CN112007637B - Bimetallic alloy-halloysite composite catalyst and preparation method and application thereof - Google Patents
Bimetallic alloy-halloysite composite catalyst and preparation method and application thereof Download PDFInfo
- Publication number
- CN112007637B CN112007637B CN202010753808.2A CN202010753808A CN112007637B CN 112007637 B CN112007637 B CN 112007637B CN 202010753808 A CN202010753808 A CN 202010753808A CN 112007637 B CN112007637 B CN 112007637B
- Authority
- CN
- China
- Prior art keywords
- halloysite
- precursor solution
- catalyst
- bimetallic
- fdca
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229910052621 halloysite Inorganic materials 0.000 title claims abstract description 65
- 239000003054 catalyst Substances 0.000 title claims abstract description 63
- 239000002131 composite material Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 claims abstract description 42
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 31
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 claims abstract description 30
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 claims abstract description 28
- 230000003197 catalytic effect Effects 0.000 claims abstract description 27
- 239000010931 gold Substances 0.000 claims abstract description 26
- 239000002243 precursor Substances 0.000 claims abstract description 21
- 230000003647 oxidation Effects 0.000 claims abstract description 18
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 18
- CHTHALBTIRVDBM-UHFFFAOYSA-N furan-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)O1 CHTHALBTIRVDBM-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000011259 mixed solution Substances 0.000 claims abstract description 13
- 229910052737 gold Inorganic materials 0.000 claims abstract description 12
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 12
- 238000011065 in-situ storage Methods 0.000 claims abstract description 6
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000725 suspension Substances 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- 239000011591 potassium Substances 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 6
- 238000006722 reduction reaction Methods 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 3
- 229960005070 ascorbic acid Drugs 0.000 claims description 3
- 235000010323 ascorbic acid Nutrition 0.000 claims description 3
- 239000011668 ascorbic acid Substances 0.000 claims description 3
- 229940074391 gallic acid Drugs 0.000 claims description 3
- 235000004515 gallic acid Nutrition 0.000 claims description 3
- 239000012279 sodium borohydride Substances 0.000 claims description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 abstract description 7
- 239000000956 alloy Substances 0.000 abstract description 7
- 239000002105 nanoparticle Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 2
- 238000007598 dipping method Methods 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- 238000004064 recycling Methods 0.000 abstract 1
- 229910018949 PtAu Inorganic materials 0.000 description 19
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 9
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 8
- 238000006555 catalytic reaction Methods 0.000 description 6
- 238000009210 therapy by ultrasound Methods 0.000 description 6
- 238000011068 loading method Methods 0.000 description 5
- 229910052763 palladium Inorganic materials 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 239000000969 carrier Substances 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000007873 sieving Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 229910001701 hydrotalcite Inorganic materials 0.000 description 2
- 229960001545 hydrotalcite Drugs 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 230000010718 Oxidation Activity Effects 0.000 description 1
- -1 amino organosilane Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/52—Gold
-
- B01J35/394—
-
- B01J35/60—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention discloses a bimetallic alloy-halloysite composite catalyst and a preparation method and application thereof. The method comprises the steps of dipping modified tubular halloysite into a precursor mixed solution of platinum and gold, and preparing a catalyst of bimetallic alloy nanoparticles, wherein platinum and gold are uniformly loaded inside and outside a halloysite tube by an in-situ reduction method; the bimetallic alloy nanoparticles loaded by the catalyst show high dispersibility and excellent alloy effect, can efficiently catalyze and oxidize 5-Hydroxymethylfurfural (HMF) into 2, 5-furandicarboxylic acid (FDCA), and the yield of the FDCA is as high as more than 95%; meanwhile, the catalyst takes the cheap and stable tubular halloysite as a carrier, so that the catalyst is favorable for recycling and reusing, and the cost is reduced; in addition, the preparation method of the catalyst has the advantages of simple process, mild conditions and the like, and has wide application prospect in the field of preparing FDCA by catalytic oxidation of HMF.
Description
Technical Field
The invention belongs to the technical field of synthesis of organic chemical products, and particularly relates to a bimetallic alloy-halloysite composite catalyst, and a preparation method and application thereof.
