CN111135870B - Titanium dioxide nanobelt @ MOF composite material and application thereof - Google Patents
Titanium dioxide nanobelt @ MOF composite material and application thereof Download PDFInfo
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- CN111135870B CN111135870B CN201911386648.6A CN201911386648A CN111135870B CN 111135870 B CN111135870 B CN 111135870B CN 201911386648 A CN201911386648 A CN 201911386648A CN 111135870 B CN111135870 B CN 111135870B
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 227
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 85
- 239000000463 material Substances 0.000 title claims abstract description 62
- 239000002127 nanobelt Substances 0.000 claims abstract description 58
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 52
- 239000002131 composite material Substances 0.000 claims abstract description 19
- 230000001699 photocatalysis Effects 0.000 claims abstract description 19
- -1 carboxyl Chemical group 0.000 claims abstract description 17
- 239000011258 core-shell material Substances 0.000 claims abstract description 4
- 229910052751 metal Inorganic materials 0.000 claims description 38
- 239000002184 metal Substances 0.000 claims description 28
- 239000002074 nanoribbon Substances 0.000 claims description 28
- 239000013246 bimetallic metal–organic framework Substances 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 230000005540 biological transmission Effects 0.000 abstract description 6
- 238000011065 in-situ storage Methods 0.000 abstract description 4
- 230000031700 light absorption Effects 0.000 abstract description 4
- 230000004044 response Effects 0.000 abstract description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 53
- 239000000243 solution Substances 0.000 description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 36
- 239000008367 deionised water Substances 0.000 description 33
- 229910021641 deionized water Inorganic materials 0.000 description 33
- 239000000047 product Substances 0.000 description 32
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 30
- 238000005406 washing Methods 0.000 description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 27
- 238000006243 chemical reaction Methods 0.000 description 27
- 238000010438 heat treatment Methods 0.000 description 27
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 21
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 20
- 150000003839 salts Chemical class 0.000 description 18
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 17
- 238000002156 mixing Methods 0.000 description 16
- 238000009210 therapy by ultrasound Methods 0.000 description 15
- 238000001291 vacuum drying Methods 0.000 description 15
- 238000003756 stirring Methods 0.000 description 14
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 12
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 12
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 12
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 10
- 238000001035 drying Methods 0.000 description 10
- 238000010335 hydrothermal treatment Methods 0.000 description 9
- 239000011259 mixed solution Substances 0.000 description 9
- 239000013110 organic ligand Substances 0.000 description 9
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 8
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 8
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 description 8
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 8
- 238000002791 soaking Methods 0.000 description 8
- 229910001415 sodium ion Inorganic materials 0.000 description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000002425 crystallisation Methods 0.000 description 7
- 230000008025 crystallization Effects 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 description 5
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 238000003917 TEM image Methods 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 230000021523 carboxylation Effects 0.000 description 4
- 238000006473 carboxylation reaction Methods 0.000 description 4
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- 239000011592 zinc chloride Substances 0.000 description 4
- 235000005074 zinc chloride Nutrition 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000011941 photocatalyst Substances 0.000 description 3
- 230000006798 recombination Effects 0.000 description 3
- 238000005215 recombination Methods 0.000 description 3
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 2
- 238000005411 Van der Waals force Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- 239000002077 nanosphere Substances 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- GROMGGTZECPEKN-UHFFFAOYSA-N sodium metatitanate Chemical compound [Na+].[Na+].[O-][Ti](=O)O[Ti](=O)O[Ti]([O-])=O GROMGGTZECPEKN-UHFFFAOYSA-N 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 1
- LNYYKKTXWBNIOO-UHFFFAOYSA-N 3-oxabicyclo[3.3.1]nona-1(9),5,7-triene-2,4-dione Chemical compound C1=CC(C(=O)OC2=O)=CC2=C1 LNYYKKTXWBNIOO-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 239000013179 MIL-101(Fe) Substances 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004098 Tetracycline Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000007540 photo-reduction reaction Methods 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
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- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229960002180 tetracycline Drugs 0.000 description 1
- 229930101283 tetracycline Natural products 0.000 description 1
- 235000019364 tetracycline Nutrition 0.000 description 1
- 150000003522 tetracyclines Chemical class 0.000 description 1
- 229920000428 triblock copolymer Polymers 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
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- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1616—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts
- B01J31/1625—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts immobilised by covalent linkages, i.e. pendant complexes with optional linking groups
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
- B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B01J35/397—Egg shell like
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Abstract
The disclosure provides a titanium dioxide nanobelt @ MOF composite material and an application thereof as a photocatalytic material, wherein the composite material comprises a porous core-shell structure with a shell layer and an inner core, the inner core is the titanium dioxide nanobelt, and the shell layer is an MOF layer which is connected with the surface of the inner core through a covalent bond. The composite material is prepared by modifying TiO with carboxyl2The metal organic framework material connected with the covalent bond is uniformly grown on the surface of the nano-belt in situ, so that the electron transmission capability between the titanium dioxide nano-belt and the MOF material is effectively enhanced; in addition, the shell MOF material also has excellent visible light absorption capacity, increases the response capacity of the composite material to visible light, and has good application prospect as a photocatalytic material.
