CN112264100A - Bifunctional graphene oxide catalyst, and preparation method and application thereof - Google Patents
Bifunctional graphene oxide catalyst, and preparation method and application thereof Download PDFInfo
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- CN112264100A CN112264100A CN202011125545.7A CN202011125545A CN112264100A CN 112264100 A CN112264100 A CN 112264100A CN 202011125545 A CN202011125545 A CN 202011125545A CN 112264100 A CN112264100 A CN 112264100A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 106
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- 239000003054 catalyst Substances 0.000 title claims abstract description 83
- 230000001588 bifunctional effect Effects 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
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- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims abstract description 17
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 17
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 15
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/226—Sulfur, e.g. thiocarbamates
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
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- C—CHEMISTRY; METALLURGY
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/36—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms
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- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/58—One oxygen atom, e.g. butenolide
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Abstract
The invention discloses a bifunctional graphene oxide catalyst and a preparation method and application thereof, wherein the preparation method comprises the following steps: the first step is to sulfonate graphene oxide by adding organic acid to obtain single functionalized graphene oxide with an acid active center, and the second step is to fix noble metal nanoparticles on carbon nanosheets of the sulfonated graphene oxide in situ, so that the method is simpler and more convenient than the existing synthesis method of the bifunctional catalyst. The bifunctional graphene oxide catalyst is provided with two catalytic active centers (an acid active center and a noble metal active center), can provide a proper acidity and high-efficiency redox sites, can be applied to etherification-oxidation reaction, transesterification-hydrogenation reaction and dehydration-hydrogenation reaction besides the reaction for preparing 2, 5-diformylfuran by fructose one-pot catalytic conversion, and improves the catalytic activity of the reaction and the selectivity of a product by regulating and controlling the space structures of the two active centers.
Description
Technical Field
The invention relates to the technical field of graphene oxide catalysts, in particular to a bifunctional graphene oxide catalyst and a preparation method and application thereof.
Background
Carbon-supported catalysts have been extensively studied in the last two decades, and the novel two-dimensional carbon nanomaterials including graphene and Graphene Oxide (GO) have attracted more and more attention due to their advantages of high specific surface area, thermal stability, easy functionalization, and high dispersibility, and are beneficial to the contact between reactants and catalytic active centers. In view of the advantages, the graphene is expected to be widely applied in the fields of selective dehydrogenation of hydrocarbons, oxidation of aromatic compounds and furan, decarboxylation of organic acids, Claisen-Schmidt coupling reaction, ring-opening polymerization and the like. Due to the ultra-small volume, high solubility in various organic and/or aqueous solutions, a large number of active centers derived from defect sites and oxygen-containing functional groups on graphene sheets, and good adjustability through chemical functionalization or heteroatom doping, the catalytic performance of graphene and GO (two-dimensional carbon nanosheet) is superior to that of conventional carbon materials (such as activated carbon and graphite), and the unique properties make the graphene and GO (two-dimensional carbon nanosheet) an ideal carrier for synthesizing a nano catalyst.
The catalytic conversion of fructose to 2, 5-Diformylfuran (DFF) is one of the most attractive research directions at present because the product has high added value, great potential in organic synthesis and pharmaceutical industry, and low-cost and easily available raw materials. DFF is typically synthesized from fructose by a two-step conversion process involving the catalytic dehydration of fructose acids to 5-HMF and the catalytic oxidation of 5-HMF with a metal-based catalyst to DFF. If the two-step process is integrated into one-step operation, the process is more economical and environment-friendly, and the development of the bifunctional/multifunctional catalyst can realize the integration of the domino/cascade reaction of the process into one-step operation. However, the bifunctional catalysts developed and used at present have extremely low catalytic efficiency. This problem is associated with the bifunctional design of the catalyst, such as too close a distance between the acid active center and the metal site, resulting in some sugar intermediates produced on the acid active center from fructose being oxidized by the adjacent metal site before 5-HMF is formed, or 5-HMF being unstable in a single solvent phase (usually the aqueous phase) and a change in the concentration gradient on the acid active center resulting in the oligomerization of 5-HMF to humic substances as a by-product. The development of highly efficient bifunctional catalysts is therefore still under investigation.