Background
With the continuous decrease of non-renewable fossil energy such as coal, petroleum, natural gas and the like and the increasing demand of the society for fossil energy, the search for alternative energy is urgent. The biomass energy is considered as an alternative energy with huge potential due to the characteristics of wide sources, abundant reserves, renewability, low price and the like. 5-Hydroxymethylfurfural (HMF) is a biomass-derived carbohydrate and can be converted into a variety of high value-added chemicals and fuels, among others. Of these, catalytic oxidation of HMF to 2, 5-furandicarboxylic acid (FDCA) is of great interest. FDCA is an important organic synthetic intermediate, and was listed as one of the 12 most potential bio-based platform compounds by the U.S. department of energy in 2004. In particular, FDCA is used as an ideal substitute for terephthalic acid to synthesize biodegradable, high-performance, inexpensive, environmentally friendly, sustainably-produced bio-based plastics, etc., because of its structural similarity to terephthalic acid. Furthermore, the market demand for FDCA is increasing due to the development of new uses for more FDCA in recent years.
In view of the potential application value and requirement of FDCA, the preparation of FDCA by catalytic oxidation of HMF becomes a research hotspot. At present, the catalysts for preparing FDCA by catalytic oxidation of HMF are mainly supported metal catalysts such as Pt, Au, Pd, Ru and the like, but the metal catalysts have the problems of low yield, poor stability and the like of FDCA. In addition, the carrier of the catalyst mainly comprises carbon materials, metal oxides, Hydrotalcite (HT) compounds and the like; however, most of these carriers need to be synthesized, and the process is complex and expensive, which is not suitable for large-scale production and industrial application. The carbon material and the metal oxide have low dispersity and low specific surface area, so that the catalytic activity and the FDCA yield of the catalyst are influenced; HT and the like are easy to generate Mg in the catalytic reaction process2+Leaching reduces the stability of the catalyst. In addition, most studies have adopted a method of synthesizing nanoparticles or carriers and then loading the nanoparticles or carriers to prepare catalysts, and meanwhile, a dispersant or a stabilizer needs to be added, so that the preparation process is complicated, and the cost is increased. Therefore, in view of the problems of low yield and poor stability of FDCA in the existing catalysts and the influence of the carrier on the performance and cost of the catalyst, a new carrier material is urgently needed to be found, and a supported metal catalyst with high catalytic activity, high yield and good stability of FDCA and low cost is prepared by a simple method.
Halloysite is a natural nano mineral, has a unique hollow tubular structure, and is high in specific surface area and good in stability. In addition, the halloysite has the characteristics of abundant reserves, low price, easy dispersion and the like. However, at present, no report on the use of halloysite-supported metal composite catalysts for preparing FDCA by catalytic oxidation of HMF is available. In addition, Pt and Au have high catalytic activity and are widely used for preparing FDCA by catalytic oxidation of HMF; compared with single metal, the bimetallic catalyst has higher catalytic activity, product yield and stability, but the research on preparing FDCA by catalytic oxidation of HMF by Pt and Au bimetallic catalysts is not available at present.
The Chinese patent of invention for the preparation of 2, 5-furandicarboxylic acid (publication No. CN105026383A) discloses a method for preparing FDCA by catalytic oxidation of HMF with a homogeneous metal salt catalyst, which requires high reaction temperature and pressure, but the yield of FDCA is still low, and the catalyst is not easy to recover. Chinese patent of invention monatomic palladium catalyst and preparation method thereof and method for preparing 2,5-FDCA by catalytic oxidation of HMF (publication number: CN 109046349A) discloses a catalyst with monatomic palladium supported by manganese dioxide as a carrier, and the catalyst is used for preparing 2,5-FDCA by catalytic oxidation of 5-HMF. The preparation of the catalyst adopts a hydrothermal method to synthesize the manganese dioxide carrier and the palladium particles at the same time, but the low dispersibility of the manganese dioxide causes part of the palladium particles to be coated by the manganese dioxide, which is not beneficial to exposing more metal surface catalytic active centers. The Chinese invention patent "catalyst for preparing 2, 5-furandicarboxylic acid and method for preparing 2, 5-furandicarboxylic acid by using the catalyst" (publication number: CN108712931A) discloses a method for preparing 2,5-FDCA by using spinel type oxide carrier supported noble metal catalyst and by using 5-HMF catalytic oxidation, but the preparation process of the catalyst is complex.