Description
Technical Field
The disclosure relates to the technical field of composite materials, in particular to a titanium dioxide nanobelt @ MOF composite material and application thereof.
Background
Titanium dioxide (TiO) having a one-dimensional structure2) The nanobelt can not only keep stable oxidation-reduction characteristics, but also overcome the defects of powder materials in application, and is always a research hotspot in the field of energy conversion. However, the titanium dioxide material has a small specific surface area and a wide forbidden band width, and the exposed surface is mostly a stable low-energy surface, so that the photocatalytic performance of the titanium dioxide material is far lower than that expected by theory.
In recent years, in order to overcome the above defects, researchers have tried different methods for titanium dioxide nano-materials to improve the photocatalytic activity thereof, wherein a relatively high-efficiency modification method is to make up for the advantages of TiO in photo-excited electron conduction and pore channel structure by using Metal Organic Framework (MOF)2To build a novel TiO2@ MOF heterojunction. For example, the Camile Petit group successfully designs a novel heterojunction photocatalyst by utilizing Zr-based MOF and titanium dioxide, and the novel heterojunction photocatalyst shows excellent performance in the reaction of photo-reduction of carbon dioxide; zhang Yaqiian topic group constructs a class of MIL-101(Fe)@TiO2Composite photocatalyst, MOF and TiO2The synergistic effect of (A) promotes the reaction rate of photodegradation of tetracycline.
However, most of the reports related to the present use TiO2Nanospheres and TiO2The nano-sheet and MOF construct a heterojunction, and the MOF is mostly MOF and TiO of single metal2The combination mode with MOF is mostly electrostatic force or van der Waals force with limited electron transmission capability, and TiO with uniform microstructure, controllable shell thickness and covalent bond connection is constructed2Methods for nanobelt @ bimetallic MOF composites are rarely reported.
It is noted that the information disclosed in the foregoing background section is only for enhancement of background understanding of the present disclosure and therefore it may contain information that does not constitute prior art that is known to a person of ordinary skill in the art.
Disclosure of Invention
A primary object of the present disclosure is to overcome at least one of the above-mentioned drawbacks of the prior art, and to provide a titanium dioxide nanobelt @ MOF composite and its application as a photocatalytic material, so as to solve the problems of limited electron transport ability, low photocatalytic activity, etc. of the existing titanium dioxide nanobelt @ MOF composite.
In order to achieve the purpose, the following technical scheme is adopted in the disclosure:
the disclosure provides a titanium dioxide nanobelt @ MOF composite material, which comprises a porous core-shell structure with a shell layer and an inner core, wherein the inner core is a carboxyl modified titanium dioxide nanobelt, and the shell layer is an MOF layer connected to the surface of the inner core through a covalent bond.
According to one embodiment of the present disclosure, the MOF is a bimetallic MOF.
According to one embodiment of the present disclosure, the bimetallic MOF contains a first metallic element and a second metallic element, each of which is independently selected from one of iron, cobalt, nickel, zinc, zirconium, and copper.
According to one embodiment of the present disclosure, the molar ratio of the first metal element to the second metal element is 1 (1 to 4).
According to one embodiment of the present disclosure, the titanium dioxide nanoribbons comprise 15% to 45% of the composite material by mass percent.
According to one embodiment of the present disclosure, the shell layer has a thickness of 50nm to 100 nm.
According to one embodiment of the present disclosure, the titanium dioxide nanobelt has a length of 0.2 to 10um, a width of 200 to 500nm, and a height of 20 to 50 nm.
According to one embodiment of the present disclosure, the shell layer has a pore size of 2nm to 20 nm.
The disclosure also provides an application of the titanium dioxide nanobelt @ MOF composite material as a photocatalytic material.
According to the technical scheme, the beneficial effects of the disclosure are as follows:
the titanium dioxide nanobelt @ MOF composite material provided by the disclosure is prepared by modifying TiO with carboxyl2The metal organic framework Material (MOF) connected by covalent bonds is uniformly grown on the surface of the nano-belt in situ, so that the electronic transmission capacity between the titanium dioxide nano-belt and the MOF material is effectively enhanced, a heterostructure with good photo-generated carrier transmission capacity is obtained, and the photocatalysis performance is further improved; in addition, the excellent visible light absorption capability of the shell MOF material can be utilized to enhance the visible light response capability, and the shell MOF material is combined with TiO2The formed heterostructure can effectively transmit photon-generated carriers, inhibit the higher recombination rate of the heterostructure and further improve the photocatalytic activity. The composite material has good application prospect as a photocatalytic material.
Drawings
The following drawings are included to provide a further understanding of the disclosure and are incorporated in and constitute a part of this specification, illustrate embodiments of the disclosure and together with the description serve to explain the principles of the disclosure and not to limit the disclosure.
