CN114950410B - Synthetic method of zirconium-manganese composite material - Google Patents
Synthetic method of zirconium-manganese composite material Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 56
- DSGIMNDXYTYOBX-UHFFFAOYSA-N manganese zirconium Chemical compound [Mn].[Zr] DSGIMNDXYTYOBX-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 238000010189 synthetic method Methods 0.000 title description 3
- 239000013207 UiO-66 Substances 0.000 claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 claims abstract description 22
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000001035 drying Methods 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000008367 deionised water Substances 0.000 claims abstract description 11
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 11
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 8
- 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 6
- 238000000926 separation method Methods 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims abstract description 4
- 238000001308 synthesis method Methods 0.000 claims abstract description 3
- 230000003197 catalytic effect Effects 0.000 claims description 15
- 239000011572 manganese Substances 0.000 claims description 10
- 230000003647 oxidation Effects 0.000 claims description 10
- 238000007254 oxidation reaction Methods 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 8
- -1 polytetrafluoroethylene Polymers 0.000 claims description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 8
- 238000009210 therapy by ultrasound Methods 0.000 claims description 7
- 238000003760 magnetic stirring Methods 0.000 claims description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- 239000010935 stainless steel Substances 0.000 claims description 5
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 5
- 150000002696 manganese Chemical class 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 238000009777 vacuum freeze-drying Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 17
- 238000002360 preparation method Methods 0.000 abstract description 11
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 8
- 239000002086 nanomaterial Substances 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 13
- 239000000463 material Substances 0.000 description 10
- 238000002156 mixing Methods 0.000 description 9
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 7
- 239000012621 metal-organic framework Substances 0.000 description 7
- 239000002243 precursor Substances 0.000 description 7
- 239000012295 chemical reaction liquid Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 6
- 239000006228 supernatant Substances 0.000 description 6
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 229910052726 zirconium Inorganic materials 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 238000000975 co-precipitation Methods 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000004811 liquid chromatography Methods 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000002356 single layer Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910021642 ultra pure water Inorganic materials 0.000 description 3
- 239000012498 ultrapure water Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 238000000089 atomic force micrograph Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 238000010952 in-situ formation Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000008093 supporting effect Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
-
- B01J35/40—
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- 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 belongs to the technical field of nano material preparation, and discloses a synthesis method of a zirconium-manganese composite material, which utilizes a hydrothermal method to prepare ultrathin two-dimensional sheet delta-MnO formed on the surface of UiO-66 2 The method comprises the steps of carrying out a first treatment on the surface of the Potassium permanganate and UiO-66 are used as raw materials, deionized water is used as a solvent, constant temperature reaction is carried out under the condition of specific temperature, and the uniformly dispersed delta-MnO with ultrathin two-dimensional flaky surface growth is prepared through centrifugal separation, sample washing and drying 2 Zirconium-manganese composite of (a). The zirconium-manganese composite material prepared by the invention can efficiently catalyze and oxidize 5-Hydroxymethylfurfural (HMF) to generate 2, 5-furandicarboxylic acid (FDCA). The preparation method has the advantages of simple preparation process, short period and low cost, can realize large-scale industrial production, and has good economic and environmental benefits.
Description
Technical Field
The invention belongs to the technical field of nano material preparation, and particularly relates to a synthesis method and application of a zirconium-manganese composite material.
Background
Ultra-thin two-dimensional (2D) nanomaterials have a thickness of only one or a few atoms (typically 5 nm). Shows unusual mechanical, optical and electronic properties, and is an ideal low-dimensional material for basic research and a basic component for design and assembly. However, achieving good dispersibility of two-dimensional (2D) nanomaterials to avoid agglomeration thereof remains a great challenge, which also limits the practical application of two-dimensional (2D) nanomaterials in the catalytic field.
MOFs are materials with well-defined active sites and functional structures that have shown good catalytic oxidation properties, but low permeability and stability limit their development.