Disclosure of Invention
The invention aims to provide a bimetallic alloy-halloysite composite catalyst, and a preparation method and application thereof, aiming at the defects of preparation and use of a supported metal catalyst for preparing FDCA by catalytic oxidation of HMF in the prior art.
The preparation method of the bimetallic alloy-halloysite composite catalyst comprises the following steps:
a. mixing aminoorganosilane and organic solvent in a volume ratio of 1: 5-100 to obtain a mixed solution, mixing 1g of halloysite: adding halloysite into the mixed solution according to the proportion of 10-50mL of the mixed solution, and performing ultrasonic dispersion to obtain a halloysite suspension;
b. stirring the halloysite suspension at 80-120 ℃, carrying out reflux reaction for 12-24h, carrying out centrifugal separation, retaining solids, drying at 50-150 ℃ for 4-12h, and grinding to obtain modified halloysite;
c. modified halloysite at 1 g: adding the modified halloysite into water according to the proportion of 41-120mL of water, performing ultrasonic dispersion, adding a Pt precursor solution and an Au precursor solution, and stirring for 12-24h to obtain a suspension of the bimetallic ion-halloysite compound;
d. adding a reducing agent: the mass ratio of the total metal atoms of Pt and Au in the suspension of the bimetal ion-halloysite composite is 10-280: 1, adding a reducing agent into the suspension of the bimetallic ion-halloysite compound, carrying out in-situ reduction reaction for 1-3h, carrying out centrifugal separation, retaining the solid, drying at 50-150 ℃ for 4-12h, and grinding to obtain the bimetallic alloy-halloysite composite catalyst.
The amino organosilane in the step a is 3-aminopropyl triethoxysilane or 3-aminopropyl trimethoxysilane, and the organic solvent in the step a is ethanol or toluene.
The ultrasonic dispersion of the steps a and c is 100W ultrasonic for 0.5-2 h.
The precursor solution of Pt in the step c is a chloroplatinic acid, sodium chloroplatinate or potassium chloroplatinate aqueous solution with the concentration of 1-10mg/mL, and the precursor solution of Au in the step c is a chloroauric acid, sodium chloroaurate or potassium chloroaurate aqueous solution with the concentration of 1-10 mg/mL.
The mass ratio of the platinum to the gold atom substances in the Pt precursor solution and the Au precursor solution in the step c is 1: 0.25-4, and taking the total metal mass of Pt and Au in the Pt precursor solution and the Au precursor solution as follows: the mass of the modified halloysite is 0.3-2.7: adding Pt precursor solution and Au precursor solution according to the proportion of 100.
The reducing agent in the step d is sodium borohydride, ascorbic acid or gallic acid.
The invention also provides the bimetallic alloy-halloysite composite catalyst prepared by the preparation method.
The invention also provides application of the bimetallic alloy-halloysite composite catalyst in preparation of 2, 5-furandicarboxylic acid (FDCA) by catalytic oxidation of 5-Hydroxymethylfurfural (HMF).
Experiments prove that the bimetallic alloy-halloysite catalyst provided by the invention has high catalytic activity and FDCA yield (up to more than 95%) in the aspect of preparing FDCA by catalytic oxidation of HMF, and has good stability.
Compared with the prior art, the invention has the following advantages:
(1) the catalyst of the invention takes natural halloysite nano-minerals as carriers, and improves the loading amount and the dispersion degree of metal nano-particles by utilizing the unique tubular structure and surface property adjustability (such as surface amino modification). In addition, the prepared PtAu bimetallic alloy-halloysite composite catalyst can obtain higher stability due to the low-cost and stable halloysite, and the catalyst is easy to recover and reuse, so that the cost is reduced.
