CN114950410A - Synthesis method of zirconium-manganese composite material - Google Patents
Synthesis method of zirconium-manganese composite material Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 58
- DSGIMNDXYTYOBX-UHFFFAOYSA-N manganese zirconium Chemical compound [Mn].[Zr] DSGIMNDXYTYOBX-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 238000001308 synthesis method Methods 0.000 title claims description 5
- 239000013207 UiO-66 Substances 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 14
- 239000008367 deionised water Substances 0.000 claims abstract description 11
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 11
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 10
- 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
- 239000002904 solvent Substances 0.000 claims abstract description 4
- 239000011572 manganese Substances 0.000 claims description 26
- 230000003197 catalytic effect Effects 0.000 claims description 14
- 230000003647 oxidation Effects 0.000 claims description 11
- 238000007254 oxidation reaction Methods 0.000 claims description 11
- 239000012295 chemical reaction liquid Substances 0.000 claims description 10
- 238000001816 cooling 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
- 238000003756 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
- 150000002696 manganese Chemical class 0.000 claims description 4
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 4
- 238000004108 freeze drying Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 abstract description 11
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 6
- 239000002086 nanomaterial Substances 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 abstract description 2
- 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 11
- 239000007788 liquid Substances 0.000 description 7
- 239000012621 metal-organic framework Substances 0.000 description 7
- 239000002243 precursor Substances 0.000 description 7
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000000975 co-precipitation Methods 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 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 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
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- 238000004811 liquid chromatography Methods 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 239000002356 single layer Substances 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
- 229910052726 zirconium Inorganic materials 0.000 description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000010335 hydrothermal treatment Methods 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
- 238000011065 in-situ storage Methods 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 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
- 238000003917 TEM image Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000000089 atomic force micrograph Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000013329 compounding Methods 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
- 239000013078 crystal Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000724 energy-dispersive X-ray spectrum Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000004570 mortar (masonry) 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
- 239000002245 particle Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004094 surface-active agent Substances 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
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- 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
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- 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
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- 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
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- 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
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Abstract
The invention belongs to the technical field of preparation of nano materials, and discloses a method for synthesizing a zirconium-manganese composite material, which is characterized in that a hydrothermal method is utilized to prepare ultrathin two-dimensional flaky delta-MnO formed on the surface of UiO-66 2 (ii) a Potassium permanganate and UiO-66 are used as raw materials, deionized water is used as a solvent, a constant temperature reaction is carried out under the condition of a specific temperature, and uniformly dispersed delta-MnO with an ultrathin two-dimensional sheet-shaped surface growing is prepared by centrifugal separation, sample washing and drying 2 The zirconium manganese composite material. The zirconium-manganese composite material prepared by the invention can efficiently catalyze and oxidize 5-hydroxymethyl furfural (HMF) to generate 2, 5-furandicarboxylic acid (FDCA). The preparation method has the advantages of simple preparation process, short period, low cost, large-scale industrial production and good economic benefit and environmental benefit.
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). The material shows unusual mechanical, optical and electronic properties, and is an ideal low-dimensional material for basic research and a basic component for designing and assembling. However, achieving good dispersibility of the two-dimensional (2D) nanomaterial to avoid agglomeration is still a great challenge, which also limits the practical application of the two-dimensional (2D) nanomaterial in the field of catalysis.
MOFs are materials with well-defined active sites and functional structures that have shown good catalytic oxidation performance, but their development is limited by low permeability and stability.
MnO is commonly used at present 2 Catalytic material having 0D MnO 2 、1D MnO 2 、2D MnO 2 Wherein 0D, 1D MnO 2 Less exposed active sites, relative to 2D MnO in catalysis 2 The performance is poor. Preparation of two-dimensional MnO 2 Common methods include a coprecipitation method, a hydrothermal method, a 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 is 2 The thickness of the sheet is generally between 3 and 7 nm; the sol-gel method is more uniform than a sample generated by a coprecipitation method, but the production period is generally longer, the process flow is troublesome, the large-scale production is limited, and the prepared single-layer MnO is 2 The thickness of the sheet is generally between 0.5 and 5 nm; therefore, the invention adopts a hydrothermal synthesis method which is relatively convenient and uniform in growth. However, the traditional hydrothermal method generally adopts direct hydrothermal KMnO 4 Two-dimensional MnO thus prepared 2 Poor dispersibility and easy agglomeration, and the prepared single-layer MnO is 2 The thickness of the sheet is typically between 2-6 nm.