MnO is commonly used at present 2 Catalytic material has 0D MnO 2 、1D MnO 2 、2D MnO 2 Wherein 0D, 1D MnO 2 Fewer active sites are exposed, catalytically opposite to 2D MnO 2 The performance is poor. Preparation of two-dimensional MnO 2 Common methods of (a) are coprecipitation method, hydrothermal method, sol-gel method and the like-, wherein the coprecipitation method influences the uniformity of the prepared catalyst due to uncontrollable process caused by rapid reaction of the coprecipitation method, and the prepared single-layer MnO 2 The thickness of the sheet is typically between 3-7 a nm a; compared with the coprecipitation method, the sol-gel method has more uniform sample but longer production period, troublesome process flow and limited mass production, and the prepared single-layer MnO 2 The thickness of the sheet is typically between 0.5 and 5 a nm a; the invention adopts a hydrothermal synthesis method which is relatively convenient and has uniform growth. However, conventional hydrothermal methods generally employ direct hydrothermal KMnO 4 The two-dimensional MnO thus prepared 2 Poor dispersibility and easy agglomeration, and the prepared single-layer MnO 2 The thickness of the sheet is typically between 2-6 a nm a.
Therefore, in order to design a highly efficient thermal catalyst, the present invention uses two-dimensional MnO 2 It may be a suitable strategy to co-construct a catalyst with a three-dimensional self-supporting structure and a two-dimensional catalytic surface with the nanoplatelets and the MOF matrix.
Based on the above, the invention provides a preparation method of a zirconium-manganese composite material, which uses a classical MOF material UiO-66 as a matrix and uses a certain method to make KMnO 4 React with UiO-66, during which KMnO 4 As an oxidant, the organic functional group on UiO-66 is used as a reducing agent to perform oxidation-reduction reaction, delta-MnO 2 In-situ growth to the surface of UiO-66, and the growth time is controlled to adjust MnO 2 The specific surface area of the zirconium-manganese composite material is increased to increase the catalytic active site of the material, and the zirconium-manganese composite material with regular morphology is designed and prepared.
Disclosure of Invention
The invention aims to provide a delta-MnO with an ultrathin two-dimensional lamellar surface 2 Zirconium-manganese composite material and a preparation method thereof.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a synthetic method of a zirconium-manganese composite material comprises the following raw materials: potassium permanganate (KMnO) 4 ）、UiO-66（C 48 H 28 O 32 Zr 6 ）。
A method for synthesizing a zirconium-manganese composite material comprises the following steps: mixing and dissolving potassium permanganate in deionized water to prepare uniformly dispersed reaction precursor liquid; then adding UiO-66 into the reaction precursor liquid, carrying out ultrasonic stirring treatment, transferring to a polytetrafluoroethylene lining in a stainless steel autoclave, and carrying out constant-temperature reaction in a drying oven; after the reaction is finished, cooling, centrifugal separation, washing and drying are carried out until the moisture is completely volatilized, so that the black solid zirconium-manganese composite material with uniform powder size and high dispersion is obtained.
The zirconium-manganese composite material with uniform size and high dispersion concretely comprises the following steps:
(1) Adding seven-valent manganese salt into deionized water, and fully mixing and dissolving to prepare uniformly dispersed reaction precursor liquid;
(2) Adding UiO-66 into the reaction precursor liquid, carrying out certain ultrasonic stirring treatment, and then averagely transferring the reaction precursor liquid into a plurality of stainless steel autoclaves with polytetrafluoroethylene liners, and carrying out constant-temperature reaction in a drying oven;
(3) After the reaction is finished, cooling, centrifugal separation, washing and drying are carried out until the moisture is completely volatilized, so that the black solid powdery two-dimensional zirconium-manganese composite material is obtained.
Further, the heptavalent manganese salt in the step (1) is nontoxic potassium permanganate (KMnO) 4 ）；
Further, uiO-66 (C) in step (2) 48 H 28 O 32 Zr 6 ) KMnO 4 The mol ratio of the medium element Zr to Mn is 1:1-1:4, and the dosage of deionized water is 250 mL.
Further, the mixing and dissolving in the step (2) specifically comprises the following steps: ultrasonic dispersion and magnetic stirring, wherein the ultrasonic dispersion time is 10-30 min; the magnetic stirring speed is 500 rpm; the magnetic stirring time is 20-30 min.
Further, the specification of the polytetrafluoroethylene lining in the step (2) is 25 mL.
Further, the constant temperature reaction in the step (2) specifically comprises the following steps: reacting at 180 ℃ for 30 min-4 h.
Further, the cooling in the step (3) specifically includes: cooling the mixture to room temperature along with the furnace.