(2) The catalyst takes PtAu bimetal as an active component, and combines the characteristics of high HMF catalytic oxidation activity of Pt and Au, so that bimetal particles show strong alloy effect; meanwhile, the alloy particles have high dispersity and small particle size, more metal catalytic active centers can be exposed, and the catalytic activity, the FDCA yield and the stability of the catalyst can be improved.
(3) The catalyst has mild catalytic reaction system conditions, and the conversion rate of the raw material HMF is high (the conversion rate is 100%); the yield of the target product FDCA is high (the yield is as high as more than 95 percent).
(4) The preparation method and the application process of the catalyst have the characteristics of simplicity, environmental protection, economy, high efficiency and the like, and the obtained product FDCA has high industrial application value, meets the requirement of green chemistry and belongs to a green chemical process for sustainable development.
Drawings
Fig. 1 is an X-ray diffraction pattern of the PtAu bimetal alloy-halloysite composite catalyst prepared in example 1 of the present invention.
Fig. 2 is a transmission electron microscope image of the PtAu bimetal alloy-halloysite composite catalyst prepared in example 2 of the present invention.
Fig. 3 is a graph of HMF conversion and FDCA yield over time for the catalytic reaction of the PtAu bimetallic alloy-halloysite composite catalyst prepared in example 3 of the present invention.
Detailed Description
The following examples are further illustrative of the present invention and are not intended to be limiting thereof.
Example 1
(1) Uniformly mixing 40mL of 3-aminopropyltrimethoxysilane and 360mL of ethanol to obtain a mixed solution, adding 40g of halloysite into the mixed solution, and carrying out 100W ultrasonic treatment for 2 hours to obtain a uniform halloysite suspension;
(2) stirring the halloysite suspension obtained in the step (1) at 80 ℃, carrying out reflux reaction for 24h, then centrifuging at 4000rpm for 10min for separation, retaining solids, then drying at 50 ℃ for 12h, manually grinding and sieving by a 100-mesh sieve to obtain modified halloysite;
(3) adding 20g of the modified halloysite obtained in the step (2) into 2000mL of water, performing 100W ultrasonic treatment for 2h to uniformly disperse the modified halloysite, adding 242mL of 10mg/mL sodium chloroplatinate aqueous solution and 43mL of 10mg/mL sodium chloroaurate aqueous solution, and stirring at room temperature for 24h to obtain a suspension of the bimetallic ion-halloysite compound;
(4) and (3) finally adding 10g of gallic acid into the suspension of the bimetallic ion-halloysite compound obtained in the step (3), carrying out in-situ reduction reaction for 2h, centrifuging at 4000rpm for 10min for separation, retaining the solid, drying at 50 ℃ for 12h, manually grinding and sieving by a 100-mesh sieve to obtain a product with the metal loading of about 5.0 wt%, wherein the Pt: the Au atomic ratio is 4: 1 PtAu bimetallic alloy-halloysite composite catalyst.
The phase analysis of the PtAu bimetal alloy-halloysite composite catalyst prepared in this example was performed by X-ray diffraction (XRD). The XRD pattern (fig. 1) shows that characteristic diffraction between Au (111) and Pt (111) occurs at 38.4 °, assigned to PtAu (111); the characteristic diffraction at 45.1 ° is between Au (200) and Pt (200), assigned to PtAu (200). The above results indicate that the homogeneous PtAu bimetal alloy is formed in the PtAu bimetal alloy-halloysite composite catalyst prepared in this example.
The batch catalysis experiment is adopted to test the catalytic performance of the PtAu bimetallic alloy-halloysite composite catalyst prepared in the embodiment for preparing FDCA by HFM oxidation. The result shows that the reaction is carried out for 8 hours at the temperature of 110 ℃, the conversion rate of the reactant HMF reaches 100 percent, and the yield of the target product FDCA is 96 percent.