Thus, to design a highly efficient thermal catalyst, the present invention uses two-dimensional MnO 2 Nanosheets andit may be a suitable strategy for the MOF matrix to together construct a catalyst with a three-dimensional self-supporting structure and a two-dimensional catalytic surface.
Based on the method, the invention provides a preparation method of a zirconium-manganese composite material, which takes a classical MOF material UiO-66 as a matrix and uses a certain method to ensure that KMnO is subjected to surface modification 4 And UiO-66, in the course of which KMnO 4 As an oxidizing agent, organic functional groups on UiO-66 as a reducing agent, a redox reaction, delta-MnO 2 Growing in situ to UiO-66 surface, controlling growth time to regulate MnO 2 The specific surface area of the zirconium manganese composite material is improved to increase the catalytic active sites of the material, and the zirconium manganese composite material with regular morphology is designed and prepared.
Disclosure of Invention
The invention aims to provide the delta-MnO with the surface growing with ultrathin two-dimensional flakes 2 The zirconium manganese composite material and the preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
a synthesis 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 the 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; and after the reaction is finished, cooling, centrifugally separating, washing and drying until the water is completely volatilized to obtain the black solid powdery zirconium-manganese composite material with uniform size and high dispersion.
The zirconium-manganese composite material with uniform size and high dispersion specifically comprises the following steps:
(1) adding heptavalent manganese salt into deionized water, fully mixing and dissolving to prepare uniformly dispersed reaction precursor liquid;
(2) then adding the UiO-66 into the reaction precursor liquid, carrying out certain ultrasonic stirring treatment, averagely transferring the reaction precursor liquid to a plurality of stainless steel high-pressure kettles with polytetrafluoroethylene linings, and carrying out constant-temperature reaction in a drying oven;
(3) and after the reaction is finished, cooling, centrifugally separating, washing and drying until the water is completely volatilized to obtain the black solid powdery two-dimensional zirconium-manganese composite material.
Further, the heptavalent manganese salt in the step (1) is non-toxic potassium permanganate (KMnO) 4 ）；
Further, UiO-66 (C) in step (2) 48 H 28 O 32 Zr 6 ) And KMnO 4 The molar ratio of the Zr to Mn is 1:1-1:4, and the dosage of the deionized water is 250 mL.
Further, the mixing and dissolving in the step (2) specifically comprises: ultrasonic dispersion and magnetic stirring, wherein the ultrasonic dispersion time is 10-30 min; the magnetic stirring speed is 500 rpm; magnetic stirring time is 20-30 min.
Further, the specification of the polytetrafluoroethylene lining in the step (2) is 25 mL.
Further, the isothermal reaction in the step (2) is specifically as follows: reacting for 30 min-4 h at constant temperature of 180 ℃.
Further, the cooling in the step (3) is specifically as follows: and cooling the mixture along with the furnace to room temperature.
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-53 ℃ freeze drying, and the drying time is 12 h.
The invention has the following remarkable advantages:
(1) the invention synthesizes the zirconium-manganese composite oxide step by using raw materials which are low in price and easy to obtain and a simple and easy-to-operate hydrothermal method, and the size distribution of the zirconium-manganese composite oxide is 200-500 nm. The preparation process is economic, simple, convenient and efficient, and does not need to add any surfactant.
(2) The zirconium manganese composite oxide prepared 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 by compounding with the MOF structure.
(3) The preparation method has the advantages of easily obtained equipment and materials, simple process operation, concise process conditions, low cost, safety and high efficiency; the invention obtains an eco-friendly material, which has good popularization and application values.
