 0.5h；
3) aqueous solution I is added in suspension II, ultrasonic 20min, be well mixed, in 600mW/cm2Under xenon lamp irradiation,
Photo-reduction is carried out under 200~500r/min magnetic stirrers, load single-metal reforming catalyst suspension III is obtained；
4) suspension III is filtered, solid particle is obtained, makes to be washed with deionized, is dried in vacuo, obtains support type Dan Jin
Metal catalyst.
The bimetallic catalyst for preparing glucarate for glucose selective oxidation can be using the side for being distributed light deposition
Prepared by method, its preparation method comprises the following steps：
1) water-soluble metal salt of metal element A is configured to 0.01~0.5M aqueous solution I, by metallic element B water
Soluble metal salts is configured to 0.01~0.5M solution II as presoma；
2) semiconductor carrier, sacrifice agent and water are mixed, suspension III is made in stirring 0.5h；
3) aqueous solution I is added in suspension III, ultrasonic 20min, be well mixed, in 600mW/cm2Under xenon lamp irradiation,
200~500r/min magnetic stirrers carry out photo-reduction, obtain suspension IV；
4) aqueous solution II, 200~500r/min magnetic stirrer 30min is added in suspension IV, in 600mW/
cm2Lower 200~500r/min the magnetic stirrers of xenon lamp irradiation carry out photo-reduction, obtain A-B bimetallic catalyst suspensions
V；
5) suspension V is filtered, solid particle is obtained, makes to be washed with deionized, is dried in vacuo, obtains load type double-metal
Catalyst.
In the method for preparing load type metal catalyst, the sacrifice agent may be selected from methanol, ethanol, ethylene glycol, propane diols,
At least one of the alcohol or aldehyde such as glycerine, formaldehyde, acetaldehyde, glucose, fructose.
The mass ratio of the carrier, water and sacrifice agent can be 1 ︰ (10~200) ︰ (0.1~50).
The time of the photo-reduction can be 0.5~10h, different according to the metal reduced.
The monometallic or bimetallic catalyst of glucarate are prepared for glucose selective oxidation.
The load type metal or bimetallic catalyst of the present invention is to be prepared by carrier of semiconductor using light deposition method, tool
The characteristics of active component decentralization is high.Obtained catalyst prepares glucarate applied to selective oxidation glucose
Reaction, can obtain higher glucarate yield.
The present invention utilizes photocatalysis principle, on the semiconductor carried metal active component.Utilize semiconductor carrier surface light
Reduction prepare polymolecularity small particle (<5nm) metallic catalyst, the advantage is that the metal active constituent high dispersive, small of preparation
The catalyst of particle diameter, reduces noble metal usage amount.The performance of catalyst is adjusted using the second active metal component, single gold is improved
Category component is easy to the shortcoming of poisoning in the reaction, lifts catalyst activity.Glucarate can be made in high yield by the present invention,
Product is stable compared with glucaric acid, it is easy to preserve transport.Glucarate can obtain glucose two by simple acidifying
Acid.
The present invention prepares support type monometallic or bimetallic catalyst using semiconductor as carrier, catalyst using metal from
It is prepared by the method that son receives light induced electron reduction deposition on semiconductor carrier.Catalyst made from this method, particle diameter is small, activity
Component decentralization is high, and the high catalytic activity under low metal load capacity can be achieved.Catalyst prepared by present invention report this method is used
Glucarate is prepared in selective oxidation glucose.
The catalyst of preparation is applied to the glycoxidative reaction for preparing glucarate of grape.The reaction is in autoclave
It is middle to carry out.20ml water, 0.1g catalyst and 0.5g glucose is added in the reactor with polytetrafluoroethyllining lining, with
2.5mmol sodium hydroxide or sodium acid carbonate is auxiliary agent, and oxidizing reaction temperature control is at 40~80 DEG C, and oxygen pressure control exists
0.1~3MPa, the reaction time is 1~20h.Glucose can generate gluconic acid, glucuronic acid, glucaric acid and other
Oxidation product.Generated in course of reaction acid can with the alkali in solution and generate salt.