Example 2
(1) Uniformly mixing 100mL of 3-aminopropyltriethoxysilane and 500mL of ethanol to obtain a mixed solution, adding 12g of halloysite into the mixed solution, and performing 100W ultrasonic treatment for 0.5h to obtain a uniform halloysite suspension;
(2) stirring the halloysite suspension obtained in the step (1) at 100 ℃, carrying out reflux reaction for 18h, centrifuging at 4000rpm for 10min for separation, retaining solids, drying at 150 ℃ for 4h, manually grinding, and screening by using a 100-mesh screen to obtain modified halloysite;
(3) adding 10g of the modified halloysite obtained in the step (2) into 500mL of water, performing 100W ultrasonic treatment for 0.5h to uniformly disperse the modified halloysite, adding 26mL of 5mg/mL chloroplatinic acid aqueous solution and 26mL of 5mg/mL chloroauric acid aqueous solution, and stirring at room temperature for 12h to obtain a suspension of the bimetallic ion-halloysite compound;
(4) and (3) finally adding 6g of sodium borohydride into the suspension of the bimetallic ion-halloysite compound obtained in the step (3), carrying out in-situ reduction reaction for 1h, centrifuging at 4000rpm for 10min for separation, retaining the solid, drying at 150 ℃ for 4h, manually grinding and sieving by a 100-mesh sieve to obtain a product with metal loading of about 2.5 wt%, wherein the Pt: the Au atomic ratio is 1: 1 PtAu bimetallic alloy-halloysite composite catalyst.
The structure and morphology of the PtAu bimetallic alloy-halloysite composite catalyst prepared in the embodiment are observed through a transmission electron microscope, and the PtAu alloy nanoparticles are uniformly loaded inside and outside the halloysite nanotube and have good dispersibility (fig. 2).
The batch catalysis experiment is adopted to test the catalytic performance of the PtAu bimetallic alloy-halloysite composite catalyst prepared by the embodiment in preparing FDCA by HMF oxidation. The result shows that the reaction is carried out for 7 hours at the temperature of 95 ℃, the conversion rate of the reactant HMF is 100 percent, and the yield of the target product FDCA is 98 percent.
Example 3
(1) Uniformly mixing 10mL of 3-aminopropyltriethoxysilane and 1000mL of toluene to obtain a mixed solution, adding 25g of halloysite into the mixed solution, and performing 100W ultrasonic treatment for 2 hours to obtain a uniform halloysite suspension;
(2) stirring the halloysite suspension obtained in the step (1) at 120 ℃, carrying out reflux reaction for 12h, centrifuging at 4000rpm for 10min for separation, retaining solids, drying at 100 ℃ for 10h, manually grinding, and screening by using a 100-mesh screen to obtain modified halloysite;
(3) adding 15g of the modified halloysite obtained in the step (2) into 3000mL of water, performing 100W ultrasonic treatment for 2h to uniformly disperse the modified halloysite, adding 38mL of 1mg/mL potassium chloroplatinate aqueous solution and 116mL of 1mg/mL potassium chloroaurate aqueous solution, and stirring at room temperature for 18h to obtain a suspension of the bimetallic ion-halloysite compound;
(4) and (3) finally adding 7g of ascorbic acid into the suspension of the bimetallic ion-halloysite compound obtained in the step (3), carrying out in-situ reduction reaction for 3h, centrifuging at 4000rpm for 10min, separating, retaining the solid, drying at 100 ℃ for 10h, manually grinding and sieving by a 100-mesh sieve to obtain a product with the metal loading of about 0.5 wt%, wherein the weight ratio of Pt: the Au atomic ratio is 1: 4 PtAu bimetallic alloy-halloysite composite catalyst.
The batch catalysis experiment is adopted to test the catalytic performance of the PtAu bimetallic alloy-halloysite composite catalyst prepared by the embodiment in preparing FDCA by HMF oxidation. Fig. 3 is a graph showing the conversion of HMF catalyzed by the PtAu bimetal alloy-halloysite composite catalyst prepared in this example and the FDCA yield over time (when the temperature is increased to the target temperature of 100 ℃), wherein HMF is completely converted when T is 0 (i.e., the conversion of HMF is 100%) and the FDCA yield is 54%; after the reaction is carried out for 4 hours at the temperature of 100 ℃, the yield of the target product FDCA is 98 percent; with the reaction time increasing to 5h, the yield of FDCA reaches more than 99%.