FIG. 1 is a process flow diagram for the preparation of a titanium dioxide nanobelt @ MOF composite according to one embodiment of the present disclosure;
FIG. 2 is a schematic diagram of the synthesis mechanism of a titanium dioxide nanobelt @ MOF composite according to one embodiment of the present disclosure;
FIG. 3 is a TEM image of the titania nanobelts of example 1;
figure 4 is a TEM image of the titanium dioxide nanobelt @ MOF composite of example 1.
Wherein the reference numbers are as follows:
100: titanium dioxide nanobelt
200: a carboxyl modified titanium dioxide nanobelt,
300: titanium dioxide nanobelt @ MOF composite material
301: layer of MOF material
Detailed Description
The following presents various embodiments or examples in order to enable those skilled in the art to practice the invention with reference to the description herein. These are, of course, merely examples and are not intended to limit the present disclosure. The endpoints of the ranges and any values disclosed in the present disclosure are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to yield one or more new ranges of values, which ranges of values should be considered as specifically disclosed herein.
The following presents various embodiments or examples in order to enable those skilled in the art to practice the invention with reference to the description herein. These are, of course, merely examples and are not intended to limit the present disclosure. The endpoints of the ranges and any values disclosed in the present disclosure are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to yield one or more new ranges of values, which ranges of values should be considered as specifically disclosed herein.
One aspect of the disclosure provides a titanium dioxide nanobelt @ MOF composite material, which comprises a porous core-shell structure having a shell layer and an inner core, wherein the inner core is a carboxyl-modified titanium dioxide nanobelt, and the shell layer is a MOF layer covalently bonded to the surface of the inner core.
In light of the present disclosure, as previously mentioned, the use of titanium dioxide (TiO) has been reported2) Materials composited with metal organic framework Materials (MOF), but mostly made of TiO2Nanospheres or TiO2The nano-sheets and the MOF construct a heterojunction, and the combination mode is mostly electrostatic force or van der Waals force with limited electron transmission capability. The inventors of the present disclosure found that the responsiveness of a catalyst to available light is enhanced by utilizing the excellent visible light absorption ability of a shell MOF material, and that the catalyst reacts with TiO2The heterostructure forming covalent bond connection can effectively transmit photon-generated carriers, inhibit higher recombination rate of the heterostructure and improve photocatalytic activity.
In some embodiments, the foregoing MOFs are bimetallic MOFs, i.e., the composite is a titanium dioxide nanobelt @ bimetallic MOF composite. As known to those skilled in the art, a metal-organic framework material refers to a crystalline porous material with a periodic network structure formed by self-assembly of metal ions and organic ligands. Because the crystallization capacity of the single metal MOF is strong, perfect pore channels can be formed when the MOF structure is formed, and the number of defect sites in the crystal is small, namely the number of active sites is low. For bimetallic MOFs, on the one hand, the presence of multiple metals can extend the range of available spectra that the catalyst can absorb; on the other hand, due to different coordination modes and atom sizes of different metal ions, a large number of coordination defects can be caused by ion replacement or ion doping, and the existence of the coordination unsaturated bond provides a large number of Lewis acid sites for the catalyst, so that more titanium dioxide can be combined, and the performance of the composite material is further improved synergistically.
In some embodiments, the bimetallic MOFs contain a first metallic element and a second metallic element different from the first metallic element, which may each be independently selected from one of iron, cobalt, nickel, zinc, zirconium, and copper. Alternatively, the molar ratio of the first metal element and the second metal element is 1 (1-4), such as 1:1, 1:2, 1:3, 1:4, and the like, to which the present disclosure is not limited.
In some embodiments, the titanium dioxide nanoribbons comprise 15% to 45% of the composite material by mass percent. By adjusting the proportion of the titanium dioxide nanobelts and the MOF or the proportion of metal elements in the MOF, composite materials with different structures and properties can be obtained.
In some embodiments, the shell layer has a thickness of 50nm to 100nm, i.e., the MOF layer has a thickness of 50nm to 100 nm. With MOF layer on TiO2The larger the thickness of the nanobelt coating is, the higher the performance of the composite material is, however, the larger the thickness is, the less the interface effect is, and the synergistic effect is reduced, so the thickness of 50nm to 100nm is preferable.
In some embodiments, the titanium dioxide nanoribbons of the titanium dioxide nanoribbons have a length of 0.2um to 10um, a width of 200nm to 500nm, and a height of 20nm to 50 nm.
In some embodiments, the shell has a pore size of 2nm to 20 nm.
Another aspect of the present disclosure provides a preparation method of the above titanium dioxide nanobelt @ MOF composite, fig. 1 shows a flow chart of a preparation process of the titanium dioxide nanobelt @ MOF composite according to an embodiment of the present disclosure, and fig. 2 shows a schematic diagram of a synthesis mechanism of the titanium dioxide nanobelt @ MOF composite. With reference to fig. 1 and 2, the preparation method of the titanium dioxide nanobelt @ MOF composite material comprises the following steps: preparing a titanium dioxide nanobelt; carrying out carboxylation treatment on the titanium dioxide nanobelt to obtain a carboxyl modified titanium dioxide nanobelt; and mixing the carboxyl modified titanium dioxide nanobelt, metal salt and an organic ligand, and then carrying out heating crystallization treatment to obtain the titanium dioxide nanobelt @ MOF composite material.