(4) The invention utilizes a hydrothermal method to form ultrathin two-dimensional flaky delta-MnO on the surface of UiO-66 2 The thickness is distributed between 0.9 nm and 1.5 nm; potassium permanganate and UiO-66 are used as raw materials, deionized water is used as a solvent, a constant temperature reaction is carried out under the condition of a specific temperature, and uniformly dispersed delta-MnO with an ultrathin two-dimensional sheet-shaped surface growing is prepared by centrifugal separation, sample washing and drying 2 The zirconium manganese composite material. The zirconium-manganese composite material prepared by the invention can efficiently catalyze and oxidize 5-hydroxymethyl furfural (HMF) to generate 2, 5-furandicarboxylic acid (FDCA).
(5) UiO-66 is a MOF formed by coordination of Zr with terephthalic acid, which is complexed with KMnO 4 Oxidation-reduction reaction in situ to generate layered delta-MnO 2 Layered delta-MnO with extended reaction time 2 Gradually grows up to finally form delta-MnO with a three-dimensional self-supporting structure 2 . UiO-66 provides support to avoid layered structure delta-MnO 2 And (3) agglomeration. While the MOF material is generally unstable in water, the structure can collapse or be damaged in the hydrothermal synthesis process, and UiO-66 is relatively stable and can be used as a stable support structure. Zirconium has acid-base property, has certain activation effect on a substrate, but is used as a matrix and MnO due to the fact that the oxygen of the crystal lattice of zirconium is relatively stable and lacks certain oxidation capacity 2 And the catalyst is compounded, so that the catalytic oxidation of HMF is facilitated. The manganese oxide has strong selective oxidation capability, can selectively oxidize HMF into FDCA, manganese dioxide with a layered structure has more exposed surfaces and more catalytic active sites, and is favorable for quick reaction.
Drawings
FIG. 1 is an X-ray diffraction (XRD) pattern of a zirconium manganese composite material with Zr: Mn =1:1 to 1:4 prepared in example 1 of the present invention with a hydrothermal time of 3 h;
FIG. 2 is a comparison graph of the micro-morphology of the zirconium-manganese composite material prepared from 30 min-12 h for the hydrothermal time with Mn =1:2 for Zr in example 1 of the invention and an EDS energy spectrum of the zirconium-manganese composite material prepared from 3h for Zr Mn =1:2 for hydrothermal time;
FIG. 3 is a microscopic morphology of UiO-66 prepared by comparative example 1 of the present invention;
FIG. 4 is a transmission electron microscope image of a zirconium manganese composite material prepared in example 1 of the present invention with Zr: Mn =1:2 and a hydrothermal time of 3 h;
FIG. 5 is an AFM of the Zr-Mn composite material obtained in example 1 of the present invention with Zr/Mn =1:2 and hydrothermal time of 3 h;
FIG. 6 is a transmission electron micrograph of UiO-66 obtained in comparative example 1 of the present invention;
FIG. 7 is a comparison graph of the performance of the zirconium manganese composite material prepared in example 1 of the present invention, in which Zr: Mn =1:2, the hydrothermal time is 30 min, 3h, and 12 h, and HMF is catalyzed under the conditions of 130 ℃, 1.5 MPa, and 18 h reaction;
FIG. 8 shows Zr/Mn =1:2 for example 1 of the present invention, a Zr-Mn composite material obtained by hydrothermal treatment for 3h, UiO-66 obtained in comparative example 1, and UiO-66 and MnO obtained in comparative example 2 2 A graph comparing the properties of the mechanically mixed material;
FIG. 9 is a graph of the cycle performance of the zirconium manganese composite material prepared by hydrothermal treatment for 3h with Zr: Mn =1:2 in example 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail below with reference to the accompanying drawings, which are examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features mentioned in the embodiments of the present invention described below may be combined as long as they do not conflict with each other.
Example 1
Preparing a zirconium-manganese composite material:
(1) weighing 0.22-0.88 g of potassium permanganate (KMnO) by using an electronic balance 4 ) Adding into 250 mL deionized water, ultrasonic dispersing for 10 min, magnetically stirring for 30 min, and stirringThe speed is 500 rpm, a solution A is obtained, and the solution A is evenly distributed in the polytetrafluoroethylene lining according to 14 mL of each part;
(2) weighing 0.02 g of UiO-66 (Zr: Mn =1:1-1: 4) by using an electronic balance, adding the weighed UiO-66 into the polytetrafluoroethylene lining, and magnetically stirring the mixture for 10 min at the stirring speed of 500 rpm to prepare uniformly dispersed solution B;
(3) then transferring the polytetrafluoroethylene lining into a stainless steel autoclave, carrying out constant temperature reaction in a drying oven at 180 ℃ for 3h (30 min, 1 h, 2 h, 4 h and 12 h), and cooling to room temperature along with the furnace after the reaction is finished;
(4) centrifuging the sample by a centrifuge to obtain black solid powder, wherein the rotating speed is 9000 rpm; and washing with deionized water for three times;
(5) and (4) freeze-drying overnight until the water is completely volatilized to obtain the zirconium-manganese composite material.
FIG. 1 is an X-ray diffraction (XRD) pattern of a zirconium-manganese composite material having Zr: Mn =1:1 to 1:4 and obtained in example 1 of the present invention with a hydrothermal time of 3h, and it can be seen from the graph that UiO-66 in the synthesized zirconium-manganese composite material is converted into monoclinic-phase ZrO with Zr: Mn =1:1 to 1:4 2 （m-ZrO 2 ) Reconversion to tetragonal phase ZrO 2 （t-ZrO 2 ) While Mn exists in a phase of delta-MnO 2 And the energy spectrum chart shows that the Mn, Zr and O are uniformly distributed. FIG. 2 is a comparison of the micro-morphology of the Zr-Mn composite material obtained in example 1 of the present invention with Zr/Mn =1:2 and hydrothermal time from 30 min to 12 h and an EDS spectrum of the Zr-Mn composite material obtained in example 1 with Zr/Mn =1:2 and hydrothermal time of 3h, and it can be seen from the graph that MnO on the surface of UiO-66 is present as the hydrothermal time is increased from 30 min to 3h 2 Gradually changed into obvious two-dimensional sheet shape from thin filaments attached to the surface, and gradually changed into one-dimensional linear shape at 4 h. FIGS. 3 and 6 are the microscopic morphology and transmission electron microscope images of UiO-66 prepared in comparative example 1 of the present invention, from which it can be seen that the prepared UiO-66 has regular and uniform morphology and size distribution between 0.5-2 μm. FIG. 4 is a transmission electron microscope image of the zirconium-manganese composite material prepared in example 1 of the present invention with Zr: Mn =1:2 and hydrothermal time of 3h, from which it can be seen that the particle size distribution of the hydrothermally synthesized zirconium-manganese composite material is slightly larger than the original UiO-66 size and is distributed between 0.6 μm and 2.1 μm,simultaneous edge sheet MnO 2 Is clearly visible. FIG. 5 is an atomic force microscope image of a Zr-Mn composite material prepared in example 1 of the present invention with Zr: Mn =1:2 and hydrothermal time of 3h, from which an ultra-thin two-dimensional surface delta-MnO can be seen 2 The thickness of the nano-sheets is distributed between 0.9 nm and 1.5 nm. Fig. 7 is a comparison graph of performance of the zirconium-manganese composite material prepared in example 1 of the present invention, in which Zr: Mn =1:2 and the hydrothermal time is 30 min, 3h, and 12 h, for catalyzing HMF, and it can be seen from the graph that the HMF conversion rate of the three materials can reach one hundred percent, wherein the yield of FDCA of the sample prepared in hydrothermal 3h is the highest, reaches 99.2%, and exceeds 62.8% in hydrothermal 30 min and 74.2% in hydrothermal 12 h. The performance of the sample is better than that of the hydrothermal sample for 30 min because MnO is added in the process of prolonging the hydrothermal time from 30 min to 3h 2 Gradually grows, does not completely grow at 30 min, but when the hydrothermal time is further prolonged to 12 h, the layered delta-MnO on the surface 2 Converted into a linear form
α-MnO 2 The active sites that are catalytically active are thus reduced, resulting in a certain reduction in performance.
Comparative example 1
Preparation of UiO-66:
(1) 0.0469 g of zirconium chloride (AlCl) was weighed using an electronic balance 3 ·6H 2 O) and 0.0.0348 g of terephthalic acid (PTA) are added into 40 mL of DMF, stirred for 30 min, then 5 mL of acetic acid is added, and stirred for 30 min again to prepare reaction precursor liquid;
(2) then transferring the reaction precursor liquid into a stainless steel autoclave with a polytetrafluoroethylene lining, carrying out constant-temperature reaction for 24 hours in a drying oven at 120 ℃, and cooling to room temperature along with the oven after the reaction is finished;
(3) centrifuging the sample by a centrifuge to obtain white solid powder, wherein the rotating speed is 9000 rpm; and washed three times with DMF and formic acid, respectively;
(4) by vacuum drying overnight until the water was completely evaporated, a uniform size of highly dispersed UiO-66 was obtained.
Comparative example 2
UiO-66 and MnO 2 Preparation of mechanically mixed samples:
(1) 0.1 g of UiO-66 (C) was weighed out on an electronic balance 48 H 28 O 32 Zr 6 ) 0.062 g of delta-MnO 2 Then uniformly mixed, UiO-66 and delta-MnO 2 The molar ratio of the medium element Zr to Mn is 1: 2;
(2) grinding the two uniformly mixed samples for 20 min by using a mortar, and then sieving the ground samples for 3 times by using a screen.
HMF catalytic Oxidation experiment
Application example 1
The zirconium-manganese composite material obtained in example 1 is used for catalytic oxidation of 5-Hydroxymethylfurfural (HMF), and the specific steps are as follows:
(1) putting 10 mL of ultrapure water into a liner of a high-pressure reaction kettle, adding 50 mg of HMF, adding 50 mg of sodium bicarbonate, adding 100 mg of zirconium-manganese composite catalyst, and performing ultrasonic treatment;
(2) introducing oxygen, keeping the pressure at 1.5 MPa, and starting timing after heating to 130 ℃;
(3) taking out reaction liquid after reacting for 18 h, quantifying the reaction liquid into a 10 mL volumetric flask, pouring the reaction liquid into a 50 mL centrifuge tube, centrifuging, taking 1 mL of supernate, dripping the supernate into a 100 mL volumetric flask, quantifying the supernate to 100 mL, carrying out ultrasonic treatment for five minutes, taking a proper amount of solution, and placing the solution in a liquid chromatography test.
Application comparative example 1
The UiO-66 obtained in comparative example 1 was used for the catalytic oxidation of HMF, with the following specific steps:
(1) putting 10 mL of ultrapure water into an inner container of a high-pressure reaction kettle, adding 50 mg of HMF, adding 50 mg of sodium bicarbonate, adding 100 mg of UiO-66 catalyst, and then carrying out ultrasonic treatment;
(2) introducing oxygen, keeping the pressure at 1.5 MPa, and starting timing after heating to 130 ℃;
(3) taking out reaction liquid after reacting for 18 h, quantifying the reaction liquid into a 10 mL volumetric flask, pouring the reaction liquid into a 50 mL centrifuge tube, centrifuging, taking 1 mL of supernate, dripping the supernate into a 100 mL volumetric flask, quantifying the supernate to 100 mL, carrying out ultrasonic treatment for five minutes, taking a proper amount of solution, and placing the solution in a liquid chromatography test.
Comparative application example 2
UiO-66 and MnO obtained in comparative example 2 2 The mechanical mixing sample is used for the catalytic oxidation of HMF, and the specific steps are as follows:
(1) 10 mL of ultrapure water is takenAdding HMF 50 mg, then adding sodium bicarbonate 50 mg, and adding UiO-66 and MnO 100 mg into the liner of the high-pressure reaction kettle 2 Mechanically mixing the catalyst and then carrying out ultrasonic treatment;
(2) introducing oxygen, keeping the pressure at 1.5 MPa, and starting timing after heating to 130 ℃;
(3) taking out reaction liquid after reacting for 18 h, quantifying the reaction liquid into a 10 mL volumetric flask, pouring the reaction liquid into a 50 mL centrifuge tube, centrifuging, taking 1 mL of supernate, dripping the supernate into a 100 mL volumetric flask, quantifying the supernate to 100 mL, carrying out ultrasonic treatment for five minutes, taking a proper amount of solution, and placing the solution in a liquid chromatography test.
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 properties of the mechanically mixed samples shows that the zirconium manganese composite material has the optimal catalytic performance, and the yield of the FDCA reaches 99.2 percent, which is more than 64.8 percent of that of the mechanically mixed sample and 3.9 percent of that of pure UiO-66. The zirconium-manganese composite material can be used for completely catalyzing and reducing 100 percent of HMF after 18 hours, and the performance of the zirconium-manganese composite material is far superior to that of UiO-66, 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, 99.2% FDCA yield, and excellent cycle performance, each cycle can maintain 100% conversion rate of HMF, the FDCA yield is above 90%, and the zirconium-manganese composite material still maintains excellent catalytic oxidation performance to HMF after 4 cycles.
It will be understood 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, and that any modification, equivalent replacement or improvement made within the spirit and principle of the invention should be included within the scope of protection of the invention.
Claims (10)
1. A method for synthesizing a zirconium-manganese composite material is characterized by comprising the following steps: the method comprises the following steps:
(1) adding heptavalent 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, and carrying out ultrasonic treatment on the reaction solution B after stirring at room temperature;
(3) then transferring the reaction liquid B to a polytetrafluoroethylene lining in a stainless steel high-pressure autoclave, and carrying out constant-temperature reaction in a drying oven;
(4) after the reaction is finished, cooling, centrifugally separating, washing and drying are carried out until the moisture is completely volatilized, and the ultra-thin two-dimensional flaky delta-MnO grown on the surface is obtained 2 The zirconium manganese composite material.
2. The method for synthesizing the zirconium-manganese composite material according to claim 1, wherein the method comprises the following steps: the heptavalent manganese salt in the step (1) is potassium permanganate KMnO 4 。
3. The method for synthesizing the zirconium-manganese composite material according to claim 1, wherein the method comprises the following steps: the dosage of the potassium permanganate in the step (1) is 0.002-0.005 mol, and the dosage of the deionized water is 250 mL.
4. The method for synthesizing the zirconium-manganese composite material according to claim 1, wherein the method comprises the following steps: the dissolving in the step (1) is specifically as follows: ultrasonic dispersion and magnetic stirring, wherein the ultrasonic dispersion time is 10-30 min; the magnetic stirring speed is 500 rpm; magnetic stirring time is 20-30 min.
5. The method for synthesizing the zirconium-manganese composite material according to claim 1, wherein the method comprises the following steps: in the step (2), UiO-66 is added according to the Zr/Mn molar ratio of 1:1-1: 4.
6. The method for synthesizing the zirconium-manganese composite material according to claim 1, wherein the method comprises the following steps: the constant temperature reaction in the step (3) is specifically as follows: reacting for 30 min-4 h at constant temperature of 180 ℃.
7. The method for synthesizing the zirconium-manganese composite material according to claim 1, wherein the method comprises the following steps: the cooling in the step (4) is specifically as follows: and cooling the mixture along with the furnace to room temperature.
8. The method for synthesizing the zirconium-manganese composite material according to claim 1, wherein the method comprises the following steps: and (4) the washing solvent is deionized water, and the washing times are 3 times.
9. The method for synthesizing the zirconium-manganese composite material according to claim 1, wherein the method comprises the following steps: the drying mode in the step (4) is vacuum-53 ℃ freeze drying, and the drying time is 8-12 h.
10. Use of the zirconium manganese composite obtained by the synthesis method according to claim 1, characterized in that it is used as a catalyst for the catalytic oxidation of 5-hydroxymethylfurfural to 2, 5-furandicarboxylic acid.
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