Disclosure of Invention
In order to overcome the defects of the prior art, one of the purposes of the invention is to provide a bifunctional graphene oxide catalyst and a preparation method thereof, the preparation method is simpler and more convenient than the existing synthesis method of the bifunctional catalyst, the catalyst prepared by the method has two active centers on the surface of a graphene oxide sheet, namely a metal active center and an acid active center, can provide a proper acidity and a high-efficiency redox site, and can be repeatedly used; the invention also provides an application of the bifunctional graphene oxide catalyst, and the catalyst is suitable for one-pot cascade reactions, such as etherification-oxidation reactions, transesterification-hydrogenation reactions and dehydration-hydrogenation reactions, and is particularly suitable for preparing 2, 5-diformylfuran by fructose one-pot conversion.
One of the purposes of the invention is realized by adopting the following technical scheme:
a preparation method of a bifunctional graphene oxide catalyst comprises the following steps:
1) adding graphene oxide into a sulfonating agent solution, and carrying out mixing on the mixed solution at 70 ℃ and N2Stirring and refluxing vigorously, centrifuging and washing the suspension obtained by refluxing, and freeze-drying to obtain monofunctional graphene oxide;
2) adding monofunctional graphene oxide into ethylene glycol, performing ultrasonic oscillation, adding noble metal chloride, adjusting the pH to 13, and thenHeating the solution to 120 ℃ and mixing the solution with a glycol solution of a reducing agent; wherein the reducing agent is NaBH4One or more of KBH, hydrazine hydrate and polyamine; the mass ratio of the reducing agent to the noble metal chloride is 3-8%;
3) refluxing the solution obtained in the step 2) at 120 ℃, cooling to room temperature, dropwise adding deionized water into the solution, adjusting the pH value to the pH value in the step 1), filtering, washing with water, and drying in vacuum to obtain the bifunctional graphene oxide catalyst.
Further, in the step 1), the carbon raw material of the graphene oxide is one or more of carbon black, coal, graphite, bituminous coal, carbon fiber and coke.
Further, in the step 1), the sulfonating agent solution is one or more of chlorosulfonic acid solution, fuming sulfuric acid solution and alkyl sultone solution; the concentration of the sulfonating agent solution is 0.5-3 mol/L; the time of vigorous stirring and refluxing is 24 h; the freeze-drying time was 24 h.
Further, in the step 2), the concentration of the ethylene glycol solution is 1-3 mg/mL.
Further, in the step 2), the noble metal in the noble metal chloride is one or more of ruthenium, rhodium, platinum and palladium; the concentration of the noble metal chloride is 10-20 mg/mL.
Further, in the step 3), the grain diameter of the bifunctional graphene oxide catalyst is less than or equal to 20nm, the average pore diameter is greater than or equal to 20nm, and the specific surface is 200-300 m2/g。
Further, in the step 3), the sulfur content in the bifunctional graphene oxide catalyst is 5-6%, and the metal content is 1-3%.
A bifunctional graphene oxide catalyst is prepared by the preparation method. It should be added that the noble metal active center in the bifunctional graphene oxide catalyst includes one of Pt, Pd, Ru, and Rh; the acid active center comprises-SO3H. One or more of-COOH and-TsOH. Specifically, the particle size of the nanoparticles of the noble metal active center is 2-10 nm.
The second purpose of the invention is realized by adopting the following technical scheme:
the bifunctional graphene oxide catalyst can be synthesized by a one-pot method, such as etherification-oxidation reaction, transesterification-hydrogenation reaction and dehydration-hydrogenation reaction.
Specifically, the bifunctional graphene oxide catalyst is applied to preparation of 2, 5-diformylfuran from fructose (dehydration-hydrogenation reaction), the reaction temperature is 120-200 ℃, and the reaction time is 3-8 hours.
As a highly functionalized two-dimensional carbon nanomaterial, graphene is used as an ideal support for the dual/multi-functionalization of the catalyst, and different active centers can be located on graphene nanoplatelets. The acid active center of the bifunctional catalyst is used for preparing 5-HMF by fructose catalytic hydrolysis, and the noble metal active center is used for preparing DFF by 5-HMF selective catalytic oxidation.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention discloses a preparation method of a bifunctional graphene oxide catalyst, which comprises the first step of sulfonating graphene oxide by adding organic acid to realize single functionalization of an acid active center, and the second step of fixing noble metal nanoparticles on a carbon nano-chip of the graphene oxide in situ to realize double functionalization of the acid active center and a metal active center, and is simpler and more convenient than the existing synthesis method of the bifunctional catalyst.
(2) The bifunctional graphene oxide catalyst prepared by the preparation method provided by the invention has double catalytic active centers (acid active center and noble metal active center), can provide a proper acidity and high-efficiency redox sites, can be applied to etherification-oxidation reaction, transesterification-hydrogenation reaction and dehydration-hydrogenation reaction besides the reaction for preparing 2, 5-diformylfuran by fructose one-pot catalytic conversion, and improves the catalytic activity of the reaction and the selectivity of the product by regulating and controlling the spatial structure of the two active centers.
(3) The prepared bifunctional graphene oxide catalyst can be repeatedly used, and researches show that the bifunctional graphene oxide catalyst can be repeatedly used for more than 5 times under the condition that the catalytic activity is not obviously reduced.
Drawings
FIG. 1 is a Raman spectrum of example 1, comparative example 1 and comparative example 2;
FIG. 2 is XRD spectra of example 1, comparative example 1 and comparative example 2;
FIG. 3 is a TEM and HRTEM image of example 1;
FIG. 4 is a TEM image of comparative example 1;
fig. 5 is a TEM image of comparative example 2.
Detailed Description
The present invention will be further described with reference to the accompanying drawings and the detailed description, and it should be noted that any combination of the embodiments or technical features described below can be used to form a new embodiment without conflict.
The bifunctional graphene oxide catalyst prepared by the invention is suitable for various reactors, such as a moving bed reactor, a tubular reactor, a stirred tank reactor and the like.
The bifunctional graphene oxide catalyst prepared by the invention is applied to one-pot cascade reaction, and multistep reaction in the one-pot reaction can directly obtain molecules with complex structures from relatively simple and easily-obtained raw materials without separation of intermediates, such as etherification-oxidation reaction, transesterification-hydrogenation reaction and dehydration-hydrogenation reaction.
Etherification-oxidation reaction:
transesterification-hydrogenation reaction:
specific examples of dehydration-hydrogenation reactions are: preparation of 2, 5-diformylfuran from fructose
Example 1
A preparation method of a bifunctional graphene oxide catalyst comprises the following steps:
1) graphene oxide (Cobat Corporation) was added to a chloroform solution of 3mol/L chlorosulfonic acid (98%, Sigma-Aldrich), and the mixed solution was heated at 70 ℃ and in N2Stirring and refluxing vigorously for 24h, cooling the suspension obtained by refluxing to room temperature, repeatedly centrifuging and washing in an ice bath by using deionized water and ethanol, and freeze-drying for 24h to obtain monofunctional graphene oxide;
2) adding monofunctional graphene oxide into 1mg/mL of ethylene glycol, carrying out ultrasonic oscillation for 1-3 h, adding 20mg/mL ruthenium (III) chloride hydrate (ruthenium content is 40.00 wt%, Sigma-Aldrich) in concentration, standing for 3h, adding NaOH solution to adjust the pH value to 13, heating the solution to 120 ℃, and reacting with NaBH with the concentration of 20mg/mL4The ethylene glycol solution is slowly mixed; wherein, NaBH4The mass ratio of the ethylene glycol solution to the ruthenium trichloride solution is 3 percent;
3) refluxing the solution obtained in the step 2) at 120 ℃ for 1h, cooling to room temperature, dropwise adding 1L of deionized water into the solution, adjusting the pH value to the pH value in the step 1) by using 0.1mol/L HCl solution, filtering, washing with water, and drying in vacuum at 80 ℃ for 12h to obtain the bifunctional graphene oxide catalyst.
In this embodiment, the bifunctional graphene oxide catalyst has a particle size of 20nm or less, an average pore size of 20nm or more, and a specific surface area of 298m2(ii) in terms of/g. The sulfur content in the bifunctional graphene oxide catalyst is 6%, and the metal content is 3%.
The catalyst in the embodiment is a bifunctional graphene oxide catalyst taking sulfonic acid groups as acid active centers and ruthenium (Ru) as metal active centers, and is named as Ru/S-rGO.
Example 2
A preparation method of a bifunctional graphene oxide catalyst comprises the following steps:
1) graphene oxide (Cobat Corporation) was added to 0.5mol/L oleum (SO)3 Content 30%, Sigma-Aldrich), the mixture was heated at 70 ℃ and in N2Refluxing with vigorous stirring for 24hAfter the suspension is cooled to room temperature, repeatedly centrifuging and washing the suspension in an ice bath by using deionized water and ethanol, and freeze-drying the suspension for 24 hours to obtain monofunctional graphene oxide;
2) adding monofunctional graphene oxide into 3mg/mL ethylene glycol, carrying out ultrasonic oscillation for 1-3 h, adding a platinum (II) chloride solution with the concentration of 10mg/mL (the Pt content is not less than 73%, Alfa Aesar), standing for 1h, adding a NaOH solution, adjusting the pH value to 13, heating the solution to 120 ℃, and slowly mixing the solution with an ethylene glycol solution of 10 mg/mLKBH; wherein the mass ratio of the ethylene glycol solution of KBH to the rhodium trichloride solution is 8%;
3) refluxing the solution obtained in the step 2) at 120 ℃ for 1h, cooling to room temperature, dropwise adding 2L of deionized water into the solution, adjusting the pH value to the pH value in the step 1) by using 0.1mol/L HCl solution, filtering, washing with water, and drying in vacuum at 80 ℃ for 8h to obtain the bifunctional graphene oxide catalyst.