The preparation process of the titanium dioxide nanobelt @ MOF composite material is specifically described as follows:
in some embodiments, the titania nanoribbons of the present disclosure are prepared using a hydrothermal process comprising:
firstly, dissolving titanium dioxide in an alkali solution, and then carrying out an alkali-heat reaction to obtain the titanate nanoribbon. Taking sodium hydroxide as an example of an alkaline solution, 0.2g to 0.6g of titanium dioxide is dissolved in 8M to 10M of an aqueous solution of sodium hydroxide, stirred for 1h to 2h, mixed uniformly, and then transferred to a 100ml polytetrafluoroethylene reaction kettle for carrying out an alkaline thermal reaction. Wherein the temperature of the alkali thermal reaction is 160-180 ℃, and the reaction time can be 36-72 h. The obtained product can be washed by deionized water for several times for later use.
And then, placing the titanate nanoribbon obtained by the alkali-thermal reaction in a first acid solution for ion exchange to obtain a titanate nanoribbon, and then placing the titanate nanoribbon in a second acid solution for hydrothermal treatment. Wherein the first acid solution and the second acid solution are independently selected from dilute hydrochloric acid solution or dilute sulfuric acid solution, and the like, and the first acid solution and the second acid solution can be the same or different. Taking a dilute hydrochloric acid solution as a first acid solution and a dilute sulfuric acid solution as a second acid solution as an example, soaking the sodium titanate nanobelt washed by the deionized water for several times in the dilute hydrochloric acid solution, standing for 24-48 h to replace sodium ions, then performing hydrothermal treatment on the sodium titanate nanobelt by using the dilute sulfuric acid solution at the temperature of 100-120 ℃ for 12-18 h, washing the obtained product by using the deionized water and ethanol for several times in sequence, and drying.
And then, calcining the dried product in an air atmosphere at the temperature of 500-650 ℃ for 1-3 h to obtain the titanium dioxide nanobelt.
As shown in fig. 2, the obtained titanium dioxide nanobelt 100 is further subjected to carboxylation treatment to obtain a carboxyl group (-COOH) -modified titanium dioxide nanobelt 200. Through carrying out carboxyl functional modification with the titanium dioxide nanobelt, not only can improve the adsorption binding capacity to metal ion, more can strengthen the electron transfer ability between titanium dioxide nanobelt and the MOF material, and then promote combined material's photocatalysis performance.
Specifically, the carboxylation treatment includes: and mixing the carboxyl-containing compound and the titanium dioxide nanobelt in an alcohol water solution for heating treatment, and drying to obtain the carboxyl-modified titanium dioxide nanobelt. The carboxyl-containing compound can be a carboxyl organic ligand and/or an organic acid anhydride, the carboxyl organic ligand is selected from one or more of terephthalic acid, trimesic acid and pyromellitic acid, the organic acid anhydride is selected from one or more of phthalic anhydride, isophthalic anhydride, trimellitic anhydride and pyromellitic dianhydride, alcohol in an alcohol-water solution can be ethanol, methanol and the like, and the volume ratio of the alcohol to the water is (4-14): 1, for example: 4:1, 9:1, 14:1, etc.
In some embodiments, the mass ratio of the titanium dioxide nanoribbons to the carboxyl-containing compound is (0.25-2.5): 1. For example, 1.0g to 2.5g of titanium dioxide nanobelt and 1.0g to 4.0g of carboxyl-containing compound are dissolved in 50ml to 60ml of mixed solution of deionized water and ethanol, treated for 10h to 15h at 100 ℃ to 120 ℃ after ultrasonic oscillation for 1h to 2h, washed for several times by deionized water and ethanol in sequence, and then dried in vacuum at 80 ℃ to 120 ℃ to obtain the carboxyl-modified titanium dioxide nanobelt 200.
Further, the obtained carboxyl-modified titanium dioxide nanobelt 200 is mixed with a metal salt and an organic ligand to perform a heat crystallization treatment. Metal salts include, but are not limited to, one or more of ferric trichloride, cobalt dichloride, nickel dichloride, zinc dichloride, copper nitrate, ferric nitrate, zirconium tetrachloride, and cobalt nitrate; organic ligands include, but are not limited to, one or more of terephthalic acid, 2-aminoterephthalic acid, trimesic acid, and 2-methylimidazole.
In some embodiments, the metal salt can comprise two different metal salts, a first metal salt and a second metal salt, to produce the foregoing titanium dioxide nanobelt @ bimetallic MOF composite. Wherein the first metal salt is selected from one of ferric trichloride, cobalt dichloride, nickel dichloride, zinc dichloride, copper nitrate, ferric nitrate, zirconium tetrachloride and cobalt nitrate, and the first metal salt is selected from one of ferric trichloride, cobalt dichloride, nickel dichloride, zinc dichloride, copper nitrate, ferric nitrate, zirconium tetrachloride and cobalt nitrate. The molar ratio of the first metal salt to the second metal salt is 1 (1-4).
