WO2022083142A1 - Bifunctional graphene oxide catalyst, preparation method therefor and use thereof - Google Patents
Bifunctional graphene oxide catalyst, preparation method therefor and use thereof Download PDFInfo
- Publication number
- WO2022083142A1 WO2022083142A1 PCT/CN2021/099939 CN2021099939W WO2022083142A1 WO 2022083142 A1 WO2022083142 A1 WO 2022083142A1 CN 2021099939 W CN2021099939 W CN 2021099939W WO 2022083142 A1 WO2022083142 A1 WO 2022083142A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- graphene oxide
- oxide catalyst
- bifunctional
- solution
- preparation
- Prior art date
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 104
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 88
- 239000003054 catalyst Substances 0.000 title claims abstract description 80
- 230000001588 bifunctional effect Effects 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 239000005715 Fructose Substances 0.000 claims abstract description 17
- 229930091371 Fructose Natural products 0.000 claims abstract description 17
- 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
- PXJJKVNIMAZHCB-UHFFFAOYSA-N 2,5-diformylfuran Chemical compound O=CC1=CC=C(C=O)O1 PXJJKVNIMAZHCB-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 12
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 11
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 10
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims description 51
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 238000010992 reflux Methods 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 239000010970 precious metal Substances 0.000 claims description 7
- 229910052707 ruthenium Inorganic materials 0.000 claims description 7
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 6
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 5
- 229910001510 metal chloride Inorganic materials 0.000 claims description 5
- 239000011148 porous material Substances 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- 239000011593 sulfur Substances 0.000 claims description 5
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 4
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 claims description 4
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 239000010948 rhodium Substances 0.000 claims description 3
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- -1 alkyl sultone Chemical class 0.000 claims description 2
- 239000002802 bituminous coal Substances 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- 239000003245 coal Substances 0.000 claims description 2
- 239000000571 coke Substances 0.000 claims description 2
- 238000004108 freeze drying Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229920000768 polyamine Polymers 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 15
- 239000002253 acid Substances 0.000 abstract description 13
- 238000005580 one pot reaction Methods 0.000 abstract description 7
- 239000002135 nanosheet Substances 0.000 abstract description 4
- 150000007524 organic acids Chemical class 0.000 abstract description 3
- 238000001308 synthesis method Methods 0.000 abstract description 3
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 230000001276 controlling effect Effects 0.000 abstract 1
- 230000003100 immobilizing effect Effects 0.000 abstract 1
- 239000002082 metal nanoparticle Substances 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 description 7
- 239000012071 phase Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000003917 TEM image Methods 0.000 description 5
- 239000002105 nanoparticle Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 238000010523 cascade reaction Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 238000001069 Raman spectroscopy Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000007306 functionalization reaction Methods 0.000 description 3
- 239000002608 ionic liquid Substances 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000009977 dual effect Effects 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 150000002240 furans Chemical class 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- 229910021604 Rhodium(III) chloride Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000005882 aldol condensation reaction Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010812 external standard method Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 229940110728 nitrogen / oxygen Drugs 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000011514 reflex Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- BIXNGBXQRRXPLM-UHFFFAOYSA-K ruthenium(3+);trichloride;hydrate Chemical compound O.Cl[Ru](Cl)Cl BIXNGBXQRRXPLM-UHFFFAOYSA-K 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Images
Classifications
-
- 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
- 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
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
- 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
-
- 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
- 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
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- 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
- C07D307/56—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
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/821—Ruthenium
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/822—Rhodium
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/824—Palladium
Definitions
- 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.
- Carbon-supported catalysts have been extensively studied in the past two decades, among which graphene and graphene oxide (GO) are novel 2D carbon nanomaterials due to their high specific surface area, thermal stability, ease of functionalization, and extremely high performance. Advantages such as dispersibility have received increasing attention, favoring the contact of reactants with catalytically active sites.
- graphene is expected to be widely used in fields including selective dehydrogenation of hydrocarbons, oxidation of aromatic compounds and furans, decarboxylation of organic acids, Claisen-Schmidt coupling reaction, and ring-opening polymerization.
- DFF 2,5-diformylfuran
- the bifunctional catalysts currently developed and used have extremely low catalytic efficiency.
- the problem is related to the bifunctional design of the catalyst, such as the fact that the distance between the acid active center and the metal site is too close, causing some sugar intermediates generated by fructose on the acid active center to be blocked by the adjacent metal before the formation of 5-HMF Site oxidation, or the instability of 5-HMF in a single solvent phase (usually an aqueous phase), changes the concentration gradient across the acid active site resulting in oligomerization of 5-HMF to form humic by-products. Therefore, the development of efficient bifunctional catalysts is still being explored.
- one of the objects of the present invention is to provide a bifunctional graphene oxide catalyst and a preparation method thereof, which is simpler than the synthesis method of the existing bifunctional catalyst, and the catalyst prepared by the method is used.
- the application of graphene oxide catalyst, the catalyst is suitable for one-pot cascade reaction, such as etherification-oxidation reaction, transesterification-hydrogenation reaction, dehydration-hydrogenation reaction, especially suitable for fructose one-pot conversion preparation 2, 5-Diformylfuran.
- a preparation method of bifunctional graphene oxide catalyst comprising the following steps:
- the reducing agent is one or more of NaBH 4 , KBH, hydrazine hydrate and polyamine; the mass ratio of the reducing agent to the noble metal chloride is 3-8%;
- step 2) The solution obtained in step 2) was refluxed at 120°C, cooled to room temperature, and deionized water was added dropwise to the solution, and the pH was adjusted to the pH value of step 1). Functional graphene oxide catalyst.
- the carbon raw material of graphene oxide is one or more of carbon black, coal, graphite, bituminous coal, carbon fiber and coke.
- the sulfonating agent solution is one or more of chlorosulfonic acid solution, oleum solution and alkyl sultone solution; the concentration of sulfonating agent solution is 0.5 ⁇ 3mol/ L; the time of vigorous stirring and reflux is 24h; the time of freeze-drying is 24h.
- step 2) the concentration of the ethylene glycol solution is 1-3 mg/mL.
- the precious metal in the precious metal chloride is one or more of ruthenium, rhodium, platinum and palladium; the concentration of the precious metal chloride is 10-20 mg/mL.
- the particle size of the bifunctional graphene oxide catalyst is less than or equal to 20 nm, the average pore diameter is greater than or equal to 20 nm, and the specific surface is 200-300 m 2 /g.
- 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 above-mentioned 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 includes one or more of -SO 3 H, -COOH and -TsOH. kind. Specifically, the particle size of the nanoparticles of the noble metal active center is 2-10 nm.
- the second purpose of the present invention adopts the following technical scheme to realize:
- Bifunctional graphene oxide catalysts can be applied in one-pot synthesis, such as etherification-oxidation, transesterification-hydrogenation, and dehydration-hydrogenation.
- the bifunctional graphene oxide catalyst is used in fructose to prepare 2,5-diformylfuran (dehydration-hydrogenation reaction), the reaction temperature is 120-200°C, and the reaction time is 3-8h.
- graphene is used as an ideal support for bifunctionalization/multifunctionalization of this catalyst, and different active centers can be localized on the graphene nanosheets.
- the acid active center of the bifunctional catalyst is used for fructose catalytic hydrolysis to prepare 5-HMF, while the noble metal active center is used for the selective catalytic oxidation of 5-HMF to prepare DFF.
- the present invention discloses a preparation method of a bifunctional graphene oxide catalyst.
- the first step is to sulfonate graphene oxide by adding an organic acid to realize the monofunctionalization of the acid active center.
- the particles are in situ immobilized on the carbon nanosheets of graphene oxide to realize the bifunctionalization of the acid active center and the metal active center, which is simpler than the synthesis method of existing bifunctional catalysts.
- the bifunctional graphene oxide catalyst prepared by the preparation method of the present invention has dual catalytic active centers (acid active center and precious metal active center), which can provide suitable acidity and efficient redox sites.
- catalytic active centers acid active center and precious metal active center
- it can also be used in etherification-oxidation reaction, transesterification-hydrogenation reaction and dehydration-hydrogenation reaction, and the bifunctional graphene oxide catalyst passes through
- the regulation of the spatial structure of the two active centers improves the catalytic activity and product selectivity of the reaction.
- the bifunctional graphene oxide catalyst prepared by the present invention can be reused, and studies have shown that it can be reused more than 5 times without significantly reducing the catalytic activity.
- Fig. 1 is the Raman spectrogram of embodiment 1, comparative example 1 and comparative example 2;
- Fig. 2 is the XRD spectrum of embodiment 1, comparative example 1 and comparative example 2;
- Fig. 3 is the TEM and HRTEM images of Example 1;
- Fig. 4 is the TEM image of comparative example 1;
- FIG. 5 is a TEM image of Comparative Example 2.