Further, the washing solvent in the step (3) is deionized water, and the washing times are 3 times.
Further, the drying mode in the step (3) is vacuum freeze drying at-53 ℃ and the drying time is 12 h.
The invention has the remarkable advantages that:
(1) The invention synthesizes the zirconium-manganese composite oxide step by using the raw materials which are low in price and easy to obtain and adopting a hydrothermal method which is simple and easy to operate, and the size distribution of the zirconium-manganese composite oxide is 200-500 nm. The preparation process of the invention is economical, simple and efficient, and no surfactant is needed.
(2) The zirconium-manganese composite oxide obtained by the invention not only can keep the basic structure of the matrix MOF, but also can improve the catalytic oxidation performance of the zirconium-manganese composite oxide through the combination with the MOF structure.
(3) The preparation method has the advantages of easy acquisition of equipment and materials, simple process operation, simple process conditions, low cost, safety and high efficiency; the invention provides an ecological environment-friendly material which has good popularization and application values.
(4) The invention forms ultrathin two-dimensional flaky delta-MnO on the surface of UiO-66 by utilizing a hydrothermal method 2 The thickness distribution is between 0.9 and 1.5 and nm; potassium permanganate and UiO-66 are used as raw materials, deionized water is used as a solvent, constant temperature reaction is carried out under the condition of specific temperature, and the uniformly dispersed delta-MnO with ultrathin two-dimensional flaky surface growth is prepared through centrifugal separation, sample washing and drying 2 Zirconium-manganese composite of (2)A material. The zirconium-manganese composite material prepared by the invention can efficiently catalyze and oxidize 5-Hydroxymethylfurfural (HMF) to generate 2, 5-furandicarboxylic acid (FDCA).
(5) UiO-66 is a MOF formed by coordination of Zr with terephthalic acid, wherein terephthalic acid is coordinated with KMnO 4 In-situ formation of layered delta-MnO by redox reaction 2 Lamellar delta-MnO with prolonged reaction time 2 Gradually grow up to finally form delta-MnO with three-dimensional self-supporting structure 2 . UiO-66 provides support to avoid lamellar structure delta-MnO 2 Is not limited, and is not limited. MOF materials are generally unstable in water, and the structure collapses or is destroyed during hydrothermal synthesis, so UiO-66 is more stable and can be used as a stable support structure. Zirconium has acid-base property and certain activation effect on a substrate, but because the zirconium has relatively stable lattice oxygen and lacks certain oxidizing capability, the zirconium is used as a matrix and MnO is used as a matrix 2 And the composition is favorable for the catalytic oxidation of HMF. The manganese oxide has stronger selective oxidation capability, can selectively oxidize HMF into FDCA, has more exposed surfaces and more catalytic active sites, is favorable for quick reaction, avoids aggregation of layered manganese dioxide due to the supporting effect of a three-dimensional matrix, and maintains the high-efficiency activity of the catalyst.
Drawings
FIG. 1 is an X-ray diffraction (XRD) pattern of a Zr: mn=1:1 to 1:4 zirconium manganese composite prepared with a hydrothermal time of 3h in example 1 of the present invention;
FIG. 2 is a microstructure comparison chart of a zirconium manganese composite material prepared by Zr: mn=1:2 and hydrothermal time of 30 min-12 h in example 1, and an EDS energy spectrum of the zirconium manganese composite material prepared by Zr: mn=1:2 and hydrothermal time of 3 h;
FIG. 3 is a microstructure of UiO-66 produced in comparative example 1 of the present invention;
FIG. 4 is a transmission electron microscope image of a zirconium manganese composite prepared by hydrothermal time 3h with Zr: mn=1:2 in example 1 of the present invention;
FIG. 5 is an atomic force microscope image of a Zr: mn=1:2, hydrothermal time 3h composite material according to example 1 of the present invention;
FIG. 6 is a transmission electron microscope image of UiO-66 prepared in comparative example 1 of the present invention;
FIG. 7 is a graph showing the performance of the zirconium manganese composite of example 1 of the present invention for catalyzing HMF at 130℃and 1.5 MPa under 18. 18 h conditions, wherein the zirconium manganese composite is prepared with Mn=1:2 and has a hydrothermal time of 30 min, 3h, and 12 h;
FIG. 8 shows Zr: mn=1:2, zirconium manganese composite prepared by hydrothermal treatment of 3h, uiO-66 prepared by comparative example 1, and UiO-66 and MnO prepared by comparative example 2 in example 1 of the present invention 2 Performance comparison of mechanical hybrid materials;
fig. 9 is a graph showing the cycle performance of the zirconium manganese composite prepared by hydrothermal method 3 and h in example 1 of the present invention, wherein Zr: mn=1:2.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be further described in detail below with reference to the accompanying drawings, i.e., embodiments. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention. In addition, the technical features of the embodiments of the present invention described below may be combined as long as they do not collide with each other.