In some embodiments, the molar ratio of the carboxyl-modified titanium dioxide nanobelt 200, the metal salt and the organic ligand is (12-1): (4-1): 1, such as 12:4:1, 2:2:1, 3:1:1, and the like. The adjustment and control of the shell thickness of the MOF material can be realized by changing the feeding amount of metal salt and organic monomer for synthesizing the MOF material, and the composite materials with different structures can be prepared by adjusting the proportion of different metal salts.
In some embodiments, before the thermal crystallization treatment, a stabilizer is further added to mix with the carboxyl-modified titanium dioxide nanobelt 200, the metal salt and the organic ligand, wherein the stabilizer is selected from one or more of polyvinylpyrrolidone (PVP), polyacrylamide, polyethylene glycol and a polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (P123), and the mass percentage of the stabilizer in the carboxyl-modified titanium dioxide nanobelt is 30% to 150%. The MOF material can be made on TiO by using PVP and the like as a stabilizer and dispersant2The surface of the nano-belt grows uniformly in situ to form a compact and uniform shell layer.
Specifically, for example, 0.1g to 0.4g of carboxyl-modified titanium dioxide nanobelt is dissolved in 40ml to 80ml of N, N-Dimethylformamide (DMF) solution of 1 mg to 4mg/ml PVP, uniformly dispersed by ultrasonic, then metal salt and organic ligand are added, stirring is carried out for 1h to 2h, and then heating crystallization treatment is carried out, wherein the heating crystallization treatment temperature is 110 ℃ to 150 ℃, the heating crystallization treatment time is 12h to 72h, the product is sequentially washed and centrifuged by DMF and methanol, and then vacuum drying is carried out for 12h to 18h at 80 ℃ to 120 ℃, so that the titanium dioxide nanobelt @ MOF composite material 300 shown in figure 2 is obtained, wherein the surface of the carbon dioxide nanobelt is coated with an MOF material layer 301.
The present disclosure will be further illustrated by the following specific examples, but the present disclosure is not limited thereto in any way. Unless otherwise specified, the reagents used in the present invention are all analytical and commercially available.
Example 1
1) Dissolving 0.4g of P25 titanium dioxide in 10M aqueous solution of sodium hydroxide, stirring for 1h, uniformly mixing, transferring to a 100mL polytetrafluoroethylene reaction kettle, heating at 180 ℃ for 72h, washing a product with deionized water for a plurality of times, soaking in a dilute hydrochloric acid solution, standing for 24h to replace sodium ions, performing hydrothermal treatment with a dilute sulfuric acid solution at 100 ℃ for 12h, washing the product with deionized water and ethanol for a plurality of times in sequence, drying, and treating at 600 ℃ for 2h in an air atmosphere to obtain TiO2A nanoribbon.
2) 1g of the prepared TiO2The nanobelt and 3g of terephthalic acid are dissolved inAdding 45ml deionized water and 5ml ethanol into mixed solution, ultrasonic treating for 1 hr, heating at 100 deg.C for 12 hr, washing with deionized water and ethanol, centrifuging, and vacuum drying at 80 deg.C to obtain carboxyl modified TiO2A nanoribbon;
3) 0.2g of carboxyl-modified TiO2Dissolving the nanobelt in 60mL of 4mg/mL PVP DMF solution, performing ultrasonic treatment for 1h, uniformly mixing, adding 0.1mmol of nickel dichloride, 0.4mmol of zirconium tetrachloride and 0.5mmol of 2-amino terephthalic acid, stirring for 1h, heating at 120 ℃ for 24h, washing the product with DMF and methanol in sequence, and performing vacuum drying at 80 ℃ for 12h to obtain TiO2Nanobelt @ MOF composites.
FIG. 3 shows the TiO of example 12TEM image of nanobelts, FIG. 4 shows TiO of example 12TEM image of a nanobelt @ MOF composite. As can be seen from FIGS. 3 and 4, the TiO compound2The nanobelts are coated with a MOF material layer after reaction.
Example 2
1) Dissolving 0.2g of P25 titanium dioxide in 8M aqueous solution of sodium hydroxide, stirring for 2h, uniformly mixing, transferring to a 100ml polytetrafluoroethylene reaction kettle, heating at 160 ℃ for 72h, washing a product with deionized water for a plurality of times, soaking in dilute hydrochloric acid solution, standing for 36h to replace sodium ions, performing hydrothermal treatment with dilute sulfuric acid solution at 100 ℃ for 24h, washing the product with deionized water and ethanol for a plurality of times in sequence, drying, and treating at 650 ℃ for 3h in an air atmosphere to obtain TiO2A nanoribbon.
2) 2g of the prepared TiO2Dissolving nanobelt and 4g trimesic acid in a mixed solution containing 52ml deionized water and 3ml ethanol, performing ultrasonic treatment for 2h, heating at 100 ℃ for 12h, washing and centrifuging the product with deionized water and ethanol in sequence, and performing vacuum drying at 80 ℃ to obtain carboxyl modified TiO2A nanoribbon;
3) 0.15g of carboxyl-modified TiO2Dissolving the nanobelt in 60mL of 2mg/mL PVP DMF solution, performing ultrasonic treatment for 30min, uniformly mixing, adding 0.375mmol of nickel chloride, 0.375mmol of copper nitrate and 0.375mmol of pyromellitic acid, stirring for 2h, heating at 120 ℃ for 24h, washing the product with DMF and methanol in sequence, and performing vacuum drying at 120 ℃ for 12h to obtain TiO2Nano meterTape @ MOF composite.
Example 3
1) Dissolving 0.6g of P25 titanium dioxide in 9M aqueous solution of sodium hydroxide, stirring for 2h, uniformly mixing, transferring to a 100mL polytetrafluoroethylene reaction kettle, heating at 180 ℃ for 36h, washing a product with deionized water for several times, soaking in a dilute hydrochloric acid solution, standing for 24h to replace sodium ions, performing hydrothermal treatment with a dilute sulfuric acid solution at 110 ℃ for 12h, washing the product with deionized water and ethanol for several times in sequence, drying, and treating at 600 ℃ for 1h in an air atmosphere to obtain TiO2A nanoribbon.
2) 2g of the prepared TiO2Dissolving the nanobelt and 1g of terephthalic acid in a mixed solution containing 45ml of deionized water and 5ml of ethanol, carrying out ultrasonic treatment for 1h, heating at 100 ℃ for 12h, washing and centrifuging the product by using the deionized water and the ethanol in sequence, and carrying out vacuum drying at 80 ℃ to obtain carboxyl modified TiO2A nanoribbon;
3) 0.3g of carboxyl-modified TiO2Dissolving the nanobelt in 70ml of 4mg/ml PVP DMF solution, performing ultrasonic treatment for 30min, uniformly mixing, adding 0.4mmol of zirconium tetrachloride, 0.4mmol of ferric trichloride and 0.8mmol of 2-amino terephthalic acid, stirring for 2h, heating at 120 ℃ for 24h, washing the product with DMF and methanol in sequence, and performing vacuum drying at 80 ℃ for 16h to obtain TiO2Nanobelt @ MOF composites.
Example 4
1) Dissolving 0.4g of P25 titanium dioxide in 10M aqueous solution of sodium hydroxide, stirring for 1h, uniformly mixing, transferring to a 100ml polytetrafluoroethylene reaction kettle, heating at 160 ℃ for 72h, washing a product with deionized water for a plurality of times, soaking in dilute hydrochloric acid solution, standing for 36h to replace sodium ions, then performing hydrothermal treatment with dilute sulfuric acid solution at 110 ℃ for 16h, washing the product with deionized water and ethanol for a plurality of times in sequence, drying, and treating at 650 ℃ for 2h in an air atmosphere to obtain TiO2A nanoribbon.
2) 3g of the prepared TiO2Dissolving nanobelt and 1g trimesic acid in a mixed solution containing 45ml deionized water and 5ml ethanol, performing ultrasonic treatment for 1h, heating at 100 ℃ for 12h, washing and centrifuging the product with deionized water and ethanol in sequence, and performing vacuum drying at 80 ℃ to obtain carboxyl modified TiO2A nanoribbon;
3) 0.3g of carboxyl-modified TiO2Dissolving the nanobelt in 50ml of 4mg/ml PVP DMF solution, performing ultrasonic treatment for 30min, uniformly mixing, adding 0.4mmol of nickel chloride, 0.4mmol of cobalt chloride and 0.75mmol of terephthalic acid, performing ultrasonic treatment for 30min, heating at 120 ℃ for 24h, washing the product with DMF and methanol in sequence, and performing vacuum drying at 100 ℃ for 16h to obtain TiO2Nanobelt @ MOF composites.
Example 5
1) Dissolving 0.5g of P25 titanium dioxide in 10M aqueous solution of sodium hydroxide, stirring for 1h, uniformly mixing, transferring to a 100ml polytetrafluoroethylene reaction kettle, heating at 180 ℃ for 72h, washing the product with deionized water for a plurality of times, soaking in dilute hydrochloric acid solution, standing for 48h to replace sodium ions, then carrying out hydrothermal treatment with dilute sulfuric acid solution at 100 ℃ for 24h, washing the product with deionized water and ethanol for a plurality of times in sequence, drying, and treating at 500 ℃ for 3h in air atmosphere to obtain TiO2A nanoribbon.
2) 2g of the prepared TiO2Dissolving nanobelt and 1g pyromellitic acid in a mixed solution containing 45ml deionized water and 5ml ethanol, performing ultrasonic treatment for 2h, heating at 100 ℃ for 12h, washing the product with deionized water and ethanol in sequence, centrifuging, and vacuum drying at 80 ℃ to obtain carboxyl modified TiO2A nanoribbon;
3) 0.3g of carboxyl-modified TiO2Dissolving the nanobelt in 60ml of 4mg/ml PVP DMF solution, performing ultrasonic treatment for 30min, uniformly mixing, adding 0.4mmol of nickel chloride, 0.4mmol of zinc chloride and 0.8mmol of 2-methylimidazole, continuously stirring for 2h, heating at 110 ℃ for 24h, washing the product with DMF and methanol in sequence, and performing vacuum drying at 100 ℃ for 18h to obtain TiO2Nanobelt @ MOF composites.
Example 6
1) Dissolving 0.4g of P25 titanium dioxide in 9M aqueous solution of sodium hydroxide, stirring for 2h, uniformly mixing, transferring to a 100ml polytetrafluoroethylene reaction kettle, heating at 180 ℃ for 72h, washing the product with deionized water for a plurality of times, soaking in dilute hydrochloric acid solution, standing for 24h to replace sodium ions, then carrying out hydrothermal treatment with dilute sulfuric acid solution at 100 ℃ for 12h, washing the product with deionized water and ethanol for a plurality of times in sequence, drying, and carrying out 55M air atmosphereTreating at 0 deg.C for 2h to obtain TiO2A nanoribbon.
2) 1g of the prepared TiO2Dissolving nanobelt and 1g pyromellitic acid in a mixed solution containing 45ml deionized water and 5ml ethanol, performing ultrasonic treatment for 2h, heating at 100 ℃ for 12h, washing the product with deionized water and ethanol in sequence, centrifuging, and vacuum drying at 80 ℃ to obtain carboxyl modified TiO2A nanoribbon;
3) 0.3g of carboxyl-modified TiO2Dissolving the nanobelt in 80ml of 4mg/ml PVP DMF solution, performing ultrasonic treatment for 30min, uniformly mixing, adding 0.4mmol of ferric nitrate, 0.8mmol of copper nitrate and 0.6mmol of trimesic acid, performing ultrasonic treatment for 30min, heating at 120 ℃ for 24h, washing the product with DMF and methanol in sequence, and performing vacuum drying at 80 ℃ for 12h to obtain TiO2Nanobelt @ MOF composites.
Example 7
1) Dissolving 0.4g of P25 titanium dioxide in 10M aqueous solution of sodium hydroxide, stirring for 1h, uniformly mixing, transferring to a 100mL polytetrafluoroethylene reaction kettle, heating at 180 ℃ for 72h, washing a product with deionized water for a plurality of times, soaking in a dilute hydrochloric acid solution, standing for 24h to replace sodium ions, performing hydrothermal treatment with a dilute sulfuric acid solution at 100 ℃ for 12h, washing the product with deionized water and ethanol for a plurality of times in sequence, drying, and treating at 600 ℃ for 2h in an air atmosphere to obtain TiO2A nanoribbon.
2) 1g of the prepared TiO2Dissolving the nanobelt and 3g of terephthalic acid in a mixed solution containing 45ml of deionized water and 5ml of ethanol, carrying out ultrasonic treatment for 1h, heating at 100 ℃ for 12h, washing and centrifuging the product by using the deionized water and the ethanol in sequence, and carrying out vacuum drying at 80 ℃ to obtain carboxyl modified TiO2A nanoribbon;
3) 0.2g of carboxyl-modified TiO2Dissolving the nanobelt in 40mL of 4mg/mL PVP DMF solution, performing ultrasonic treatment for 1h, uniformly mixing, adding 0.2mmol of zirconium tetrachloride and 0.5mmol of 2-amino terephthalic acid, stirring for 1h, heating at 120 ℃ for 24h, washing the product with DMF and methanol in sequence, and performing vacuum drying at 80 ℃ for 12h to obtain TiO2Nanobelt @ MOF composites.
Comparative example 1
The preparation method is the same as example 1 except thatWithout further MOF material coating, only step 1) is carried out to obtain TiO2A nanoribbon.
Comparative example 2
Dissolving 0.1mmol of nickel dichloride, 0.4mmol of zirconium tetrachloride and 0.5mmol of 2-amino terephthalic acid into 60mL of a 4mg/mL PVP DMF solution, ultrasonically stirring for 1h, heating at 120 ℃ for 24h, washing the product with DMF and methanol in sequence, and drying in vacuum at 80 ℃ for 12h to obtain the ZrNi-MOF material.
Comparative example 3
The preparation method is the same as example 1, except that the TiO obtained in step 1)2The nanobelt is not subjected to carboxylation treatment, and is directly subjected to the step 3) to obtain the non-covalent bond-bonded TiO2Nanobelt @ bimetallic MOF composites.
Test example
Photocatalytic performance tests were performed on the materials prepared in examples 1 to 7 and comparative examples 1 to 3, respectively. The experiment is carried out by using a PCX50B multi-channel photocatalytic reaction system of Beijing Pofely science and technology Limited, and the light source of the instrument is LED artificial visible light and has a magnetic stirring function. Before the reaction starts, the catalyst is dried in an oven at 80 ℃ for 3h, and then 20mg of the catalyst, 33. mu.L of benzyl alcohol (0.3mmol), 3mL of acetonitrile and magnetons are put into a 50mL reaction bottle matched with the reaction system in sequence. After the reaction system is vacuumized for 10min, oxygen is introduced, a light source of the reaction system and a magnetic stirring switch are turned on, and a reaction bottle is placed on a reaction instrument for reaction for 18 h. During the reaction, the system is ensured to be carried out under the condition of room temperature. After the reaction is finished, the mixed solution needs to be centrifuged for 6min to remove the solid catalyst, and 50 μ L of the obtained clear solution is extracted by using a microsyringe and is subjected to gas chromatography-mass spectrometry (GC-MS) to detect and analyze the reaction product.
The catalytic results are shown in table 1. As can be seen from example 1, comparative example 1 and comparative example 2, compared to TiO alone2In the case of nanoribbon or MOF materials, TiO of the present disclosure2The nanobelt @ MOF composite can enable reactionThe conversion rate and the selectivity are higher; as can be seen from example 1 and comparative example 3, the present disclosure binds TiO by covalent bond, compared to by physical binding2The nano-belt and the MOF material have better photocatalytic performance.
From examples 1 and 7, it can be seen that bimetallic MOF materials are used with TiO as compared to single metal MOF materials2The nanobelts are compounded, so that the reaction conversion rate and the selectivity are greatly improved. The main reason is that the bimetallic MOF of the shell layer can expand the range of the catalyst capable of absorbing and utilizing the spectrum, and the catalytic activity can enhance the catalytic capability of the catalyst due to more coordination unsaturated bonds. Furthermore, MOF and TiO2The built internal electric field can effectively promote the separation of electrons and holes, improve the utilization rate of photons and enhance the catalytic activity. On the other hand, it can be seen from examples 1 to 7 that different metal elements and the ratio of the metal elements also have a certain influence on the catalytic performance of the material. In practical application, different catalytic materials can be applied according to different requirements.
TABLE 1
In summary, the present disclosure is directed to TiO2Carboxyl functional modification is carried out on the surface of the nanobelt, and the MOF material is further grown in situ, so that the performance of the obtained composite material is obviously improved. Wherein, carboxyl functional modification not only can improve the adsorption and combination capacity to metal ions, but also can enhance TiO2Electron transmission capacity between the nanobelts and the MOF material, so that the photocatalytic performance is improved; the excellent visible light absorption capability of the shell MOF material is utilized to enhance the response capability of the catalyst to visible light, and the catalyst and TiO are utilized2The formed heterostructure can effectively transmit photon-generated carriers, inhibit the higher recombination rate of the heterostructure and further improve the photocatalytic activity; in addition, the method can also realize the regulation and control of the shell thickness of the MOF material by changing the feeding amount of metal salt and organic monomer for synthesizing the MOF materialAnd the titanium dioxide nanobelts @ MOF composite materials with different structures can be prepared by adjusting the proportion of different metal salts. In conclusion, the method disclosed by the invention is simple and suitable for large-scale industrial production, and the obtained TiO2The nanobelt @ MOF composite material is high in photocatalytic performance and has a good application prospect when being used as a photocatalytic material.
It should be noted by those skilled in the art that the described embodiments of the present disclosure are merely exemplary, and that various other substitutions, alterations, and modifications may be made within the scope of the present disclosure. Accordingly, the present disclosure is not limited to the above-described embodiments, but is only limited by the claims.
Claims (9)
1. The titanium dioxide nanobelt @ MOF composite material is characterized by comprising a porous core-shell structure with a shell layer and an inner core, wherein the inner core is a carboxyl modified titanium dioxide nanobelt, and the shell layer is an MOF layer connected to the surface of the inner core through a covalent bond.
2. The titanium dioxide nanobelt @ MOF composite of claim 1, wherein the MOF is a bimetallic MOF.
3. The titania nanobelt @ MOF composite of claim 2, wherein the bimetallic MOF comprises a first metallic element and a second metallic element, each of the first and second metallic elements being independently selected from one of iron, cobalt, nickel, zinc, zirconium, and copper.
4. The titanium dioxide nanobelt @ MOF composite material according to claim 3, wherein the molar ratio of the first metal element to the second metal element is 1 (1-4).
5. The titanium dioxide nanoribbon @ MOF composite of claim 1, wherein the titanium dioxide nanoribbon comprises 15% to 45% of the composite by mass percent.
6. The titanium dioxide nanobelt @ MOF composite material according to claim 1, wherein the shell layer thickness is 50 to 100 nm.
7. The titanium dioxide nanoribbon @ MOF composite of claim 1, wherein the titanium dioxide nanoribbon has a length of 0.2 to 10um, a width of 200 to 500nm, and a height of 20 to 50 nm.
8. The titanium dioxide nanobelt @ MOF composite material according to claim 1, wherein the pore size of the shell layer is 2nm to 20 nm.
9. Use of the titanium dioxide nanobelt @ MOF composite material according to any one of claims 1 to 8 as a photocatalytic material.
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