- the bifunctional graphene oxide catalyst prepared by the invention is suitable for various types of reactors, such as moving bed reactors, tubular reactors and stirred tank reactors.
- the bifunctional graphene oxide catalyst prepared by the invention is applied to the one-pot cascade reaction, and the multi-step reaction in the one-pot reaction can start from relatively simple and readily available raw materials, without separation of intermediates, to directly obtain complex structures.
- Molecules such as etherification-oxidation, transesterification-hydrogenation, dehydration-hydrogenation.
- a specific example of the dehydration-hydrogenation reaction is: the preparation of 2,5-diformylfuran from fructose
- a preparation method of bifunctional graphene oxide catalyst comprising the following steps:
- step 3 Reflux the solution obtained in step 2) at 120°C for 1 h, and after cooling to room temperature, dropwise add 1 L of deionized water to the solution, and adjust the pH to the pH value of step 1) with 0.1 mol/L HCl solution, then After filtration and washing, and vacuum drying at 80 °C for 12 h, a bifunctional graphene oxide catalyst was obtained.
- the particle size of the bifunctional graphene oxide catalyst is less than or equal to 20 nm, the average pore diameter is greater than or equal to 20 nm, and the specific surface is 298 m 2 /g.
- the sulfur content in the bifunctional graphene oxide catalyst was 6% and the metal content was 3%.
- the catalyst in this embodiment is a bifunctional graphene oxide catalyst with a sulfonic acid group as an acid active center and ruthenium (Ru) as a metal active center, named Ru/S-rGO.
- a preparation method of bifunctional graphene oxide catalyst comprising the following steps:
- step 3 Reflux the solution obtained in step 2) at 120° C. for 1 h, and after cooling to room temperature, dropwise add 2 L of deionized water to the solution, and adjust the pH to the pH value of step 1) with 0.1 mol/L HCl solution, then After filtration and washing, and vacuum drying at 80 °C for 8 h, a bifunctional graphene oxide catalyst was obtained.
- the particle size of the bifunctional graphene oxide catalyst is less than or equal to 20 nm, the average pore size is greater than or equal to 20 nm, and the specific surface area is 201 m 2 /g.
- the sulfur content in the bifunctional graphene oxide catalyst is 5%, and the metal content is 1%.
- a preparation method of bifunctional graphene oxide catalyst comprising the following steps:
- step 3 Reflux the solution obtained in step 2) at 120°C for 1 h, and after cooling to room temperature, dropwise add 1 L of deionized water to the solution, and adjust the pH to the pH value of step 1) with 0.1 mol/L HCl solution, then After filtration and washing, and vacuum drying at 80 °C for 10 h, a bifunctional graphene oxide catalyst was obtained.
- the particle size of the bifunctional graphene oxide catalyst is less than or equal to 20 nm, the average pore size is greater than or equal to 20 nm, and the specific surface area is 258 m 2 /g.
- the sulfur content in the bifunctional graphene oxide catalyst is 5%, and the metal content is 2%.
- a preparation method of monofunctional graphene oxide catalyst comprising the following steps:
- Comparative Example 2 has a diffraction peak at 10.3°, corresponding to a crystal plane with a lattice spacing of 8.6A; while the characteristic structures of Comparative Example 1 and Example 1 both 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 phases 002 and 101, respectively. Due to the low loading of Ru, the characteristic hexagonal phase of Ru was not found in the spectrum (JCPDS Card No. 60663).
- TEM and STEM tests were performed on the catalyst of Example 1, and TEM tests were performed on Comparative Examples 1 and 2.
- the TEM images were measured with a JEOL 2100F microscope equipped with a ZrO/W Schottky field emission gun at 200kV.
- Raman spectrum (Renishaw InVia Reflex Raman) was measured at the excitation wavelength of 633 nm, and Figures 3 to 5 were obtained
- the TEM images showed that Ru nanoparticles with an average size of 3 nm were supported on the sulfonated graphene oxide (SGO) sheets.
- the HRTEM image shows that the characteristic spacing of the 101 crystal plane of metallic Ru is 1.88A, which is consistent with the XRD characterization structure in Figure 2.
- the catalytic reaction was carried out in a 50 ml high pressure reactor with mechanical stirring.
- the reactor is provided with a plurality of inlet and outlet ports, the raw materials enter the reactor through the feeding conduit, and the air with a specific nitrogen/oxygen volume ratio enters the liquid phase through the nozzle.
- the reaction conditions can be scaled up according to industrial needs. During routine experiments, specific masses of fructose, catalyst, and water/organic solvent were added to the reaction kettle, and the mixture was heated to a set temperature with stirring. After the reaction, the reactor was cooled in an ice bath, and the catalyst was recovered and reused by simple centrifugal separation.
- the furan-based products in the organic and aqueous phases were analyzed by HPLC (Agilent 1100 Series) equipped with a 282 nm UV detector, a C18 reversed-phase column, and acetonitrile:acetic acid (3:7 v/v) was used as the mobile phase.
- the product was quantified using an external standard method, and an autosampler (Agilent G1329A) was used to improve detection reproducibility.
- Furan derivative yields and fructose conversions were calculated in carbon-based form based on the product concentrations in the two phases (obtainable from HPLC measurements).
- Catalyst group selection Example 1, Ru 3+ /H 2 SO 4 , Ru 3+ /ionic liquid, MoO 3 /SGO, MoO 3 /ZSM-5 and V 2 O 5 /ZSM-5.
- Ru 3+ in the Ru 3+ /H 2 SO 4 catalyst was provided by the same amount of ruthenium (III) chloride hydrate (ruthenium content: 40.00 wt%, Sigma-Aldrich) as in Example 1.
- the SGO in MoO 3 /SGO was prepared in the same way as in Comparative Example 1.
- Catalytic reaction conditions 0.5 g of fructose ( ⁇ 99%, Alfa Aesar) and 10 mg of catalyst were added to 10 mL of methyl isobutyl ketone, and the reaction was carried out at 140° C. for 2 h.
- the catalytic effect of the catalyst group is as follows:
- Example 1 exhibits extremely high fructose conversion (up to 100%) compared to commonly used heterogeneous catalysts such as MoO3/SGO, MoO3/ZSM - 5 and V2O5 /ZSM- 5 . %) and excellent 2,5-diformylfuran selectivity.
- Ru 3+ /H 2 SO 4 and Ru 3+ /ionic liquid also have excellent yields of 2,5-diformylfuran compared with Example 1, they are directly limited due to their harmfulness to the environment or high price. Its application in the large-scale production of 2,5-diformylfuran.
- Example 1 is an inexpensive carbon-based material.
- Example 1 Due to its efficient acid groups and good dispersion of metal active centers on the surface of graphene oxide sheets, Example 1 (Ru/S-rGO) exhibits Efficient reactivity similar to homogeneous catalysts. Since the yield of 2,5-diformylfuran catalyzed in Example 1 is as high as 83.2%, on the basis of optimizing the process conditions (reactor design, feed rate, product purification, etc.) of the catalytic reaction process, it is expected to achieve 2 , Large-scale production of 5-diformylfuran.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
Disclosed are a bifunctional graphene oxide catalyst, a preparation method therefor and the use thereof. The preparation method comprises: step I. sulfonating graphene oxide by adding an organic acid to obtain monofunctional graphene oxide with an acid active center; and step II. in situ immobilizing noble metal nanoparticles on carbon nanosheets of the sulfonated graphene oxide. The method is simpler and more convenient than existing bifunctional catalyst synthesis methods. The bifunctional graphene oxide catalyst, which is provided with double catalytic active centers (an acid active center and a noble metal active center), can provide an appropriate acidity and a high-efficiency redox site. In addition to being applied to a reaction for the catalytic conversion of fructose into 2,5-diformylfuran in one pot, the catalyst can also be applied to an etherification-oxidation reaction, a transesterification-hydrogenation reaction and a dehydration-hydrogenation reaction. By regulating and controlling the spatial structures of the two active centers of the bifunctional graphene oxide catalyst, the reaction catalytic activity and product selectivity are improved.
Description
本发明涉及氧化石墨烯催化剂的技术领域，具体涉及一种双功能氧化石墨烯催化剂及其制备方法和应用。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.