Example 1
Preparing a zirconium-manganese composite material:
(1) Weighing potassium permanganate (KMnO) of 0.22-0.88 g with electronic balance 4 ) Adding the solution A into 250 mL deionized water, performing ultrasonic dispersion for 10 min, magnetically stirring for 30 min at a stirring speed of 500 rpm to obtain a solution A, and uniformly placing the solution A into a polytetrafluoroethylene lining according to each 14: 14 mL;
(2) Weighing UiO-66 (Zr: mn=1:1-1:4) of 0.02 g by an electronic balance, adding into the polytetrafluoroethylene lining, magnetically stirring for 10 min at a stirring speed of 500 rpm to obtain a uniformly dispersed solution B;
(3) Transferring the polytetrafluoroethylene lining into a stainless steel autoclave, and carrying out constant-temperature reaction at 180 ℃ in a drying oven for 3h (30 min, 1 h, 2 h, 4 h and 12 h), and cooling to room temperature along with the furnace;
(4) Centrifuging the sample by using a centrifugal machine to obtain black solid powder, wherein the rotating speed is 9000 rpm; washing with deionized water for three times;
(5) And (5) obtaining the zirconium-manganese composite material by freeze drying overnight until the moisture is completely volatilized.
FIG. 1 is an X-ray diffraction (XRD) pattern of a Zr/Mn=1:1-1:4 composite zirconium/manganese prepared in example 1 according to the invention with a hydrothermal time of 3h, from which it can be seen that UiO-66 in the composite zirconium/manganese composite synthesized converts to monoclinic phase ZrO as Zr/Mn=1:1-1:4 2 （m-ZrO 2 ) Then is converted into tetragonal ZrO 2 （t-ZrO 2 ) While the Mn existing phase is delta-MnO 2 From the energy spectrum, the three elements Mn, zr and O are uniformly distributed. FIG. 2 is a graph showing the microscopic morphology comparison of a zirconium manganese composite material prepared by Zr: mn=1:2 and hydrothermal time from 30 min to 12 h and an EDS energy spectrum of a zirconium manganese composite material prepared by Zr: mn=1:2 and hydrothermal time of 3h in example 1 of the present invention, from which it can be seen that MnO on the surface of UiO-66 increases from 30 min to 3h with hydrothermal time 2 Gradually from the filaments attached to the surface into a distinct two-dimensional sheet, gradually into a one-dimensional line at 4 h. FIGS. 3 and 6 are a microscopic morphology chart and a transmission electron microscope chart of the UiO-66 prepared in comparative example 1, and it can be seen from the graphs that the prepared UiO-66 has regular and uniform morphology and size distribution of 0.5-2 μm. FIG. 4 is a transmission electron microscope image of a zirconium-manganese composite material prepared by the method in example 1 of the present invention, wherein Zr: mn=1:2 and hydrothermal time is 3. 3h, and it can be seen from the image that the particle size distribution of the hydrothermally synthesized zirconium-manganese composite material is slightly larger than that of the original UiO-66, and is distributed between 0.6 and 2.1 μm, and meanwhile, the particle size distribution of the hydrothermally synthesized zirconium-manganese composite material is in the form of edge sheet MnO 2 Clearly visible. FIG. 5 is an atomic force microscope image of a zirconium manganese composite material prepared by the method of example 1 in which Zr: mn=1:2 and hydrothermal time is 3h, from which it can be seen that the surface is ultra-thin two-dimensional delta-MnO 2 The thickness of the nano-sheet is distributed between 0.9 and 1.5 nm. FIG. 7 is a graph showing comparison of performances of zirconium-manganese composite materials with the hydrothermal time of 30 min, 3h and 12 h for catalyzing HMF, wherein the zirconium-manganese composite materials are prepared in the embodiment 1 of the invention, and the HMF conversion rate of the zirconium-manganese composite materials can reach hundred percent, wherein the yield of FDCA of a sample with the hydrothermal time of 3h is highest and reaches 99.2 percent, and the yield exceeds 62.8 percent of the hydrothermal time of 30 min and 74.2 percent of that of 12 h. The performance of the sample is better than that of the sample heated by water for 30 min, because the sample heated by waterIn the process of prolonging the time from 30 min to 3h, mnO 2 Gradually growing, but when the hydrothermal time is further prolonged to 12 h, lamellar delta-MnO on the surface is formed after 30 min 2 Converted into a linear shape
α-MnO 2 The catalytically active sites are thereby reduced, resulting in a somewhat reduced performance.
Comparative example 1
Preparation of UiO-66:
(1) Weighing 0.0469 g zirconium chloride (AlCl) with an electronic balance 3 ·6H 2 O) and 0.0.0348 g of terephthalic acid (PTA), adding the mixture into 40 ml of DMF, stirring for 30 min, adding 5 mL acetic acid, and stirring for 30 min again to prepare a reaction precursor solution;
(2) Transferring the reaction precursor liquid into a stainless steel autoclave lined with polytetrafluoroethylene, and reacting at a constant temperature of 120 ℃ in a drying oven for 24 h, and cooling to room temperature along with a furnace after the reaction is finished;
(3) Centrifuging the sample by using a centrifugal machine to obtain white solid powder, wherein the rotating speed is 9000 rpm; and washing with DMF and formic acid three times respectively;
(4) UiO-66 of uniform size and high dispersion was obtained by vacuum drying overnight until the moisture was completely volatilized.
Comparative example 2
UiO-66 and MnO 2 Preparation of mechanically mixed samples:
(1) UiO-66 (C) of 0.1. 0.1 g was weighed out by an electronic balance 48 H 28 O 32 Zr 6 ) delta-MnO of 0.062 g 2 Uniformly mixing the components, and mixing the UiO-66 and delta-MnO 2 The mol ratio of the medium element Zr to Mn is 1:2;
(2) Grinding the sample after uniformly mixing the two with a mortar for 20 min, and then sieving with a screen for 3 times.
HMF catalytic oxidation experiments
Application example 1
The zirconium manganese composite obtained in example 1 was used for the catalytic oxidation of 5-Hydroxymethylfurfural (HMF) with the following specific steps:
(1) Placing 10 mL ultrapure water into a liner of a high-pressure reaction kettle, adding HMF 50 mg, adding 50 mg sodium bicarbonate, adding 100 mg zirconium-manganese composite catalyst, and performing ultrasonic treatment;
(2) Introducing oxygen, maintaining the pressure at 1.5 MPa, heating to 130 ℃, and starting timing;
(3) Taking out the reaction liquid after the reaction is carried out for 18 and h, quantifying to a volumetric flask of 10 mL, pouring the reaction liquid into a centrifuge tube of 50 mL, centrifuging, taking supernatant 1 mL, dripping the supernatant into the volumetric flask of 100 and mL, quantifying to 100 mL, taking a proper amount of solution after ultrasonic treatment for five minutes, and placing the solution into a liquid chromatography for testing.
Comparative example 1 was used
The UiO-66 obtained in comparative example 1 was used for the catalytic oxidation of HMF, and the specific procedure was as follows:
(1) Placing 10 mL ultrapure water into a high-pressure reaction kettle liner, adding HMF 50 mg, adding 50 mg sodium bicarbonate, adding 100 mg UiO-66 catalyst, and performing ultrasonic treatment;
(2) Introducing oxygen, maintaining the pressure at 1.5 MPa, heating to 130 ℃, and starting timing;
(3) Taking out the reaction liquid after the reaction is carried out for 18 and h, quantifying to a volumetric flask of 10 mL, pouring the reaction liquid into a centrifuge tube of 50 mL, centrifuging, taking supernatant 1 mL, dripping the supernatant into the volumetric flask of 100 and mL, quantifying to 100 mL, taking a proper amount of solution after ultrasonic treatment for five minutes, and placing the solution into a liquid chromatography for testing.
Comparative example 2 was used
The UiO-66 and MnO obtained in comparative example 2 were mixed 2 The mechanical mixing sample is used for the catalytic oxidation of HMF, and the specific steps are as follows:
(1) Placing 10 mL ultrapure water into a high-pressure reaction kettle liner, adding HMF 50 mg, adding 50 mg sodium bicarbonate, adding 100 mg UiO-66 and MnO 2 Mechanically mixing the catalyst and then carrying out ultrasonic treatment;
(2) Introducing oxygen, maintaining the pressure at 1.5 MPa, heating to 130 ℃, and starting timing;
(3) Taking out the reaction liquid after the reaction is carried out for 18 and h, quantifying to a volumetric flask of 10 mL, pouring the reaction liquid into a centrifuge tube of 50 mL, centrifuging, taking supernatant 1 mL, dripping the supernatant into the volumetric flask of 100 and mL, quantifying to 100 mL, taking a proper amount of solution after ultrasonic treatment for five minutes, and placing the solution into a liquid chromatography for testing.
FIG. 8 shows the zirconium manganese composite obtained in example 1 of the present invention and UiO-66 obtained in comparative example 1 and UiO-66 and MnO obtained in comparative example 2 2 The comparison of the performances of the mechanical mixed samples shows that the zirconium-manganese composite material has optimal catalytic performance, and the FDCA yield reaches 99.2 percent, which exceeds 64.8 percent of mechanical mixing and 3.9 percent of pure UiO-66. The zirconium-manganese composite material can completely catalyze and reduce 100 percent of HMF by 18 h, and the performance of the zirconium-manganese composite material is far better than that of UiO-66 and MnO 2 The samples were mechanically mixed. As can be seen from FIG. 9, the zirconium manganese composite material prepared by the method has 100% conversion rate to HMF, and meanwhile, the FDCA yield reaches 99.2%, and the zirconium manganese composite material has excellent cycle performance, can keep 100% conversion rate to HMF in each cycle, and can keep excellent catalytic oxidation performance to HMF after 4 times of cycle.
It will be readily appreciated by those skilled in the art that the foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention, but any modifications, equivalents and improvements made within the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (6)
1. An application of a zirconium-manganese composite material is characterized in that: the zirconium-manganese composite material is used as a catalyst in the catalytic oxidation of 5-hydroxymethylfurfural to generate 2, 5-furandicarboxylic acid;
the synthesis method of the zirconium-manganese composite material comprises the following steps:
(1) Adding seven-valence manganese salt into deionized water, and fully dissolving to form a solution A;
(2) Adding UiO-66 into the solution A to form a reaction solution B, stirring the reaction solution B at room temperature, and performing ultrasonic treatment;
(3) Transferring the reaction solution B to a polytetrafluoroethylene lining in a stainless steel autoclave, and carrying out constant-temperature reaction in a drying oven;
(4) After the reaction is finished, cooling, centrifugal separation, washing and drying are carried out until the moisture is completely volatilized, thus obtaining the ultrathin two-dimensional flaky delta-MnO with the surface growing 2 Zirconium-manganese composite material of (a);
the heptavalent manganese salt in the step (1) is potassium permanganate KMnO 4 ；
In the step (2), uiO-66 is added according to the mole ratio of Zr to Mn of 1:2;
the constant temperature reaction in the step (3) is specifically as follows: reaction 3h was carried out at a constant temperature of 180 ℃.
2. The use according to claim 1, characterized in that: in the step (1), the dosage of potassium permanganate is 0.002-0.005 mol, and the dosage of deionized water is 250 mL.
3. The use according to claim 1, characterized in that: the dissolving in the step (1) specifically comprises the following steps: ultrasonic dispersion and magnetic stirring, wherein the ultrasonic dispersion time is 10-30 min; the magnetic stirring speed is 500 rpm; the magnetic stirring time is 20-30 min.
4. The use according to claim 1, characterized in that: the cooling in the step (4) is specifically as follows: cooling the mixture to room temperature along with the furnace.
5. The use according to claim 1, characterized in that: the washing solvent in the step (4) is deionized water, and the washing times are 3 times.
6. The use according to claim 1, characterized in that: the drying mode in the step (4) is vacuum freeze drying at-53 ℃ and the drying time is 8-12 h.
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