Claims (8)
1. A preparation method of a bimetallic alloy-halloysite composite catalyst is characterized by comprising the following steps:
a. mixing aminoorganosilane and organic solvent in a volume ratio of 1: 5-100 to obtain a mixed solution, mixing 1g of halloysite: adding halloysite into the mixed solution according to the proportion of 10-50mL of the mixed solution, and performing ultrasonic dispersion to obtain a halloysite suspension;
b. stirring the halloysite suspension at 80-120 ℃, carrying out reflux reaction for 12-24h, carrying out centrifugal separation, retaining solids, drying at 50-150 ℃ for 4-12h, and grinding to obtain modified halloysite;
c. modified halloysite at 1 g: adding the modified halloysite into water according to the proportion of 41-120mL of water, performing ultrasonic dispersion, adding a Pt precursor solution and an Au precursor solution, and stirring for 12-24h to obtain a suspension of the bimetallic ion-halloysite compound;
d. adding a reducing agent: the mass ratio of the total metal atoms of Pt and Au in the suspension of the bimetal ion-halloysite composite is 10-280: 1, adding a reducing agent into the suspension of the bimetallic ion-halloysite compound, carrying out in-situ reduction reaction for 1-3h, carrying out centrifugal separation, retaining the solid, drying at 50-150 ℃ for 4-12h, and grinding to obtain the bimetallic alloy-halloysite composite catalyst.
2. The method according to claim 1, wherein the aminoorganosilane of step a is 3-aminopropyltriethoxysilane or 3-aminopropyltrimethoxysilane, and the organic solvent of step a is ethanol or toluene.
3. The method according to claim 1, wherein the ultrasonic dispersion of steps a and c is 100W ultrasonic for 0.5-2 h.
4. The method according to claim 1, wherein the precursor solution of Pt of step c is an aqueous solution of chloroplatinic acid, sodium chloroplatinate, or potassium chloroplatinate at a concentration of 1-10mg/mL, and the precursor solution of Au of step c is an aqueous solution of chloroauric acid, sodium chloroplatinate, or potassium chloroplatinate at a concentration of 1-10 mg/mL.
5. The method according to claim 1, wherein the ratio of the platinum to gold atomic species in the Pt precursor solution and the Au precursor solution in step c is 1: 0.25-4, and taking the total metal mass of Pt and Au in the Pt precursor solution and the Au precursor solution as follows: the mass of the modified halloysite is 0.3-2.7: adding Pt precursor solution and Au precursor solution according to the proportion of 100.
6. The method according to claim 1, wherein the reducing agent in step d is sodium borohydride, ascorbic acid or gallic acid.
7. The bimetallic alloy-halloysite composite catalyst prepared by the preparation method according to any one of claims 1 to 6.
8. The use of the bimetallic alloy-halloysite composite catalyst of claim 7 in the catalytic oxidation of 5-hydroxymethylfurfural to 2, 5-furandicarboxylic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010753808.2A CN112007637B (en) | 2020-07-30 | 2020-07-30 | Bimetallic alloy-halloysite composite catalyst and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010753808.2A CN112007637B (en) | 2020-07-30 | 2020-07-30 | Bimetallic alloy-halloysite composite catalyst and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112007637A CN112007637A (en) | 2020-12-01 |
| CN112007637B true CN112007637B (en) | 2021-10-15 |
Family
ID=73498870
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010753808.2A Active CN112007637B (en) | 2020-07-30 | 2020-07-30 | Bimetallic alloy-halloysite composite catalyst and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112007637B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114768789A (en) * | 2022-05-25 | 2022-07-22 | 浙江师范大学 | Gold-based bimetallic catalyst and preparation method and application thereof |
| CN115582121B (en) * | 2022-10-26 | 2023-09-26 | 江苏大学 | Preparation method and application of porous carbon coated gold-palladium alloy rod-shaped nano reactor catalyst |
| CN117138837A (en) * | 2023-08-30 | 2023-12-01 | 淮安中顺环保科技有限公司 | Modified halloysite composite material, halloysite-based three-phase interface catalytic membrane, and preparation methods and applications thereof |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102583413B (en) * | 2012-02-17 | 2013-08-14 | 中国科学院广州地球化学研究所 | Method for preparing aluminosilicate nanotube by using kaolinite raw material |