碳负载催化剂在过去二十年里得到了广泛的研究，其中石墨烯和氧化石墨烯(GO)这些新型的二维碳纳米材料因其高比表面、热稳定性、易于功能化以及极高的分散性等优点受到了越来越多的关注，有利于反应物与催化活性中心的接触。鉴于以上优点，石墨烯有望在包括碳氢化合物选择性脱氢、芳族化合物和呋喃氧化、有机酸脱羧、Claisen-Schmidt耦合反应、开环聚合等领域得到广泛应用。因其超小体积、在各种有机和/或水溶液中的高溶解性、大量的活性中心源于石墨烯片上的缺陷位和含氧官能团、通过化学功能化或杂原子掺杂具有良好的可调性，使石墨烯和GO(二维碳纳米片)的催化性能优于常规碳材料(如活性炭和石墨)，这些独特的性能使其成为合成纳米催化剂的理想载体。Carbon-supported catalysts have been extensively studied in the past two decades, among which graphene and graphene oxide (GO) are novel 2D carbon nanomaterials due to their high specific surface area, thermal stability, ease of functionalization, and extremely high performance. Advantages such as dispersibility have received increasing attention, favoring the contact of reactants with catalytically active sites. In view of the above advantages, graphene is expected to be widely used in fields including selective dehydrogenation of hydrocarbons, oxidation of aromatic compounds and furans, decarboxylation of organic acids, Claisen-Schmidt coupling reaction, and ring-opening polymerization. Due to its ultra-small size, high solubility in various organic and/or aqueous solutions, a large number of active centers originating from defect sites and oxygen-containing functional groups on graphene sheets, good availability through chemical functionalization or heteroatom doping. These unique properties make graphene and GO (two-dimensional carbon nanosheets) superior to conventional carbon materials (such as activated carbon and graphite) in catalytic performance, and these unique properties make them ideal supports for the synthesis of nanocatalysts.
果糖催化转化制备2,5-二甲酰呋喃(DFF)是目前最有吸引力的研究方向之一，因为该产品具有高附加值，在有机合成和制药工业中具有巨大的潜力，而且原料价格低廉容易获得。DFF通常由果糖通过两步法转化合成，包括果糖酸催化脱水生成5-HMF和金属基催化剂催化氧化5-HMF生成DFF。若将该两步法集成到一步操作，该过程将更为经济和环保，双功能/多功能催化剂的开发能实现将该过程的多米诺/级联反应整合到一步操作中。然而目前开发使用的双功能催化剂催化效率极低。该问题与催化剂的双功能性设计有关，比如酸活性中心和金属位点之间的距离太近，导致果糖在酸活性中心上产生的一些糖中间体 在形成5-HMF之前被相邻的金属位点氧化，又或者5-HMF在单一溶剂相(通常为水相)中不稳定，在酸活性中心上浓度梯度的变化导致5-HMF低聚生成腐殖质副产物。因此高效双功能催化剂的开发仍在探索中。Catalytic conversion of fructose to prepare 2,5-diformylfuran (DFF) is one of the most attractive research directions at present because of its high added value, great potential in organic synthesis and pharmaceutical industry, and cost of raw materials. Inexpensive and easy to obtain. DFF is usually synthesized from fructose by a two-step transformation, including fructonic acid-catalyzed dehydration to 5-HMF and metal-based catalyst-catalyzed oxidation of 5-HMF to DFF. If the two-step method is integrated into a one-step operation, the process will be more economical and environmentally friendly, and the development of bifunctional/multifunctional catalysts enables the integration of the domino/cascade reaction of the process into a one-step operation. However, the bifunctional catalysts currently developed and used have extremely low catalytic efficiency. The problem is related to the bifunctional design of the catalyst, such as the fact that the distance between the acid active center and the metal site is too close, causing some sugar intermediates generated by fructose on the acid active center to be blocked by the adjacent metal before the formation of 5-HMF Site oxidation, or the instability of 5-HMF in a single solvent phase (usually an aqueous phase), changes the concentration gradient across the acid active site resulting in oligomerization of 5-HMF to form humic by-products. Therefore, the development of efficient bifunctional catalysts is still being explored.
发明内容SUMMARY OF THE INVENTION
为了克服现有技术的不足，本发明的目的之一在于提供一种双功能氧化石墨烯催化剂及其制备方法，该制备方法比现有双功能催化剂的合成方法更简便，利用该方法制备的催化剂在氧化石墨烯片表面拥有两个活性中心，即金属活性中心和酸活性中心，能提供合适的酸度和高效的氧化还原位点，还可以重复使用；本发明的目的之二提供一种双功能氧化石墨烯催化剂的应用，该催化剂适用于一锅法级联反应，如醚化-氧化反应，转酯化-加氢反应，脱水-加氢反应，特别适用于果糖一锅法转化制备2,5-二甲酰呋喃。In order to overcome the deficiencies of the prior art, one of the objects of the present invention is to provide a bifunctional graphene oxide catalyst and a preparation method thereof, which is simpler than the synthesis method of the existing bifunctional catalyst, and the catalyst prepared by the method is used. There are two active centers on the surface of graphene oxide sheet, namely metal active center and acid active center, which can provide suitable acidity and efficient redox sites, and can also be reused; the second purpose of the present invention is to provide a dual function The application of graphene oxide catalyst, the catalyst is suitable for one-pot cascade reaction, such as etherification-oxidation reaction, transesterification-hydrogenation reaction, dehydration-hydrogenation reaction, especially suitable for fructose one-pot conversion preparation 2, 5-Diformylfuran.
本发明的目的之一采用如下技术方案实现：One of the objects of the present invention adopts the following technical scheme to realize:
一种双功能氧化石墨烯催化剂的制备方法，包括以下步骤：A preparation method of bifunctional graphene oxide catalyst, comprising the following steps:
1)将氧化石墨烯添加到磺化剂溶液中，将混合溶液在70℃和在N
2下剧烈搅拌回流，回流所得的悬浮液经过离心和洗涤后，冷冻干燥，得到单功能氧化石墨烯；
1) adding graphene oxide to the sulfonating agent solution, vigorously stirring and refluxing the mixed solution at 70° C. and under N , the suspension obtained by the reflux is centrifuged and washed, and then freeze-dried to obtain monofunctional graphene oxide;
2)将单功能氧化石墨烯添加到乙二醇中，超声震荡后，加入贵金属氯化物，再调节pH至13，然后将溶液升温至120℃并与还原剂的乙二醇溶液混合；其中，还原剂为NaBH
4、KBH、水合肼和聚胺中的一种或多种；还原剂占贵金属氯化物的质量比为3～8％；
2) adding monofunctional graphene oxide to ethylene glycol, after ultrasonic vibration, adding precious metal chloride, then adjusting pH to 13, then heating the solution to 120 ° C and mixing with the ethylene glycol solution of the reducing agent; wherein, The reducing agent is one or more of NaBH 4 , KBH, hydrazine hydrate and polyamine; the mass ratio of the reducing agent to the noble metal chloride is 3-8%;
3)将步骤2)所得溶液在120℃下回流，冷却至室温后，向溶液逐滴滴入去离子水，并调节pH至步骤1)的pH值，然后经过过滤水洗，真空干燥后得 到双功能氧化石墨烯催化剂。3) The solution obtained in step 2) was refluxed at 120°C, cooled to room temperature, and deionized water was added dropwise to the solution, and the pH was adjusted to the pH value of step 1). Functional graphene oxide catalyst.
进一步，步骤1)中，氧化石墨烯的碳原料为炭黑、煤、石墨、烟煤、碳纤维和焦炭中的一种或多种。Further, in step 1), the carbon raw material of graphene oxide is one or more of carbon black, coal, graphite, bituminous coal, carbon fiber and coke.
再进一步，步骤1)中，所述磺化剂溶液为氯磺酸溶液、发烟硫酸溶液和烷基磺内酯溶液中的一种或几种；磺化剂溶液的浓度为0.5～3mol/L；剧烈搅拌回流的时间为24h；冷冻干燥的时间为24h。Further, in step 1), the sulfonating agent solution is one or more of chlorosulfonic acid solution, oleum solution and alkyl sultone solution; the concentration of sulfonating agent solution is 0.5～3mol/ L; the time of vigorous stirring and reflux is 24h; the time of freeze-drying is 24h.
进一步，步骤2)中，乙二醇溶液的浓度为1～3mg/mL。Further, in step 2), the concentration of the ethylene glycol solution is 1-3 mg/mL.
再进一步，步骤2)中，贵金属氯化物中的贵金属金属为钌、铑、铂和钯中的一种或几种；贵金属氯化物的浓度为10～20mg/mL。Still further, in step 2), the precious metal in the precious metal chloride is one or more of ruthenium, rhodium, platinum and palladium; the concentration of the precious metal chloride is 10-20 mg/mL.
进一步，步骤3)中，所述双功能氧化石墨烯催化剂的粒径≤20nm，平均孔径≥20nm，比表面为200～300m
2/g。
Further, in step 3), the particle size of the bifunctional graphene oxide catalyst is less than or equal to 20 nm, the average pore diameter is greater than or equal to 20 nm, and the specific surface is 200-300 m 2 /g.
再进一步，步骤3)中，所述双功能氧化石墨烯催化剂中的硫含量为5～6％，金属含量为1～3％。Still further, in step 3), the sulfur content in the bifunctional graphene oxide catalyst is 5-6%, and the metal content is 1-3%.