The present invention has following outstanding advantages：
1) method for preparing catalyst is simple, and preparing raw material is nontoxic, with low cost, and obtained heterogeneous catalyst is easily isolated；
2) catalyst agent performance is stable, and can have high catalytic activity in the case of low metal load capacity；
3) obtained heterogeneous catalyst is applied to the glycoxidative glucarate processed of grape, raw materials of glucose cost is low,
It is easily obtained.The high income of product glucarate.
Brief description of the drawings
Fig. 1 is 0.25wt%Pt-0.25wt%Au/TiO prepared by substep Photodeposition2Transmission electron microscope picture.
Embodiment
With reference to embodiment, the invention will be further described, including but not limited to herein below.
Embodiment 1：
1g TiO are added into 100ml quartz flasks2Carrier, 20ml water, 2ml methanol obtains mixed liquor I.It is acute at room temperature
Strong stirring mixing 0.5h.Instill 3.320ml 0.0386M H dropwise to mixed liquor I with vigorous stirring2PtCl6The aqueous solution, and
Ultrasonic mixing is uniform, is designated as mixed liquor II.Gained mixed liquor II is stirred vigorously, in 600mW/cm2Irradiation reduction 1h under xenon lamp.Cross
Mixed liquor after filter reduction obtains solid catalyst, using the multiple washing catalyst of deionized water, until AgNO in filtrate3Detection
Without Cl ions, 6h is dried in vacuo, Pt/TiO is obtained2Catalyst.20ml is added in the reactor with polytetrafluoroethyllining lining
Water, 0.1g catalyst, 0.5g glucose, 2.5mmol sodium hydroxide and a magneton.Seal and oxygen is used after kettle by kettle
Interior air discharge, is filled with 1MPa oxygen after being repeated 6 times.Reactor is heated to 60 DEG C, reaction time 4h.Product is filtered by micropore
It is 99% to analyze inversion rate of glucose in product using high performance liquid chromatography (HPLC) after membrane filtration, and glucaric acid sodium yield is
52%.
Embodiment 2：
The addition 1g ZnO carriers into 100ml quartz flasks, 20ml water, 2ml methanol, and by gained mixed liquor I in room temperature
Under be stirred vigorously mixing 0.5h.Instill 0.261ml 0.0486M HAu (NO dropwise to mixed liquor I with vigorous stirring3)4It is water-soluble
Liquid, and ultrasonic mixing is uniform, is designated as mixed liquor II.Gained mixed liquor II is stirred vigorously, in 600mW/cm2Reduction is irradiated under xenon lamp
1h.Mixed liquor after filtering reduction obtains solid catalyst, using the multiple washing catalyst of deionized water, is dried in vacuo 6h, obtains
To Au/ZnO catalyst.20ml water, 0.1g catalyst, 0.5g grapes are added in the reactor with polytetrafluoroethyllining lining
Sugar, 2.5mmol sodium hydroxide and a magneton.Air in kettle is discharged using oxygen after sealing kettle, filled after being repeated 6 times
Enter 1MPa oxygen.Reactor is heated to 60 DEG C, reaction time 4h.Product is by using high-efficient liquid phase color after filtering with microporous membrane
It is 99% to compose inversion rate of glucose in (HPLC) analysis product, and glucaric acid sodium yield is 36%.
Embodiment 3：
1g TiO are added into 100ml quartz flasks2Carrier, 20ml water, 2ml methanol obtains mixed liquor I.It is acute at room temperature
Strong stirring mixing 0.5h.Instill 0.261ml 0.0486M HAuCl dropwise to mixed liquor I with vigorous stirring4The aqueous solution, and
Ultrasonic mixing is uniform, is designated as mixed liquor II.Gained mixed liquor II is stirred vigorously, in 600mW/cm2Irradiation reduction 1h under xenon lamp.With
0.332ml 0.0386M H is added dropwise to afterwards2PtCl6The aqueous solution, in 600mW/cm2Irradiation reduction 1h under xenon lamp.After filtering reduction
Mixed liquor obtain solid catalyst, using the multiple washing catalyst of deionized water, until filtrate in AgNO3Detection without Cl from
Son, is dried in vacuo 6h, obtains Au@Pt/TiO2Catalyst.20ml water is added in the reactor with polytetrafluoroethyllining lining,
0.1g catalyst, 0.5g glucose, 2.5mmol sodium hydroxide and a magneton.Seal in kettle after kettle using oxygen
Air is discharged, and 1MPa oxygen is filled with after being repeated 6 times.Reactor is heated to 60 DEG C, reaction time 4h.Product passes through miillpore filter
It is 99% to analyze inversion rate of glucose in product using high performance liquid chromatography (HPLC) after filtering, and glucaric acid sodium yield is
71% (referring to table 1).
Embodiment 4：
1g ZnO carriers are added into 100ml quartz flasks, 20ml water, 2ml methanol obtains mixed liquor I.It is violent at room temperature
Stirring mixing 0.5h.Instill 0.332ml 0.0386M H dropwise to mixed liquor I with vigorous stirring2PtCl6The aqueous solution, and surpass
Sound is well mixed, and is designated as mixed liquor II.Gained mixed liquor II is stirred vigorously, in 600mW/cm2Irradiation reduction 1h under xenon lamp.Then
It is added dropwise to 0.261ml 0.0486M HAuCl4The aqueous solution, in 600mW/cm2Irradiation reduction 1h under xenon lamp.It is mixed after filtering reduction
Close liquid and obtain solid catalyst, using the multiple washing catalyst of deionized water, until AgNO in filtrate3Detection is without Cl ions, very
Sky dries 6h, obtains Pt@Au/ZnO catalyst.20ml water is added in the reactor with polytetrafluoroethyllining lining, 0.1g is urged
Agent, 0.5g glucose, 2.5mmol sodium hydroxide and a magneton.Air in kettle is arranged using oxygen after sealing kettle
Go out, 1MPa oxygen is filled with after being repeated 6 times.Reactor is heated to 60 DEG C, reaction time 4h.After product is by filtering with microporous membrane
The use of inversion rate of glucose in high performance liquid chromatography (HPLC) analysis product is 99%, glucaric acid sodium yield is 58%.
Embodiment 5：
1g TiO are added into 100ml quartz flasks2Carrier, 20ml water, 2ml methanol obtains mixed liquor I.It is acute at room temperature
Strong stirring mixing 0.5h.Instill 0.664ml 0.0386M Pt (NO dropwise to mixed liquor I with vigorous stirring3)2The aqueous solution, and
Ultrasonic mixing is uniform, is designated as mixed liquor II.Gained mixed liquor II is stirred vigorously, in 600mW/cm2Irradiation reduction 1h under xenon lamp.With
0.349ml 0.0663M AgNO is added dropwise to afterwards3The aqueous solution, in 600mW/cm2Irradiation reduction 1h under xenon lamp.After filtering reduction
Mixed liquor obtains solid catalyst, using the multiple washing catalyst of deionized water, is dried in vacuo 6h, obtains Pt@Ag/TiO2Catalysis
Agent.20ml water, 0.1g catalyst, 0.5g glucose, 2.5mmol hydrogen are added in the reactor with polytetrafluoroethyllining lining
Sodium oxide molybdena and a magneton.Air in kettle is discharged using oxygen after sealing kettle, 1MPa oxygen is filled with after being repeated 6 times.Will
Reactor is heated to 60 DEG C, reaction time 4h.Product after filtering with microporous membrane using high performance liquid chromatography (HPLC) by being analyzed
Inversion rate of glucose is 99% in product, and glucaric acid sodium yield is 67%.
Embodiment 6：
The addition 1g ZnO carriers into 100ml quartz flasks, 20ml water, 2ml formaldehyde, and by gained mixed liquor I in room temperature
Under be stirred vigorously mixing 0.5h.Instill 0.664ml 0.0386M H dropwise to mixed liquor I with vigorous stirring2PtCl6It is water-soluble
Liquid, and ultrasonic mixing is uniform, is designated as mixed liquor II.Gained mixed liquor II is stirred vigorously, in 600mW/cm2Reduction is irradiated under xenon lamp
1h.Then it is added dropwise to 0.261ml 0.0486M HAuCl4The aqueous solution, in 600mW/cm2Irradiation reduction 1h under xenon lamp.Filtering is also
Mixed liquor after original obtains solid catalyst, using the multiple washing catalyst of deionized water, until AgNO in filtrate3Detection is without Cl
Ion, is dried in vacuo 6h, obtains Pt@Au/ZnO catalyst.20ml water is added in the reactor with polytetrafluoroethyllining lining,
0.1g catalyst, 0.5g glucose, 2.5mmol sodium hydroxide and a magneton.Seal in kettle after kettle using oxygen
Air is discharged, and 1MPa oxygen is filled with after being repeated 6 times.Reactor is heated to 60 DEG C, reaction time 4h.Product passes through miillpore filter
It is 87% to analyze inversion rate of glucose in product using high performance liquid chromatography (HPLC) after filtering, and glucaric acid sodium yield is
60%.
Embodiment 7：
1g TiO are added into 100ml quartz flasks2Carrier, 20ml water, 2ml methanol obtains mixed liquor I.It is acute at room temperature
Strong stirring mixing 0.5h.Instill 0.332ml 0.0386M H dropwise to mixed liquor I with vigorous stirring2PtCl6The aqueous solution and
0.261ml 0.0486M HAuCl4The aqueous solution, and ultrasonic mixing is uniform, is designated as mixed liquor II.It is stirred vigorously gained mixed liquor
II, in 600mW/cm2Irradiation reduction 1h under xenon lamp.Mixed liquor after filtering reduction obtains solid catalyst, uses deionized water
Multiple washing catalyst, until AgNO in filtrate3Detection is dried in vacuo 6h, obtains PtAu/TiO without Cl ions2Catalyst.In band
There are addition 20ml water, 0.1g catalyst, 0.5g glucose, 2.5mmol sodium hydroxide in the reactor of polytetrafluoroethyllining lining
With a magneton.Air in kettle is discharged using oxygen after sealing kettle, 1MPa oxygen is filled with after being repeated 6 times.By reactor
It is heated to 60 DEG C, reaction time 4h.Product after filtering with microporous membrane using high performance liquid chromatography (HPLC) by being analyzed in product
Inversion rate of glucose is 99%, and glucaric acid sodium yield is 62% (referring to table 1).
Embodiment 8：
1g ZnO carriers are added into 100ml quartz flasks, 20ml water, 2ml ethanol obtains mixed liquor I.It is violent at room temperature
Stirring mixing 0.5h.Instill 0.664ml 0.0386M Pt (NO dropwise to mixed liquor I with vigorous stirring3)2The aqueous solution and
0.349ml 0.0663M AgNO3The aqueous solution, and ultrasonic mixing is uniform, is designated as mixed liquor II.It is stirred vigorously gained mixed liquor
II, in 600mW/cm2Irradiation reduction 4h under xenon lamp.Mixed liquor after filtering reduction obtains solid catalyst, uses deionized water
Multiple washing catalyst, is dried in vacuo 6h, obtains PtAg/ZnO2Catalyst.In the reactor with polytetrafluoroethyllining lining
Add 20ml water, 0.1g catalyst, 0.5g glucose, 2.5mmol sodium hydroxide and a magneton.Seal and oxygen is used after kettle
Gas discharges air in kettle, and 1MPa oxygen is filled with after being repeated 6 times.Reactor is heated to 60 DEG C, reaction time 4h.Product leads to
It is 99%, glucaric acid to cross and analyze inversion rate of glucose in product using high performance liquid chromatography (HPLC) after filtering with microporous membrane
Sodium yield is 58%.
Embodiment 9：
1g TiO are added into 100ml quartz flasks2Carrier, 20ml water, 2ml methanol obtains mixed liquor I.It is acute at room temperature
Strong stirring mixing 0.5h.Instill 0.349ml 0.0663M AgNO dropwise to mixed liquor I with vigorous stirring3The aqueous solution and
0.261ml 0.0486M HAu (NO3)4The aqueous solution, and ultrasonic mixing is uniform, is designated as mixed liquor II.Gained is stirred vigorously to mix
Liquid II, in 600mW/cm2Irradiation reduction 1h under xenon lamp.Mixed liquor after filtering reduction obtains solid catalyst, uses deionization
The multiple washing catalyst of water, is dried in vacuo 6h, obtains AgAu/TiO2Catalyst.In the reactor with polytetrafluoroethyllining lining
Middle addition 20ml water, 0.1g catalyst, 0.5g glucose, 2.5mmol sodium hydroxide and a magneton.Used after sealing kettle
Oxygen discharges air in kettle, and 1MPa oxygen is filled with after being repeated 6 times.Reactor is heated to 60 DEG C, reaction time 4h.Product
It is 78%, glucose two by analyzing inversion rate of glucose in product using high performance liquid chromatography (HPLC) after filtering with microporous membrane
Sour sodium yield is 34%.
Embodiment 10：
1g ZnO carriers are added into 100ml quartz flasks, 20ml water, 2ml methanol obtains mixed liquor I.It is violent at room temperature
Stirring mixing 0.5h.Instill 1.320ml 0.0386M H dropwise to mixed liquor I with vigorous stirring2PtCl6The aqueous solution and
0.417ml 0.0287M Bi (NO3)3The aqueous solution, and ultrasonic mixing is uniform, is designated as mixed liquor II.It is stirred vigorously gained mixed liquor
II, in 600mW/cm2Irradiation reduction 1h under xenon lamp.Mixed liquor after filtering reduction obtains solid catalyst, uses deionized water
Multiple washing catalyst, until AgNO in filtrate3Detection is dried in vacuo 6h, obtains PtBi/ZnO without Cl ions2Catalyst.In band
There are addition 20ml water, 0.1g catalyst, 0.5g glucose, 2.5mmol sodium hydroxide in the reactor of polytetrafluoroethyllining lining
With a magneton.Air in kettle is discharged using oxygen after sealing kettle, 1MPa oxygen is filled with after being repeated 6 times.By reactor
It is heated to 60 DEG C, reaction time 4h.Product after filtering with microporous membrane using high performance liquid chromatography (HPLC) by being analyzed in product
Inversion rate of glucose is 99%, and glucaric acid sodium yield is 57%.
Comparative example 1：
1g TiO are added into 100ml quartz flasks2Carrier, 3ml water, 0.261ml 0.0486M HAuCl4The aqueous solution and
0.332ml 0.0386M H2PtCl6The aqueous solution, solvent evaporated is stirred at 80 DEG C, obtains solid powder I.Solid powder I exists
H is used at 350 DEG C24h is calcined, PtAu/TiO is obtained2(im) catalyst.Added in the reactor with polytetrafluoroethyllining lining
20ml water, 0.1g catalyst, 0.5g glucose, 2.5mmol sodium hydroxide and a magneton.Sealing will using oxygen after kettle
Air is discharged in kettle, and 1MPa oxygen is filled with after being repeated 6 times.Reactor is heated to 60 DEG C, reaction time 4h.Product passes through micro-
It is 45% to analyze inversion rate of glucose in product using high performance liquid chromatography (HPLC) after the membrane filtration of hole, and glucaric acid sodium is received
Rate is 9% (referring to table 1).
Table 1
0.25wt%Pt-0.25wt%Au/TiO prepared by substep Photodeposition2Transmission electron microscope picture is referring to Fig. 1.
The present invention uses illumination semiconductor carrier, is made by light induced electron reduction metal ions.Support type therein
Metallic catalyst includes monometallic or bimetallic component.Obtained supported nano-gold metal catalyst has metal component particle diameter small,
Decentralization is high, the characteristics of being evenly distributed.The method for preparing catalyst technique is simple, environmental protection.Obtained catalyst is applied to
During the glycoxidative glucaric acid reactant salt processed of grape, glucarate high income, catalyst can recycled for multiple times.
Claims (8)
1. a kind of load type metal catalyst, it is characterised in that monometallic is loaded by semiconductor carrier or bimetallic is constituted, with matter
Carrier accounts for 92%~99.7% in the percentages of amount, catalyst, and metal active constituent accounts for 0.3%~8%；The metal component
For one pack system or two-component, single group is divided into metal element A, and two-component is metal element A and metallic element B, metal element A and gold
Belong to element B mass ratio for (1~5) ︰ 1, the metal element A be selected from Cr, Mn, Fe, Co, Nb, Ru, Rh, Pd, Ag, Re, Ir,
One kind in Pt, Au, Bi；The one kind of metallic element B in Pt, Pd, Ag, Au, Bi；The metal element A and metallic element B
It is not same element, the semiconductor carrier is selected from TiO2、Cu2O、ZnO、CdS、SnO2、WO3At least one of.
2. being prepared for the single-metal reforming catalyst that glucose selective oxidation prepares glucarate using light deposition method, it is made
Preparation Method comprises the following steps：
1) aqueous solution I that the metal salt of metal element A is configured to 0.01~0.5M is used as presoma；
2) semiconductor carrier, sacrifice agent and water are mixed, suspension II is made in stirring 0.5h；
3) aqueous solution I is added in suspension II, ultrasonic 20min, be well mixed, in 600mW/cm2Under xenon lamp irradiation, 200~
Photo-reduction is carried out under 500r/min magnetic stirrers, load single-metal reforming catalyst suspension III is obtained；
4) suspension III is filtered, solid particle is obtained, makes to be washed with deionized, is dried in vacuo, is obtained support type monometallic and urge
Agent.
3. it can be prepared for the bimetallic catalyst that glucose selective oxidation prepares glucarate using coprecipitated method, its
Preparation method comprises the following steps：
1) by the common water soluble in water for being configured to total concentration for 0.01~0.5M of metal element A and metallic element B metal salt
Solution I is used as presoma；
2) semiconductor carrier, sacrifice agent and water are mixed, suspension II is made in stirring 0.5h；
3) aqueous solution I is added in suspension II, ultrasonic 20min, be well mixed, in 600mW/cm2Under xenon lamp irradiation, 200~
Photo-reduction is carried out under 500r/min magnetic stirrers, load single-metal reforming catalyst suspension III is obtained；
4) suspension III is filtered, solid particle is obtained, makes to be washed with deionized, is dried in vacuo, is obtained support type monometallic and urge
Agent.
4. can be using the method for being distributed light deposition for the bimetallic catalyst that glucose selective oxidation prepares glucarate
Prepare, its preparation method comprises the following steps：
1) water-soluble metal salt of metal element A is configured to 0.01~0.5M aqueous solution I, by metallic element B water solubility
Metal salt is configured to 0.01~0.5M solution II as presoma；
2) semiconductor carrier, sacrifice agent and water are mixed, suspension III is made in stirring 0.5h；
3) aqueous solution I is added in suspension III, ultrasonic 20min, be well mixed, in 600mW/cm2Under xenon lamp irradiation, 200~
500r/min magnetic stirrers carry out photo-reduction, obtain suspension IV；
4) aqueous solution II, 200~500r/min magnetic stirrer 30min is added in suspension IV, in 600mW/cm2Xenon
200~500r/min magnetic stirrers carry out photo-reduction under light irradiation, obtain A-B bimetallic catalyst suspensions V；
5) suspension V is filtered, solid particle is obtained, makes to be washed with deionized, is dried in vacuo, load type double-metal catalysis is obtained
Agent.
5. such as claim 2~4 methods described, it is characterised in that the sacrifice agent be selected from methanol, ethanol, ethylene glycol, propane diols,
At least one of glycerine, formaldehyde, acetaldehyde, glucose, fructose.
6. such as claim 2~4 methods described, it is characterised in that the mass ratio of the carrier, water and sacrifice agent be 1 ︰ (10~
200) ︰ (0.1~50).
7. such as claim 2~4 methods described, it is characterised in that the time of the photo-reduction is 0.5~10h.
8. the monometallic or bimetallic catalyst of glucarate are prepared for glucose selective oxidation.
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| CN107537479A (en) * | 2017-08-15 | 2018-01-05 | 武汉理工大学 | A kind of degrading volatile organic pollutant catalyst and preparation method thereof |
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| 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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| CN112642469A (en) * | 2019-10-10 | 2021-04-13 | 中国石油化工股份有限公司 | Catalyst for preparing ethylene glycol by hydrogenating oxalate, preparation method and application thereof, and method for preparing ethylene glycol |
| 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 |
| CN113751072A (en) * | 2021-08-31 | 2021-12-07 | 厦门大学 | Catalyst for preparing methyl acetate by dimethyl ether carbonylation and preparation method and application thereof |
| 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 |
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