In the embodiment, the bifunctional graphene oxide catalyst has a particle size of not more than 20nm, an average pore size of not less than 20nm, and a specific surface area of 201m2(ii) in terms of/g. The sulfur content in the bifunctional graphene oxide catalyst is 5%, and the metal content in the bifunctional graphene oxide catalyst is 1%.
Example 3
A preparation method of a bifunctional graphene oxide catalyst comprises the following steps:
1) graphene oxide (Cobat Corporation) was added to 2mol/L oleum (SO)3 Content 30%, Sigma-Aldrich), the mixture was heated at 70 ℃ and in N2Stirring and refluxing vigorously for 24h, cooling the suspension obtained by refluxing to room temperature, repeatedly centrifuging and washing in an ice bath by using deionized water and ethanol, and freeze-drying for 24h to obtain monofunctional graphene oxide;
2) adding monofunctional graphene oxide into 2mg/mL ethylene glycol, carrying out ultrasonic oscillation for 3h, adding palladium chloride (the concentration of which is not less than 99 percent and Alfa Aesar) with the concentration of 15mg/mL, standing for 1h, adding NaOH solution to adjust the pH value to 13, heating the solution to 120 ℃, and slowly mixing the solution with an ethylene glycol solution of hydrazine hydrate; wherein, the ethylene glycol solution of hydrazine hydrate accounts for 5 percent of the mass ratio of the palladium trichloride solution;
3) refluxing the solution obtained in the step 2) at 120 ℃ for 1h, cooling to room temperature, dropwise adding 1L of deionized water into the solution, adjusting the pH value to the pH value in the step 1) by using 0.1mol/L HCl solution, filtering, washing with water, and drying in vacuum at 80 ℃ for 10h to obtain the bifunctional graphene oxide catalyst.
In the embodiment, the particle size of the bifunctional graphene oxide catalyst is less than or equal to 20nm, the average pore diameter is greater than or equal to 20nm, and the specific surface area is 258m2(ii) in terms of/g. The sulfur content in the bifunctional graphene oxide catalyst is 5%, and the metal content in the bifunctional graphene oxide catalyst is 2%.
Comparative example 1
A preparation method of a monofunctional graphene oxide catalyst comprises the following steps:
1) graphene oxide (Cobat Corporation) was added to a chloroform solution of 3mol/L chlorosulfonic acid (98%, Sigma-Aldrich), the mixed solution was vigorously stirred at 70 ℃ under N2 for 24 hours under reflux, the suspension obtained by reflux was cooled to room temperature, repeatedly centrifuged and washed in an ice bath with deionized water and ethanol, and freeze-dried for 24 hours to obtain a monofunctional graphene oxide catalyst, and the catalyst of comparative example 1 was named SGO. (i.e., the same as in step 1 of example 1)
Comparative example 2
The same graphene oxide (Cobat Corporation) as in example 1 was selected and named GO.
Catalyst characterization test
Firstly, Raman spectroscopy is carried out on the sample 1, the comparative sample 1 and the comparative sample 2, 532nm excitation radiation is provided by a 50MW praseodymium laser by adopting HORIBA JY LabRAM HR Evolution equipped with a thermoelectric cooling CCD detector, and the graph 1 is obtained
As shown in fig. 1, the intensity ratios of the D peak (defect and irregular sp3 carbon atom peak) and the G peak (sp 2 carbon atom peak of two-dimensional graphite hexagonal lattice) in comparative example 1 and example 1 are similar and both are higher than in comparative example 2. Comparative example 1 in the presence of SO3H radical, example 1 in the presence of SO3H group and Ru nanoparticles, evidence of SO3The introduction of H groups and/or Ru nanoparticles both partially destroyed the graphitic structure.
Secondly, XRD test was performed on example 1, comparative example 1 and comparative example 2, and XRD patterns were measured using a RigakuUltima IV diffractometer at a Cu ka radiation source of 20mA and 40kV and a scanning rate of 0.5o/min (λ ═ 1.54056a), resulting in fig. 2
The characteristic structure of comparative example 2 has a diffraction peak at 10.3 ° corresponding to a crystal plane having a lattice spacing of 8.6A; whereas the characteristic structures of comparative example 1 and example 1 each have a typical broad diffraction peak at 24.8 °, corresponding to a crystal plane with a lattice spacing of 3.6A. The catalyst of example 1 was also found to have peaks at 42.2 ° and 44.0 ° corresponding to 002 phase and 101, respectively. Due to the low loading of Ru, the characteristic hexagonal phase of Ru (JCPDS card number 60663) was not found in the spectrum.
Thirdly, TEM and STEM tests are carried out on the catalyst of the example 1, TEM tests are carried out on the comparative example 1 and the comparative example 2, TEM images are measured at 200kV by using a JEOL 2100F microscope equipped with a ZrO/W Schottky field emission gun, STEM images are measured at 633nm excitation wavelength by using an annular dark field with EDAX Edx Raman spectroscopy (Renishaw InVia Reflex Raman), and then the images of the graph are obtained in the way of being shown in the figures 3-5
As shown in fig. 3, TEM images show that Ru nanoparticles with an average size of 3nm were supported on Sulfonated Graphene Oxide (SGO) sheets. HRTEM image showed characteristic spacing of 101 plane of metallic Ru of 1.88A, consistent with the XRD-characterized structure of FIG. 2.
Comparing fig. 3, 4 and 5, it is demonstrated that the main characteristic structure and morphology of graphene oxide is not damaged after functionalization by sulfonic acid group and/or Ru nanoparticle. The active centers of example 1 are uniformly distributed on both sides of the graphene oxide sheet, so that the reactant molecules are more easily contacted with the catalyst, and the generated product can be rapidly diffused.
Testing of catalyst in preparation of 2, 5-Diformylfuran (DFF) by catalytic conversion of fructose
The catalytic reaction was carried out in a 50ml high pressure reactor with mechanical stirring. The reactor is provided with a plurality of feed and discharge ports, raw materials enter the reactor through a feed guide pipe, and air with a specific volume ratio of nitrogen to oxygen enters a liquid phase through a nozzle. The reaction conditions can be scaled up according to the industrial requirements. In a routine experiment, fructose, catalyst and water/organic solvent of specified mass are added to a reaction kettle and the mixture is heated to a set temperature with stirring. After the reaction is finished, the reactor is cooled in ice bath, and the catalyst is recycled by simple centrifugal separation. The furyl products in the organic and aqueous phases were analyzed by HPLC (Agilent 1100Series) equipped with a 282nm UV detector, a C18 reverse phase column, using acetonitrile: acetic acid (3:7v/v) as mobile phase. The product was quantified using an external standard method and an autosampler (Agilent G1329A) was used to improve the reproducibility of the detection. The furan derivative yield and fructose conversion are calculated as carbon-based from the product concentration in the two phases, which can be derived from the HPLC measurements.
The catalyst group is selected from: example 1 Ru3+/H2SO4、Ru3+Ionic liquid, MoO3/SGO、MoO3ZSM-5 and V2O5ZSM-5. Wherein, Ru3+/H2SO4Ru in catalyst3+Supplied from ruthenium (III) chloride hydrate (ruthenium content 40.00 wt%, Sigma-Aldrich) in an amount equivalent to that of example 1. MoO3SGO in/SGO the same preparation method as in comparative example 1 was used.
The catalytic reaction conditions are as follows: to 10mL of methyl isobutyl ketone were added 0.5g of fructose (. gtoreq.99%, Alfa Aesar) and 10mg of a catalyst, and the mixture was reacted at 140 ℃ for 2 hours. The catalytic effect of the catalyst set is as follows:
TABLE 1 Effect of different catalysts on the catalytic conversion of fructose to 2, 5-Diformylfuran (DFF)
| Catalyst and process for preparing same | DFF yield (%) | Fructose conversion (%) |
| Example 1 | 83.2 | 100 |
| Ru3+/H2SO4 | 86.5 | 100 |
| Ru3+Ionic liquids | 90.2 | 100 |
| MoO3/SGO | 68.6 | 98.2 |
| MoO3/ZSM-5 | 55.7 | 99.1 |
| V2O5/ZSM-5 | 52.3 | 99.3 |
As shown in table 1, compared to as MoO3/SGO、MoO3ZSM-5 and V2O5The heterogeneous catalyst commonly used for/ZSM-5, example 1, exhibited very high fructose conversion (up to 100%) and excellent selectivity to 2, 5-diformylfuran. Despite Ru3+/H2SO4And Ru3+Ionic liquid has excellent 2, 5-diformylfuran yield compared with example 1, but the application of ionic liquid in the large-scale production of 2, 5-diformylfuran is directly limited due to the fact that ionic liquid is harmful to environment or expensive. In contrast, example 1 is an inexpensive carbon-based material, and due to its highly efficient acid groups and good dispersion of the metal active centers on the surface of the graphene oxide sheets, example 1(Ru/S-rGO) exhibits similarity to homogeneous catalystsHigh reactivity. Since the yield of the 2, 5-diformylfuran catalyzed by the catalyst in the embodiment 1 is as high as 83.2%, the large-scale production of the 2, 5-diformylfuran is expected to be realized on the basis of optimizing the process conditions (reactor design, feeding rate, product purification and the like) of the catalytic reaction process.
The above embodiments are only preferred embodiments of the present invention, and the protection scope of the present invention is not limited thereby, and any insubstantial changes and substitutions made by those skilled in the art based on the present invention are within the protection scope of the present invention.
Claims (10)
1. A preparation method of a bifunctional graphene oxide catalyst is characterized by comprising the following steps:
1) adding graphene oxide into a sulfonating agent solution, and carrying out mixing on the mixed solution at 70 ℃ and N2Stirring and refluxing vigorously, centrifuging and washing the suspension obtained by refluxing, and freeze-drying to obtain monofunctional graphene oxide;
2) adding monofunctional graphene oxide into ethylene glycol, carrying out ultrasonic oscillation, adding noble metal chloride, adjusting the pH to 13, heating the solution to 120 ℃, and mixing the solution with an ethylene glycol solution of a reducing agent; wherein the reducing agent is NaBH4One or more of KBH, hydrazine hydrate and polyamine; the mass ratio of the reducing agent to the noble metal chloride is 3-8%;
3) refluxing the solution obtained in the step 2) at 120 ℃, cooling to room temperature, dropwise adding deionized water into the solution, adjusting the pH value to the pH value in the step 1), filtering, washing with water, and drying in vacuum to obtain the bifunctional graphene oxide catalyst.
2. The method for preparing the bifunctional graphene oxide catalyst according to claim 1, wherein in the step 1), the carbon raw material of the graphene oxide is one or more of carbon black, coal, graphite, bituminous coal, carbon fiber and coke.
3. The method for preparing the bifunctional graphene oxide catalyst according to claim 1, wherein in the step 1), the sulfonating agent solution is one or more of a chlorosulfonic acid solution, a fuming sulfuric acid solution and an alkyl sultone solution; the concentration of the sulfonating agent solution is 0.5-3 mol/L; the time of vigorous stirring and refluxing is 24 h; the freeze-drying time was 24 h.
4. The preparation method of the bifunctional graphene oxide catalyst according to claim 1, wherein in the step 2), the concentration of the ethylene glycol solution is 1-3 mg/mL.
5. The preparation method of the bifunctional graphene oxide catalyst according to claim 1, wherein in the step 2), the noble metal in the noble metal chloride is one or more of ruthenium, rhodium, platinum and palladium; the concentration of the noble metal chloride is 10-20 mg/mL.
6. The preparation method of the bifunctional graphene oxide catalyst according to claim 1, wherein in the step 3), the bifunctional graphene oxide catalyst has a particle size of not more than 20nm, an average pore size of not less than 20nm, and a specific surface of 200-300 m2/g。
7. The preparation method of the bifunctional graphene oxide catalyst according to claim 1, wherein in the step 3), the sulfur content in the bifunctional graphene oxide catalyst is 5-6%, and the metal content in the bifunctional graphene oxide catalyst is 1-3%.
8. A bifunctional graphene oxide catalyst, characterized by being prepared by the preparation method of any one of claims 1 to 7.
9. The use of the bifunctional graphene oxide catalyst according to claim 8, in etherification-oxidation reactions, transesterification-hydrogenation reactions and dehydration-hydrogenation reactions.
10. The application of the bifunctional graphene oxide catalyst according to claim 8, wherein the bifunctional graphene oxide catalyst is applied to the preparation of 2, 5-diformylfuran from fructose, the reaction temperature is 120-200 ℃, and the reaction time is 3-8 h.
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