一种双功能氧化石墨烯催化剂，由上述的制备方法制成。需要补充说明的是，双功能氧化石墨烯催化剂中的贵金属活性中心包括Pt、Pd、Ru和Rh中的一种；酸活性中心包括-SO
3H、-COOH和-TsOH中的一种或几种。具体地，贵金属活性中心的纳米颗粒的粒径为2～10nm。
A bifunctional graphene oxide catalyst is prepared by the above-mentioned 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 includes one or more of -SO 3 H, -COOH and -TsOH. kind. Specifically, the particle size of the nanoparticles of the noble metal active center is 2-10 nm.
本发明的目的之二采用如下技术方案实现：The second purpose of the present invention adopts the following technical scheme to realize:
双功能氧化石墨烯催化剂可以应用在一锅法合成，如醚化-氧化反应、转酯化-加氢反应和脱水-加氢反应。Bifunctional graphene oxide catalysts can be applied in one-pot synthesis, such as etherification-oxidation, transesterification-hydrogenation, and dehydration-hydrogenation.
具体地，双功能氧化石墨烯催化剂应用在果糖制备2,5-二甲酰呋喃(脱水-加氢反应)，反应温度为120～200℃，反应时间为3～8h。Specifically, the bifunctional graphene oxide catalyst is used in fructose to prepare 2,5-diformylfuran (dehydration-hydrogenation reaction), the reaction temperature is 120-200°C, and the reaction time is 3-8h.
作为高度功能化的二维碳纳米材料，石墨烯被用作该催化剂双功能化/多功能化的理想载体，不同的活性中心可在石墨烯纳米片上定位。该双功能催化剂的酸活性中心用于果糖催化水解制备5-HMF，而贵金属活性中心用于5-HMF选择性催化氧化制备DFF。As a highly functionalized 2D carbon nanomaterial, graphene is used as an ideal support for bifunctionalization/multifunctionalization of this catalyst, and different active centers can be localized on the graphene nanosheets. The acid active center of the bifunctional catalyst is used for fructose catalytic hydrolysis to prepare 5-HMF, while the noble metal active center is used for the selective catalytic oxidation of 5-HMF to prepare DFF.
相比现有技术，本发明的有益效果在于：Compared with the prior art, the beneficial effects of the present invention are:
(1)本发明公开了一种双功能氧化石墨烯催化剂的制备方法，第一步是将氧化石墨烯通过加入有机酸磺化后，实现酸活性中心的单功能化，第二步将贵金属纳米颗粒原位固定在氧化石墨烯的碳纳米片上，实现酸活性中心和金属活性中心的双功能化，比现有双功能催化剂的合成方法更简便。(1) The present invention discloses a preparation method of a bifunctional graphene oxide catalyst. The first step is to sulfonate graphene oxide by adding an organic acid to realize the monofunctionalization of the acid active center. The particles are in situ immobilized on the carbon nanosheets of graphene oxide to realize the bifunctionalization of the acid active center and the metal active center, which is simpler than the synthesis method of existing bifunctional catalysts.
(2)利用本发明的制备方法制备的双功能氧化石墨烯催化剂带有双催化活性中心(酸活性中心和贵金属活性中心)，能提供合适的酸度和高效的氧化还原位点，该催化剂除了应用于果糖一锅法催化转化制备2,5-二甲酰呋喃反应中，还能应用在醚化-氧化反应、转酯化-加氢反应和脱水-加氢反应，双功能氧化石墨烯催化剂通过对两个活性中心空间结构的调控，提高反应催化活性和产物选择性。(2) The bifunctional graphene oxide catalyst prepared by the preparation method of the present invention has dual catalytic active centers (acid active center and precious metal active center), which can provide suitable acidity and efficient redox sites. In the one-pot catalytic conversion of fructose to prepare 2,5-diformyl furan, it can also be used in etherification-oxidation reaction, transesterification-hydrogenation reaction and dehydration-hydrogenation reaction, and the bifunctional graphene oxide catalyst passes through The regulation of the spatial structure of the two active centers improves the catalytic activity and product selectivity of the reaction.
(3)本发明制备的双功能氧化石墨烯催化剂可以重复使用，经过研究表明，在催化活性没有明显降低的情况下可重复使用5次以上。(3) The bifunctional graphene oxide catalyst prepared by the present invention can be reused, and studies have shown that it can be reused more than 5 times without significantly reducing the catalytic activity.
图1为实施例1、对比例1和对比例2的拉曼光谱图；Fig. 1 is the Raman spectrogram of embodiment 1, comparative example 1 and comparative example 2;
图2为实施例1、对比例1和对比例2的XRD谱图；Fig. 2 is the XRD spectrum of embodiment 1, comparative example 1 and comparative example 2;
图3为实施例1的TEM和HRTEM图；Fig. 3 is the TEM and HRTEM images of Example 1;
图4为对比例1的TEM图；Fig. 4 is the TEM image of comparative example 1;
图5为对比例2的TEM图。FIG. 5 is a TEM image of Comparative Example 2. FIG.
下面，结合附图以及具体实施方式，对本发明做进一步描述，需要说明的是，在不相冲突的前提下，以下描述的各实施例之间或各技术特征之间可以任意组合形成新的实施例。The present invention will be further described below with reference to the accompanying drawings and specific embodiments. It should be noted that, on the premise of no conflict, the embodiments or technical features described below can be combined arbitrarily to form new embodiments. .
本发明制备的双功能氧化石墨烯催化剂适用于各种类型的反应器，如移动床反应器、管式反应器和搅拌釜反应器等。The bifunctional graphene oxide catalyst prepared by the invention is suitable for various types of reactors, such as moving bed reactors, tubular reactors and stirred tank reactors.
本发明制备的双功能氧化石墨烯催化剂应用于一锅法级联反应，一锅法反应中的多步反应可以从相对简单易得的原料出发，不经中间体的分离，直接获得结构复杂的分子，如醚化-氧化反应，转酯化-加氢反应，脱水-加氢反应。The bifunctional graphene oxide catalyst prepared by the invention is applied to the one-pot cascade reaction, and the multi-step reaction in the one-pot reaction can start from relatively simple and readily available raw materials, without separation of intermediates, to directly obtain complex structures. Molecules such as etherification-oxidation, transesterification-hydrogenation, dehydration-hydrogenation.
醚化-氧化反应：Etherification-oxidation reaction:
转酯化-加氢反应：Transesterification-hydrogenation reaction:
脱水-加氢反应的具体例子为：果糖制备2,5-二甲酰呋喃A specific example of the dehydration-hydrogenation reaction is: the preparation of 2,5-diformylfuran from fructose
实施例1Example 1
一种双功能氧化石墨烯催化剂的制备方法，包括以下步骤：A preparation method of bifunctional graphene oxide catalyst, comprising the following steps:
1)将氧化石墨烯(Cobat Corporation)添加到3mol/L氯磺酸(98％，Sigma-Aldrich)的氯仿溶液中，将混合溶液在70℃和在N
2下剧烈搅拌回流24h，回流所得的悬浮液冷却至室温后，用去离子水和乙醇在冰浴中反复离心和洗涤，冷冻干燥24h，得到单功能氧化石墨烯；
1) Graphene oxide (Cobat Corporation) was added to a chloroform solution of 3 mol/L chlorosulfonic acid (98%, Sigma-Aldrich), and the mixed solution was vigorously stirred and refluxed at 70° C. under N for 24 h. After the suspension was cooled to room temperature, it was centrifuged and washed repeatedly in an ice bath with deionized water and ethanol, and freeze-dried for 24 hours to obtain monofunctional graphene oxide;
2)将单功能氧化石墨烯添加到1mg/mL乙二醇中，超声震荡1～3h后，加入浓度为20mg/mL氯化钌(III)水合物(钌含量为40.00wt％，Sigma-Aldrich) 静置3h，再添加NaOH溶液调节pH至13，然后将溶液升温至120℃并与浓度为20mg/mL NaBH
4的乙二醇溶液缓慢混合；其中，NaBH
4的乙二醇溶液占三氯化钌溶液的质量比为3％；
2) Add monofunctional graphene oxide to 1 mg/mL ethylene glycol, and after ultrasonic vibration for 1 to 3 hours, add 20 mg/mL ruthenium chloride (III) hydrate (ruthenium content is 40.00 wt%, Sigma-Aldrich) ) for 3 hours, and then add NaOH solution to adjust the pH to 13, then the solution was heated to 120 ° C and slowly mixed with the ethylene glycol solution with a concentration of 20 mg/mL NaBH 4 ; wherein, the ethylene glycol solution of NaBH 4 accounted for three chlorine The mass ratio of the ruthenium solution is 3%;
3)将步骤2)所得溶液在120℃下回流1h，冷却至室温后，向溶液逐滴滴入1L去离子水，并用0.1mol/L的HCl溶液调节pH至步骤1)的pH值，然后经过过滤水洗，在80℃下真空干燥12h后得到双功能氧化石墨烯催化剂。3) Reflux the solution obtained in step 2) at 120°C for 1 h, and after cooling to room temperature, dropwise add 1 L of deionized water to the solution, and adjust the pH to the pH value of step 1) with 0.1 mol/L HCl solution, then After filtration and washing, and vacuum drying at 80 °C for 12 h, a bifunctional graphene oxide catalyst was obtained.
在本实施例中，双功能氧化石墨烯催化剂的粒径≤20nm，平均孔径≥20nm，比表面为298m
2/g。双功能氧化石墨烯催化剂中的硫含量为6％，金属含量为3％。
In this embodiment, the particle size of the bifunctional graphene oxide catalyst is less than or equal to 20 nm, the average pore diameter is greater than or equal to 20 nm, and the specific surface is 298 m 2 /g. The sulfur content in the bifunctional graphene oxide catalyst was 6% and the metal content was 3%.
本实施例中的催化剂是以磺酸基为酸活性中心、钌(Ru)为金属活性中心的双功能氧化石墨烯催化剂，命名为Ru/S-rGO。The catalyst in this embodiment is a bifunctional graphene oxide catalyst with a sulfonic acid group as an acid active center and ruthenium (Ru) as a metal active center, named Ru/S-rGO.
实施例2Example 2
一种双功能氧化石墨烯催化剂的制备方法，包括以下步骤：A preparation method of bifunctional graphene oxide catalyst, comprising the following steps:
1)将氧化石墨烯(Cobat Corporation)添加到0.5mol/L发烟硫酸(SO
3含量30％，Sigma-Aldrich)溶液中，将混合溶液在70℃和在N
2下剧烈搅拌回流24h，回流所得的悬浮液冷却至室温后，用去离子水和乙醇在冰浴中反复离心和洗涤，冷冻干燥24h，得到单功能氧化石墨烯；
1) Graphene oxide (Cobat Corporation) was added to 0.5 mol/L fuming sulfuric acid (SO content 30 %, Sigma-Aldrich) solution, and the mixed solution was vigorously stirred and refluxed at 70 °C under N for 24 h, refluxed The obtained suspension was cooled to room temperature, centrifuged and washed repeatedly in an ice bath with deionized water and ethanol, and freeze-dried for 24 hours to obtain monofunctional graphene oxide;
2)将单功能氧化石墨烯添加到3mg/mL乙二醇中，超声震荡1～3h后，加入浓度为10mg/mL氯化铂(II)(Pt含量≥73％，Alfa Aesar)溶液静置1h，再添加NaOH溶液调节pH至13，然后将溶液升温至120℃并与10mg/mLKBH的乙二醇溶液缓慢混合；其中，KBH的乙二醇溶液占三氯化铑溶液的质量比为8％；2) Add monofunctional graphene oxide to 3 mg/mL ethylene glycol, and after ultrasonic vibration for 1 to 3 hours, add a solution with a concentration of 10 mg/mL platinum(II) chloride (Pt content ≥ 73%, Alfa Aesar) and let stand For 1 h, add NaOH solution to adjust the pH to 13, then heat the solution to 120 °C and slowly mix it with 10 mg/mL KBH ethylene glycol solution; wherein, the mass ratio of KBH ethylene glycol solution to rhodium trichloride solution is 8 %;
3)将步骤2)所得溶液在120℃下回流1h，冷却至室温后，向溶液逐滴滴入2L去离子水，并用0.1mol/L的HCl溶液调节pH至步骤1)的pH值，然后 经过过滤水洗，在80℃下真空干燥8h后得到双功能氧化石墨烯催化剂。3) Reflux the solution obtained in step 2) at 120° C. for 1 h, and after cooling to room temperature, dropwise add 2 L of deionized water to the solution, and adjust the pH to the pH value of step 1) with 0.1 mol/L HCl solution, then After filtration and washing, and vacuum drying at 80 °C for 8 h, a bifunctional graphene oxide catalyst was obtained.
在本实施例中，双功能氧化石墨烯催化剂的粒径≤20nm，平均孔径≥20nm，比表面为201m
2/g。所述双功能氧化石墨烯催化剂中的硫含量为5％，金属含量为1％。
In this embodiment, the particle size of the bifunctional graphene oxide catalyst is less than or equal to 20 nm, the average pore size is greater than or equal to 20 nm, and the specific surface area is 201 m 2 /g. The sulfur content in the bifunctional graphene oxide catalyst is 5%, and the metal content is 1%.
实施例3Example 3
一种双功能氧化石墨烯催化剂的制备方法，包括以下步骤：A preparation method of bifunctional graphene oxide catalyst, comprising the following steps:
1)将氧化石墨烯氧化石墨烯(Cobat Corporation)添加到2mol/L发烟硫酸(SO
3含量30％，Sigma-Aldrich)溶液中，将混合溶液在70℃和在N
2下剧烈搅拌回流24h，回流所得的悬浮液冷却至室温后，用去离子水和乙醇在冰浴中反复离心和洗涤，冷冻干燥24h，得到单功能氧化石墨烯；
1) Graphene oxide graphene oxide (Cobat Corporation) was added to a 2 mol/L oleum (SO content 30 %, Sigma-Aldrich) solution, and the mixed solution was vigorously stirred and refluxed at 70 °C under N for 24 h , after the suspension obtained by refluxing was cooled to room temperature, centrifuged and washed repeatedly in an ice bath with deionized water and ethanol, and freeze-dried for 24 h to obtain monofunctional graphene oxide;
2)将单功能氧化石墨烯添加到2mg/mL乙二醇中，超声震荡3h后，加入浓度为15mg/mL氯化钯(≥99％，Alfa Aesar)静置1h，再添加NaOH溶液调节pH至13，然后将溶液升温至120℃并与水合肼的乙二醇溶液缓慢混合；其中，水合肼的乙二醇溶液占三氯化钯溶液的质量比为5％；2) Add monofunctional graphene oxide to 2mg/mL ethylene glycol, after ultrasonic vibration for 3h, add a concentration of 15mg/mL palladium chloride (≥99%, Alfa Aesar) and let stand for 1h, then add NaOH solution to adjust pH To 13, then the solution is heated to 120 ° C and slowly mixed with the ethylene glycol solution of hydrazine hydrate; wherein, the ethylene glycol solution of hydrazine hydrate accounts for 5% of the mass ratio of the palladium trichloride solution;
3)将步骤2)所得溶液在120℃下回流1h，冷却至室温后，向溶液逐滴滴入1L去离子水，并用0.1mol/L的HCl溶液调节pH至步骤1)的pH值，然后经过过滤水洗，在80℃下真空干燥10h后得到双功能氧化石墨烯催化剂。3) Reflux the solution obtained in step 2) at 120°C for 1 h, and after cooling to room temperature, dropwise add 1 L of deionized water to the solution, and adjust the pH to the pH value of step 1) with 0.1 mol/L HCl solution, then After filtration and washing, and vacuum drying at 80 °C for 10 h, a bifunctional graphene oxide catalyst was obtained.
在本实施例中，双功能氧化石墨烯催化剂的粒径≤20nm，平均孔径≥20nm，比表面为258m
2/g。所述双功能氧化石墨烯催化剂中的硫含量为5％，金属含量为2％。
In this embodiment, the particle size of the bifunctional graphene oxide catalyst is less than or equal to 20 nm, the average pore size is greater than or equal to 20 nm, and the specific surface area is 258 m 2 /g. The sulfur content in the bifunctional graphene oxide catalyst is 5%, and the metal content is 2%.
对比例1Comparative Example 1
一种单功能氧化石墨烯催化剂的制备方法，包括以下步骤：A preparation method of monofunctional graphene oxide catalyst, comprising the following steps:
1)将氧化石墨烯(Cobat Corporation)添加到3mol/L氯磺酸(98％，Sigma-Aldrich)的氯仿溶液中，将混合溶液在70℃和在N2下剧烈搅拌回流24h，回流所得的悬浮液冷却至室温后，用去离子水和乙醇在冰浴中反复离心和洗涤，冷冻干燥24h，得到单功能氧化石墨烯催化剂，对比例1的催化剂命名为SGO。(即与实施例1的步骤1相同)1) Graphene oxide (Cobat Corporation) was added to a chloroform solution of 3 mol/L chlorosulfonic acid (98%, Sigma-Aldrich), and the mixed solution was vigorously stirred and refluxed at 70 °C under N2 for 24 h, and the resulting suspension was refluxed. After the liquid was cooled to room temperature, it was centrifuged and washed repeatedly in an ice bath with deionized water and ethanol, and freeze-dried for 24 h to obtain a monofunctional graphene oxide catalyst. The catalyst of Comparative Example 1 was named SGO. (i.e. the same as step 1 of Example 1)
对比例2Comparative Example 2
选用与实施例1相同的氧化石墨烯(Cobat Corporation)，氧化石墨烯命名为GO。Select the same graphene oxide (Cobat Corporation) as in Example 1, and the graphene oxide is named GO.
催化剂表征测试Catalyst Characterization Testing
一、对实施例1、对比例1和对比例2进行拉曼光谱测定，采用配置热电冷却CCD检测器的HORIBA JY LabRAM HR Evolution，由50MW镨激光器提供532nm激发辐射，得到图11. Carry out Raman spectrometry for Example 1, Comparative Example 1 and Comparative Example 2, using HORIBA JY LabRAM HR Evolution equipped with a thermoelectric cooling CCD detector, and 532nm excitation radiation provided by a 50MW praseodymium laser, as shown in Figure 1
如图1所示，对比例1和实施例1中D峰(缺陷和不规则sp3碳原子峰)和G峰(二维石墨六边形晶格sp2碳原子峰)的强度比相似，均比对比例2高。对比例1中存在SO
3H基团，实施例1存在SO
3H基团和Ru纳米颗粒，证明SO
3H基团和/或Ru纳米颗粒的引入均使石墨结构部分破坏。
As shown in Figure 1, the intensity ratio of D peak (defective and irregular sp3 carbon atom peak) and G peak (two-dimensional graphite hexagonal lattice sp2 carbon atom peak) in Comparative Example 1 and Example 1 are similar, and the Comparative example 2 is high. SO 3 H groups exist in Comparative Example 1, and SO 3 H groups and Ru nanoparticles exist in Example 1, which proves that the introduction of SO 3 H groups and/or Ru nanoparticles both partially destroys the graphitic structure.
二、对实施例1、对比例1和对比例2进行XRD测试，XRD图谱使用RigakuUltima IV衍射计在Cu Kα辐射源为20mA和40kV、扫描速率为0.5o/min(λ＝1.54056A)下测定，得到图22. Carry out XRD test on Example 1, Comparative Example 1 and Comparative Example 2, and the XRD pattern was measured using a RigakuUltima IV diffractometer under a Cu Kα radiation source of 20mA and 40kV and a scan rate of 0.5o/min (λ=1.54056A). , get Figure 2
对比例2的特征结构中在10.3°处存在衍射峰，对应晶格间距为8.6A的晶面；而对比例1和实施例1的特征结构中均在24.8°处存在典型宽衍射峰，对应晶格间距为3.6A的晶面。实施例1的催化剂还发现出现在42.2°和44.0°的峰分别与002相和101相对应。由于Ru的负载量低，因此谱图中未找到Ru的特征六角 相(JCPDS卡号60663)。The characteristic structure of Comparative Example 2 has a diffraction peak at 10.3°, corresponding to a crystal plane with a lattice spacing of 8.6A; while the characteristic structures of Comparative Example 1 and Example 1 both 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 phases 002 and 101, respectively. Due to the low loading of Ru, the characteristic hexagonal phase of Ru was not found in the spectrum (JCPDS Card No. 60663).
三、对实施例1的催化剂进行TEM和STEM测试，对对比例1和对比例2进行TEM测试，TEM图像采用配置ZrO/W肖特基场发射枪JEOL 2100F显微镜在200kV下测定，STEM图像采用带EDAX Edx.拉曼光谱(Renishaw InVia Reflex Raman)的环形暗场在633nm激发波长下测定，得到图3～53. TEM and STEM tests were performed on the catalyst of Example 1, and TEM tests were performed on Comparative Examples 1 and 2. The TEM images were measured with a JEOL 2100F microscope equipped with a ZrO/W Schottky field emission gun at 200kV. The annular dark field with EDAX Edx. Raman spectrum (Renishaw InVia Reflex Raman) was measured at the excitation wavelength of 633 nm, and Figures 3 to 5 were obtained
如图3所示，TEM图像显示平均尺寸为3nm的Ru纳米颗粒负载于磺化后的氧化石墨烯(SGO)片上。HRTEM图像显示金属态Ru的101晶面特性间距为1.88A，与图2的XRD表征结构一致。As shown in Fig. 3, the TEM images showed that Ru nanoparticles with an average size of 3 nm were supported on the sulfonated graphene oxide (SGO) sheets. The HRTEM image shows that the characteristic spacing of the 101 crystal plane of metallic Ru is 1.88A, which is consistent with the XRD characterization structure in Figure 2.
将图3、4和5进行对比，说明经过磺酸基和/或Ru纳米颗粒功能化后，氧化石墨烯的主要特征结构和形态没有被破坏。实施例1的活性中心均匀分布在氧化石墨烯片的两侧，使得反应物分子更容易与催化剂接触，生成的产物能迅速扩散。Comparing Figures 3, 4 and 5, it is shown that the main characteristic structure and morphology of graphene oxide are not destroyed after functionalization with sulfonic acid groups and/or Ru nanoparticles. The active centers of Example 1 are evenly 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 diffuse rapidly.
催化剂在果糖催化转化制备2,5-二甲酰呋喃(DFF)的测试Test of the catalyst in the catalytic conversion of fructose to prepare 2,5-diformylfuran (DFF)
催化反应在一个带机械搅拌的50ml高压反应器内进行。反应器设有多个进出料口，原料通过进料导管进入反应器，特定氮气/氧气体积比的空气通过喷嘴进入液相。该反应条件可根据工业需求进行放大。常规实验过程中，特定质量的果糖、催化剂和水/有机溶剂加入到反应釜中，在搅拌下将混合物加热至设定温度。反应结束后反应器在冰浴中冷却，催化剂经简单离心分离回收重复利用。有机相和水相中的呋喃基产物通过HPLC(Agilent 1100Series)进行分析，HPLC配置282nm紫外检测器、C18反相柱，采用乙腈:乙酸(3:7v/v)作为移动相。使用外标法对产物进行定量，采用自动进样器(Agilent G1329A)提高检测的再现性。呋喃衍生物产率和果糖转化率根据在两相中产物浓度(可从HPLC检测结果中得出)以碳基形式计算得出。The catalytic reaction was carried out in a 50 ml high pressure reactor with mechanical stirring. The reactor is provided with a plurality of inlet and outlet ports, the raw materials enter the reactor through the feeding conduit, and the air with a specific nitrogen/oxygen volume ratio enters the liquid phase through the nozzle. The reaction conditions can be scaled up according to industrial needs. During routine experiments, specific masses of fructose, catalyst, and water/organic solvent were added to the reaction kettle, and the mixture was heated to a set temperature with stirring. After the reaction, the reactor was cooled in an ice bath, and the catalyst was recovered and reused by simple centrifugal separation. The furan-based products in the organic and aqueous phases were analyzed by HPLC (Agilent 1100 Series) equipped with a 282 nm UV detector, a C18 reversed-phase column, and acetonitrile:acetic acid (3:7 v/v) was used as the mobile phase. The product was quantified using an external standard method, and an autosampler (Agilent G1329A) was used to improve detection reproducibility. Furan derivative yields and fructose conversions were calculated in carbon-based form based on the product concentrations in the two phases (obtainable from HPLC measurements).
催化剂组选用：实施例1、Ru
3+/H
2SO
4、Ru
3+/离子液体、MoO
3/SGO、MoO
3/ZSM-5和V
2O
5/ZSM-5。其中，Ru
3+/H
2SO
4催化剂中Ru
3+由与实施例1等量的氯化钌(III)水合物(钌含量为40.00wt％，Sigma-Aldrich)提供。MoO
3/SGO中的SGO与对比例1的制备方法相同。
Catalyst group selection: Example 1, Ru 3+ /H 2 SO 4 , Ru 3+ /ionic liquid, MoO 3 /SGO, MoO 3 /ZSM-5 and V 2 O 5 /ZSM-5. Wherein, Ru 3+ in the Ru 3+ /H 2 SO 4 catalyst was provided by the same amount of ruthenium (III) chloride hydrate (ruthenium content: 40.00 wt%, Sigma-Aldrich) as in Example 1. The SGO in MoO 3 /SGO was prepared in the same way as in Comparative Example 1.
催化反应条件：在10mL甲基异丁基酮中加入0.5g果糖(≥99％，Alfa Aesar)和10mg催化剂，140℃下反应2h。催化剂组的催化效果如下表：Catalytic reaction conditions: 0.5 g of fructose (≥99%, Alfa Aesar) and 10 mg of catalyst were added to 10 mL of methyl isobutyl ketone, and the reaction was carried out at 140° C. for 2 h. The catalytic effect of the catalyst group is as follows:
表1 不同催化剂对果糖催化转化制备2,5-二甲酰呋喃(DFF)的效果Table 1 Effects of different catalysts on the catalytic conversion of fructose to prepare 2,5-diformylfuran (DFF)
| 催化剂catalyst | DFF产率(％)DFF yield (%) | 果糖转化率(％)Fructose conversion rate (%) |
| 实施例1Example 1 | 83.283.2 | 100100 |
| Ru 3+/H 2SO 4 Ru 3+ /H 2 SO 4 | 86.586.5 | 100100 |
| Ru 3+/离子液体 Ru 3+ / ionic liquid | 90.290.2 | 100100 |
| MoO 3/SGO MoO 3 /SGO | 68.668.6 | 98.298.2 |
| MoO 3/ZSM-5 MoO 3 /ZSM-5 | 55.755.7 | 99.199.1 |
| V 2O 5/ZSM-5 V 2 O 5 /ZSM-5 | 52.352.3 | 99.399.3 |
由表1所示，相比于如MoO
3/SGO、MoO
3/ZSM-5和V
2O
5/ZSM-5常用的多相催化剂，实施例1展现出极高的果糖转化率(高达100％)和优异的2,5-二甲酰呋喃选择性。尽管Ru
3+/H
2SO
4和Ru
3+/离子液体与实施例1相比同样具备优异的2,5-二甲酰呋喃产率，但由于其对环境有害或者价格昂贵，直接限制了其在2,5-二甲酰呋喃大规模生产中的应用。相比而言，实施例1是一种廉价的碳基材料，由于其高效的酸基团和氧化石墨烯片表面金属活性中心的良好分散性，实施例1(Ru/S-rGO)展现出类似于均相催化剂的高效反应活性。由于实施例1催化的2,5-二甲酰呋喃产率高达83.2％，因此在优化该催化反应过程的工艺条件 (反应器设计、进料速率、产物提纯等)的基础上，有望实现2,5-二甲酰呋喃的大规模生产。
As shown in Table 1, Example 1 exhibits extremely high fructose conversion (up to 100%) compared to commonly used heterogeneous catalysts such as MoO3/SGO, MoO3/ZSM - 5 and V2O5 /ZSM- 5 . %) and excellent 2,5-diformylfuran selectivity. Although Ru 3+ /H 2 SO 4 and Ru 3+ /ionic liquid also have excellent yields of 2,5-diformylfuran compared with Example 1, they are directly limited due to their harmfulness to the environment or high price. Its application in the large-scale production of 2,5-diformylfuran. In contrast, Example 1 is an inexpensive carbon-based material. Due to its efficient acid groups and good dispersion of metal active centers on the surface of graphene oxide sheets, Example 1 (Ru/S-rGO) exhibits Efficient reactivity similar to homogeneous catalysts. Since the yield of 2,5-diformylfuran catalyzed in Example 1 is as high as 83.2%, on the basis of optimizing the process conditions (reactor design, feed rate, product purification, etc.) of the catalytic reaction process, it is expected to achieve 2 , Large-scale production of 5-diformylfuran.
上述实施方式仅为本发明的优选实施方式，不能以此来限定本发明保护的范围，本领域的技术人员在本发明的基础上所做的任何非实质性的变化及替换均属于本发明所要求保护的范围。The above-mentioned embodiments are only preferred embodiments of the present invention, and cannot be used to limit the scope of protection of the present invention. Any insubstantial changes and substitutions made by those skilled in the art on the basis of the present invention belong to the scope of the present invention. Scope of protection claimed.
Claims (10)
- 一种双功能氧化石墨烯催化剂的制备方法，其特征在于，包括以下步骤：A kind of preparation method of bifunctional graphene oxide catalyst, is characterized in that, comprises the following steps:1)将氧化石墨烯添加到磺化剂溶液中，将混合溶液在70℃和在N 2下剧烈搅拌回流，回流所得的悬浮液经过离心和洗涤后，冷冻干燥，得到单功能氧化石墨烯； 1) adding graphene oxide to the sulfonating agent solution, vigorously stirring and refluxing the mixed solution at 70° C. and under N , the suspension obtained by the reflux is centrifuged and washed, and then freeze-dried to obtain monofunctional graphene oxide;2)将单功能氧化石墨烯添加到乙二醇中，超声震荡后，加入贵金属氯化物，再调节pH至13，然后将溶液升温至120℃并与还原剂的乙二醇溶液混合；其中，还原剂为NaBH 4、KBH、水合肼和聚胺中的一种或多种；还原剂占贵金属氯化物的质量比为3～8％； 2) adding monofunctional graphene oxide to ethylene glycol, after ultrasonic vibration, adding precious metal chloride, then adjusting pH to 13, then heating the solution to 120 ° C and mixing with the ethylene glycol solution of the reducing agent; wherein, The reducing agent is one or more of NaBH 4 , KBH, hydrazine hydrate and polyamine; the mass ratio of the reducing agent to the noble metal chloride is 3-8%;3)将步骤2)所得溶液在120℃下回流，冷却至室温后，向溶液逐滴滴入去离子水，并调节pH至步骤1)的pH值，然后经过过滤水洗，真空干燥后得到双功能氧化石墨烯催化剂。3) The solution obtained in step 2) was refluxed at 120°C, cooled to room temperature, and deionized water was added dropwise to the solution, and the pH was adjusted to the pH value of step 1). Functional graphene oxide catalyst.
- 如权利要求1所述的双功能氧化石墨烯催化剂的制备方法，其特征在于，步骤1)中，氧化石墨烯的碳原料为炭黑、煤、石墨、烟煤、碳纤维和焦炭中的一种或多种。The preparation method of bifunctional graphene oxide catalyst as claimed in claim 1, is characterized in that, in step 1), the carbon raw material of graphene oxide is one of carbon black, coal, graphite, bituminous coal, carbon fiber and coke or variety.
- 如权利要求1所述的双功能氧化石墨烯催化剂的制备方法，其特征在于，步骤1)中，所述磺化剂溶液为氯磺酸溶液、发烟硫酸溶液和烷基磺内酯溶液中的一种或几种；所述磺化剂溶液的浓度为0.5～3mol/L；剧烈搅拌回流的时间为24h；冷冻干燥的时间为24h。The preparation method of bifunctional graphene oxide catalyst as claimed in claim 1, is characterized in that, in step 1), described sulfonating agent solution is in chlorosulfonic acid solution, oleum solution and alkyl sultone solution The concentration of the sulfonating agent solution is 0.5-3 mol/L; the time for vigorous stirring and reflux is 24h; the time for freeze-drying is 24h.
- 如权利要求1所述的双功能氧化石墨烯催化剂的制备方法，其特征在于，步骤2)中，所述乙二醇溶液的浓度为1～3mg/mL。The method for preparing a bifunctional graphene oxide catalyst according to claim 1, wherein in step 2), the concentration of the ethylene glycol solution is 1-3 mg/mL.
- 如权利要求1所述的双功能氧化石墨烯催化剂的制备方法，其特征在于， 步骤2)中，所述贵金属氯化物中的贵金属金属为钌、铑、铂和钯中的一种或几种；贵金属氯化物的浓度为10～20mg/mL。The method for preparing a bifunctional graphene oxide catalyst according to claim 1, wherein in step 2), the noble metal in the noble metal chloride is one or more of ruthenium, rhodium, platinum and palladium ; The concentration of precious metal chloride is 10～20mg/mL.
- 如权利要求1所述的双功能氧化石墨烯催化剂的制备方法，其特征在于，步骤3)中，所述双功能氧化石墨烯催化剂的粒径≤20nm，平均孔径≥20nm，比表面为200～300m 2/g。 The method for preparing a bifunctional graphene oxide catalyst according to claim 1, wherein in step 3), the particle size of the bifunctional graphene oxide catalyst is ≤20 nm, the average pore size is ≥20 nm, and the specific surface is 200～200 nm. 300m 2 /g.
- 如权利要求1所述的双功能氧化石墨烯催化剂的制备方法，其特征在于，步骤3)中，所述双功能氧化石墨烯催化剂中的硫含量为5～6％，金属含量为1～3％。The method for preparing a bifunctional graphene oxide catalyst according to claim 1, wherein in step 3), the sulfur content in the bifunctional graphene oxide catalyst is 5-6%, and the metal content is 1-3% %.
- 一种双功能氧化石墨烯催化剂，其特征在于，由权利要求1～7任一所述的制备方法制成。A bifunctional graphene oxide catalyst is characterized in that, it is made by the preparation method described in any one of claims 1-7.
- 如权利要求8所述的双功能氧化石墨烯催化剂的应用，其特征在于，所述双功能氧化石墨烯催化剂在醚化-氧化反应、转酯化-加氢反应和脱水-加氢反应中的应用。The application of bifunctional graphene oxide catalyst as claimed in claim 8, is characterized in that, described bifunctional graphene oxide catalyst in etherification-oxidation reaction, transesterification-hydrogenation reaction and dehydration-hydrogenation reaction application.
- 如权利要求8所述的双功能氧化石墨烯催化剂的应用，其特征在于，所述双功能氧化石墨烯催化剂应用在果糖制备2,5-二甲酰呋喃，反应温度为120～200℃，反应时间为3～8h。The application of the bifunctional graphene oxide catalyst according to claim 8, wherein the bifunctional graphene oxide catalyst is used in the preparation of 2,5-diformyl furan from fructose, and the reaction temperature is 120-200° C. The time is 3 ~ 8h.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011125545.7A CN112264100A (en) | 2020-10-20 | 2020-10-20 | Bifunctional graphene oxide catalyst, and preparation method and application thereof |
| CN202011125545.7 | 2020-10-20 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2022083142A1 true WO2022083142A1 (en) | 2022-04-28 |
Family
ID=74341540
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/CN2021/099939 WO2022083142A1 (en) | 2020-10-20 | 2021-06-15 | Bifunctional graphene oxide catalyst, preparation method therefor and use thereof |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN112264100A (en) |
| WO (1) | WO2022083142A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112264100A (en) * | 2020-10-20 | 2021-01-26 | 广州维港环保科技有限公司 | Bifunctional graphene oxide catalyst, and preparation method and application thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103359728A (en) * | 2013-07-26 | 2013-10-23 | 武汉理工大学 | Preparation method of sulfonated graphene |
| CN104043481A (en) * | 2014-06-12 | 2014-09-17 | 河南农业大学 | Preparation method for functionalized graphene loaded noble metal nano-crystalline composite catalyst |
| KR101640545B1 (en) * | 2015-03-27 | 2016-07-18 | 부산대학교 산학협력단 | Production method of catalyst-graphitic carbon nitride-reduced graphene oxide composite, the composite produced thereby, and an electrode using the same |
| CN105903481A (en) * | 2016-04-27 | 2016-08-31 | 中国科学院合肥物质科学研究院 | Sulfonyl-functionalized carbon-based metal catalyst and application thereof |
| KR101846783B1 (en) * | 2017-06-21 | 2018-04-06 | 성균관대학교산학협력단 | Catalyst, manufacturing method of catalyst, and manufacturing method of 2,5-dimethylfuran using catalyst |
| CN110756187A (en) * | 2019-10-28 | 2020-02-07 | 西安交通大学 | Gold-palladium/graphene catalyst growing on graphene surface in situ and preparation method thereof |
| CN111054392A (en) * | 2019-12-09 | 2020-04-24 | 山西大学 | Metal-solid acid double-center catalyst and application thereof in preparation of furfuryl alcohol by catalyzing xylose dehydration-hydrogenation |
| CN112264100A (en) * | 2020-10-20 | 2021-01-26 | 广州维港环保科技有限公司 | Bifunctional graphene oxide catalyst, and preparation method and application thereof |
-
2020
- 2020-10-20 CN CN202011125545.7A patent/CN112264100A/en active Pending
-
2021
- 2021-06-15 WO PCT/CN2021/099939 patent/WO2022083142A1/en active Application Filing
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103359728A (en) * | 2013-07-26 | 2013-10-23 | 武汉理工大学 | Preparation method of sulfonated graphene |
| CN104043481A (en) * | 2014-06-12 | 2014-09-17 | 河南农业大学 | Preparation method for functionalized graphene loaded noble metal nano-crystalline composite catalyst |
| KR101640545B1 (en) * | 2015-03-27 | 2016-07-18 | 부산대학교 산학협력단 | Production method of catalyst-graphitic carbon nitride-reduced graphene oxide composite, the composite produced thereby, and an electrode using the same |
| CN105903481A (en) * | 2016-04-27 | 2016-08-31 | 中国科学院合肥物质科学研究院 | Sulfonyl-functionalized carbon-based metal catalyst and application thereof |
| KR101846783B1 (en) * | 2017-06-21 | 2018-04-06 | 성균관대학교산학협력단 | Catalyst, manufacturing method of catalyst, and manufacturing method of 2,5-dimethylfuran using catalyst |
| CN110756187A (en) * | 2019-10-28 | 2020-02-07 | 西安交通大学 | Gold-palladium/graphene catalyst growing on graphene surface in situ and preparation method thereof |
| CN111054392A (en) * | 2019-12-09 | 2020-04-24 | 山西大学 | Metal-solid acid double-center catalyst and application thereof in preparation of furfuryl alcohol by catalyzing xylose dehydration-hydrogenation |
| CN112264100A (en) * | 2020-10-20 | 2021-01-26 | 广州维港环保科技有限公司 | Bifunctional graphene oxide catalyst, and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| HE XIAODONG: "Preparation of Functional Graphene and Its Application as a Catalyst", CHINESE MASTER'S THESES FULL-TEXT DATABASE, 1 February 2012 (2012-02-01), pages 1 - 94, XP055924477 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112264100A (en) | 2021-01-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Dharmarathna et al. | Direct sonochemical synthesis of manganese octahedral molecular sieve (OMS-2) nanomaterials using cosolvent systems, their characterization, and catalytic applications | |
| Liao et al. | An active, selective, and stable manganese oxide-supported atomic Pd catalyst for aerobic oxidation of 5-hydroxymethylfurfural | |
| Yuan et al. | Photocatalytic aerobic oxidation of toluene and its derivatives to aldehydes on Pd/Bi2WO6 | |
| Guan et al. | Pickering HIPEs derived hierarchical porous nitrogen-doped carbon supported bimetallic AuPd catalyst for base-free aerobic oxidation of HMF to FDCA in water | |
| Bai et al. | Flower-like Bi2O2CO3-mediated selective oxidative coupling processes of amines under visible light irradiation | |
| CN104069882A (en) | Preparation method of nanocrystalline metal catalyst loaded with carbon and nitrogen materials | |
| CN109482235B (en) | Preparation method and application of N-doped mesoporous carbon supported metal nano catalyst | |
| Ghorbani-Vaghei et al. | Diethylenetriamine-functionalized single-walled carbon nanotubes (SWCNTs) to immobilization palladium as a novel recyclable heterogeneous nanocatalyst for the Suzuki–Miyaura coupling reaction in aqueous media | |
| CN108380208B (en) | Pd-Mg/C catalyst for preparing 2, 3-dichloropyridine by catalytic hydrogenation of 2,3, 6-trichloropyridine and preparation method thereof | |
| CN110560085A (en) | In-situ sulfur-doped mesoporous carbon-supported palladium metal catalyst and preparation method and application thereof | |
| WO2022083142A1 (en) | Bifunctional graphene oxide catalyst, preparation method therefor and use thereof | |
| WO2017181514A1 (en) | Synthesis method for 2,2'-dipyridine using supported bimetal nano catalyst | |
| Xue et al. | Zirconium-based metal-organic framework as an efficiently heterogeneous photocatalyst for oxidation of benzyl halides to aldehydes | |
| CN110787830B (en) | Ruthenium oxide-loaded carbon nitride hollow tube photocatalyst and preparation and application thereof | |
| CN114849694A (en) | Catalyst based on metal-loaded tungsten oxide hydrogenated nitroarene and preparation method and application thereof | |
| WO2018209665A1 (en) | Preparation method for nano-nickel-based catalyst with confinement structure and hexahedral morphology, and application thereof for catalytic hydrogenation | |
| CN109731577B (en) | Copper element doped carbon material, application and reaction method for preparing primary aromatic amine through coupling reaction of halogenated aromatic compound and ammonia water | |
| Zeng et al. | Bismuth vanadate: A versatile heterogeneous catalyst for photocatalytic functionalization of C (sp2)–H bonds | |
| Zhu et al. | Visible-light-driven carbonylation reaction over palladium supported on spherical-like graphitic carbon nitride | |
| CN113546687A (en) | Preparation method and application of visible light catalyst of ultrathin titanium-based MOFs nanosheets | |
| Song et al. | Recent advance in selective hydrogenation reaction catalyzed by biomass-derived non-noble metal nanocomposites | |
| CN116178244A (en) | Fullerene pyrrolidine derivative, and preparation method and application thereof | |
| CN115555031A (en) | Preparation method and application of nickel hydroxide supported palladium monatomic catalyst | |
| CN114602554A (en) | CoMn-MOF supported catalyst and preparation method thereof | |
| CN114054100A (en) | Preparation and application of doped composite oxide catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 21881564 Country of ref document: EP Kind code of ref document: A1 |
|
| NENP | Non-entry into the national phase |
Ref country code: DE |
|
| 122 | Ep: pct application non-entry in european phase |
Ref document number: 21881564 Country of ref document: EP Kind code of ref document: A1 |