| CN103521221B (en) * | 2013-10-18 | 2016-04-06 | 大连理工大学 | A kind of load type gold-platinum bimetallic alloy Catalysts and its preparation method, application |
| KR102227904B1 (en) * | 2016-10-25 | 2021-03-12 | 제이에프이미네라르 가부시키가이샤 | Surface-modified haloysite, method for producing surface-modified halosite, and catalytic reaction |
| CN106890659A (en) * | 2017-01-10 | 2017-06-27 | 北京化工大学 | A kind of application of the 5 hydroxymethylfurfural oxidation reactions of preparation and its catalysis of high-dispersion loading type nanometer gold-palladium bimetallic catalyst |
| CN106925262B (en) * | 2017-04-06 | 2020-10-30 | 中国科学院山西煤炭化学研究所 | Catalyst for preparing 2, 5-furandicarboxylic acid by photocatalysis, preparation method and application thereof |
| CN108525697A (en) * | 2018-04-11 | 2018-09-14 | 北京化工大学 | A kind of alkalinity high-dispersion loading type Pt base nano-catalysts and its preparation and application |
-
2020
- 2020-07-30 CN CN202010753808.2A patent/CN112007637B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN112007637A (en) | 2020-12-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112007637B (en) | Bimetallic alloy-halloysite composite catalyst and preparation method and application thereof | |
| Fang et al. | Metal organic frameworks for biomass conversion | |
| CN108097316B (en) | Preparation method of MOFs nano material loaded with nano metal particles | |
| CN112871198B (en) | Catalyst for synthesizing formic acid by carbon dioxide hydrogenation, preparation method and application thereof | |
| CN109603819B (en) | Graphene-loaded PdRu bimetallic catalyst and preparation method and application thereof | |
| CN110433853B (en) | Modified mesoporous molecular sieve supported platinum-based catalyst and preparation method thereof | |
| CN108607603B (en) | CO (carbon monoxide)2Synthetic acetylenic acid catalyst, preparation and application thereof | |
| CN108654693A (en) | A kind of hydrophobic palladium/metal-organic framework material and preparation method thereof and the application for synthesizing 2,5- dimethyl furans | |
| CN107670694B (en) | Metal supported catalyst and preparation method and application thereof | |
| CN110368928B (en) | Catalyst for synthesizing benzaldehyde by oxidizing benzyl alcohol and preparation method and application thereof | |
| CN113058617B (en) | Photocatalyst and preparation method and application thereof | |
| CN109499596A (en) | A kind of metal-nitrogen-phosphorus doping porous carbon bifunctional electrocatalyst and preparation method | |
| CN112755996A (en) | Catalyst for synthesizing methanol by carbon dioxide hydrogenation, preparation method and application | |
| CN109384750B (en) | Method for preparing 2,5-dimethylfuran by catalytic hydrogenation of 5-hydroxymethylfurfural | |
| CN109894140A (en) | A kind of preparation method and its catalytic applications of solid base hydrotalcite supported precious metal catalyst | |
| CN110935481B (en) | Catalyst for selective hydrogenolysis of aromatic ether bond, preparation and application thereof | |
| CN114160169B (en) | Preparation method and application of covalent organic framework material encapsulated molybdenum-sulfur cluster | |
| CN111187238B (en) | Synthetic method of 2, 5-furandicarboxylic acid | |
| CN110721671B (en) | Amorphous SiO2-Al2O3Supported metal type catalyst and preparation method and application thereof | |
| CN111203279A (en) | Sandwich nano-material ZIF-8@ Au25@ ZIF-67 and preparation method and application thereof | |
| CN110898849B (en) | CO (carbon monoxide) treatment method 2 Process for conversion to a multi-carbon alcohol and multi-carbon hydrocarbon and catalyst therefor | |
| CN113909487A (en) | Curled PtPd nano dendrite and preparation method and application thereof | |
| CN113292519A (en) | Magnetic gold-cobalt composite catalyst and preparation method and application thereof | |
| CN113304760A (en) | High-dispersion platinum-based catalyst and preparation method and application thereof | |
| CN112221536B (en) | Titanium-silicon molecular sieve encapsulated nano copper catalyst and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |