CN110721748B - Photocatalyst and preparation method and application thereof - Google Patents
Photocatalyst and preparation method and application thereof Download PDFInfo
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- CN110721748B CN110721748B CN201911083803.7A CN201911083803A CN110721748B CN 110721748 B CN110721748 B CN 110721748B CN 201911083803 A CN201911083803 A CN 201911083803A CN 110721748 B CN110721748 B CN 110721748B
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims abstract description 87
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims abstract description 34
- 235000019445 benzyl alcohol Nutrition 0.000 claims abstract description 29
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000013096 zirconium-based metal-organic framework Substances 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 34
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 33
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 30
- 239000013207 UiO-66 Substances 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 14
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 7
- 239000003446 ligand Substances 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- AUNGANRZJHBGPY-SCRDCRAPSA-N Riboflavin Chemical compound OC[C@@H](O)[C@@H](O)[C@@H](O)CN1C=2C=C(C)C(C)=CC=2N=C2C1=NC(=O)NC2=O AUNGANRZJHBGPY-SCRDCRAPSA-N 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000011716 vitamin B2 Substances 0.000 claims description 2
- 229960004217 benzyl alcohol Drugs 0.000 claims 11
- 230000001699 photocatalysis Effects 0.000 abstract description 17
- 230000001590 oxidative effect Effects 0.000 abstract description 6
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 229930003270 Vitamin B Natural products 0.000 description 40
- 239000011720 vitamin B Substances 0.000 description 40
- 235000019156 vitamin B Nutrition 0.000 description 40
- 238000007254 oxidation reaction Methods 0.000 description 19
- 230000003647 oxidation Effects 0.000 description 14
- 239000012621 metal-organic framework Substances 0.000 description 13
- 239000000463 material Substances 0.000 description 12
- 238000012360 testing method Methods 0.000 description 10
- 238000001069 Raman spectroscopy Methods 0.000 description 5
- -1 halogen organic compounds Chemical class 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 230000004580 weight loss Effects 0.000 description 4
- 230000010718 Oxidation Activity Effects 0.000 description 3
- 229910007932 ZrCl4 Inorganic materials 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 238000004729 solvothermal method Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000003828 vacuum filtration Methods 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 2
- 229910007746 Zr—O Inorganic materials 0.000 description 2
- 238000004873 anchoring Methods 0.000 description 2
- 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 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000003642 reactive oxygen metabolite Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229930003231 vitamin Natural products 0.000 description 2
- 235000013343 vitamin Nutrition 0.000 description 2
- 239000011782 vitamin Substances 0.000 description 2
- 229940088594 vitamin Drugs 0.000 description 2
- 150000003722 vitamin derivatives Chemical class 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- AUNGANRZJHBGPY-UHFFFAOYSA-N D-Lyxoflavin Natural products OCC(O)C(O)C(O)CN1C=2C=C(C)C(C)=CC=2N=C2C1=NC(=O)NC2=O AUNGANRZJHBGPY-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910007744 Zr—N Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000005515 coenzyme Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229930003935 flavonoid Natural products 0.000 description 1
- 150000002215 flavonoids Chemical class 0.000 description 1
- 235000017173 flavonoids Nutrition 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000007539 photo-oxidation reaction Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002151 riboflavin Substances 0.000 description 1
- 229960002477 riboflavin Drugs 0.000 description 1
- 235000019192 riboflavin Nutrition 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 description 1
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 description 1
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- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/37—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups
- C07C45/38—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups being a primary hydroxyl group
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
- B01J2231/76—Dehydrogenation
- B01J2231/763—Dehydrogenation of -CH-XH (X= O, NH/N, S) to -C=X or -CX triple bond species
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
- B01J2531/48—Zirconium
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- Engineering & Computer Science (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
The invention provides a photocatalyst, a preparation method and application thereof, wherein the photocatalyst is VB2@ Zr-MOFs consisting of a single molecule VB2Doping in Zr-MOFs to obtain the Zr-MOFs. The catalyst has very good photocatalytic activity, and shows excellent cyclability, stability and extremely high selectivity in the aspect of preparing benzaldehyde by oxidizing benzyl alcohol by utilizing visible light catalysis.
Description
Technical Field
The invention relates to the technical field of MOFs (metal-organic frameworks) photocatalysts, and in particular relates to a photocatalyst and a preparation method and application thereof.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
Vitamin B2(VB2) It is also called riboflavin, an important water-soluble vitamin, and is widely present in human bodies and ecological environments. Flavonoids, which are natural photoactive compounds, are often used to catalyze oxidation reactions in artificial systems, such as benzyl alcohol, benzylamine, methylbenzene, sulfoxides, and the like. However, VB as a photocatalyst2There are three disadvantages: 1) due to VB2Has good solubility, is often used as a homogeneous photocatalyst and is difficult to recycle. 2) VB2It is readily degraded under visible light irradiation and is generally accepted because the hydrogen atoms on the side chains are incorporated into the aromatic nucleus to produce deuteroxanthin. 3) VB2Can generate multiple Reactive Oxygen Species (ROS), such as singlet oxygen (A)1O2) And superoxide radical (O)2 -). Generated O2 -Can be converted into H2O2And OH, which has non-selective oxidation capability, greatly affecting the selectivity of the photocatalytic product. To date, the inventors have found that there is no solution to the above three problems simultaneously.
Disclosure of Invention
The inventor found that the metal-organic frameworks (MOFs) are composed of metal nodes and organic ligands, and the rigidity of the framework structure due to the abundance of metal nodes seems to solve the VB mentioned in the background art2A possible choice of problem. In particular, the inventors found that Zr-based MOFs have extremely high thermal and chemical stability due to their strong metal carboxylic acid bonds, and that Zr-based MOFs have strong stability even if defects or ligand vacancies exist, which makes them likely to be excellent substrates for anchoring various high-efficiency homogeneous catalysts.
Therefore, in view of the problems in the prior art, the present invention aims to provide a photocatalyst, and a preparation method and application thereof. The catalyst is monomolecular VB2Doped Zr-MOFs photocatalysts, in particular, the catalyst being monomolecular VB2Doped UiO-66 (i.e., Zr)6O4(OH)4(BDC)12BDC is terephthalic acid) catalyst, abbreviated as VB2@ UiO-66, and the invention provides a method for preparing the photocatalyst, and a monomolecular VB is synthesized by adopting a one-step hydrothermal method2Doped Zr-MOFs, i.e. VB2Is added to a reaction vessel containing ZrCl4And terephthalic acid in DMF precursor solution to obtain VB by a hydrothermal method2Doped UiO-66. The preparation method of the invention has simple and easy operation, no pollution and synthesized VB2The @ UO-66 has very good photocatalytic activity, shows excellent cyclability, stability and extremely high selectivity in the aspect of preparing benzaldehyde by oxidizing benzyl alcohol by using visible light, and simultaneously solves the VB mentioned in the background technology2As three problems of the photocatalyst, the three problems are simultaneously solved for the first time.
Specifically, the technical scheme of the invention is as follows:
in a first aspect of the present invention, the present invention provides a photocatalyst, said photocatalyst being VB2@ Zr-MOFs consisting of a single molecule VB2Doping in Zr-MOFs to obtain the Zr-MOFs.
In the present invention, the Zr-MOFs is UiO-66, i.e., Zr6O4(OH)4(BDC)12And BDC is terephthalic acid.
In the present invention, VB in the photocatalyst2The amount to be doped (added) is 5 to 30mg, preferably 10 to 30mg, more preferably 30 mg.
Preferably, among said catalysts, VB2The actual doping amount of the catalyst is 0.69 to 1.42 percent of the mole percent of the ligand BDC, for example, when VB2The doping amounts of (a) and (b) are respectively 0.69%, 1.04%, 1.23% and 1.42% in mol% to BDC at 5mg, 10mg, 20mg and 30 mg. The actual doping amount of the invention is VB calculated according to ligand weight loss of a catalyst sample at 300-500 DEG C2The actual doping amount.
In the embodiment of the present invention, VB2The doping amount of (A) will affect the frame structure of MOFs when VB2An excessive doping, e.g. 40mg, leads to collapse of the MOFs framework, but when VB2The doping amount is 5-30mg, and VB2The doping amount of the catalyst can influence the photocatalytic oxidation, particularly the selectivity and the conversion rate of preparing benzaldehyde by photocatalytic oxidation of benzyl alcohol, VB2When the doping amount is 5-30mg, the selectivity is not lower than 93%, especially when VB2When the doping amount is 10-30mg, the conversion rate can reach 94%, and the selectivity can reach 100%.
In a second aspect of the present invention, the present invention also provides a method for preparing the photocatalyst described in the first aspect, which comprises preparing a Zr-MOFs solution, and then adding VB2Adding the mixture into a Zr-MOFs solution to carry out hydrothermal reaction.
In some embodiments of the invention, the Zr-MOFs is UiO-66, and the method comprises mixing zirconium chloride and terephthalic acid in DMF, and mixing VB2Adding the mixture into the mixed solution for hydrothermal reaction.
In some embodiments, the molar ratio of zirconium chloride to terephthalic acid is 1: (0.5-2), preferably 1: (0.5-1), the amount of DMF added is 50-120ml, preferably 80 ml.
In the embodiment of the present invention, VB2The doping amount of (A) is 5-30mg, preferably 10-30 mg.
In the invention, the temperature of the hydrothermal reaction is 80-130 ℃, and the reaction time is 20-50 h; preferably at 120 ℃ for 48 h.
In some embodiments of the present invention, the method further comprises the steps of cooling to room temperature after the hydrothermal reaction is finished, washing with DMF and methanol sequentially, and drying.
The drying condition is 60-80 ℃, the drying time is 10-12h, and the drying time is preferably 12h at 60 ℃.
In some embodiments of the invention, the method of preparing the photocatalyst comprises contacting zirconium chloride and terephthalic acid in a molar ratio of 1: (0.5-2) mixing in 50-120ml of DMF, and uniformly stirring; mixing 5-40mg of VB2Adding into the uniformly mixed solution, and stirring at room temperature for 10-30 min; will be added with VB2The mixed solution is subjected to hydrothermal reaction at the temperature of 80-130 ℃, cooled to room temperature after 20-50h of reaction, washed by DMF and methanol in sequence and then washed at 6 DEG CDrying at 0-80 deg.C for 10-12 hr.
VB prepared by the invention2The @ UiO-66 photocatalyst shows excellent photocatalytic selective oxidation activity and can anchor VB2Convert it into a heterogeneous catalyst, and also show extremely high selectivity and stability; meanwhile, the invention VB2The preparation and synthesis method of the @ UiO-66 photocatalyst has the advantages of simple conditions, no pollution and good stability.
In a third aspect of the present invention, the present invention also provides the use of the photocatalyst described in the first aspect above in photocatalytic selective oxidation of organic matter.
In particular, said application is VB2The application of the @ UiO-66 photocatalyst in preparing benzaldehyde by selectively oxidizing benzyl alcohol by utilizing visible light.
In embodiments of the present invention, the present invention varies the initial amount of VB2Is added to a reaction vessel containing ZrCl4And obtaining different VB from DMF precursor solution of terephthalic acid by a hydrothermal method2UiO-66 with doping amount is respectively named as VB2@ UiO-66-5/10/20/30, and the photocatalytic oxidation activity of these catalysts was tested, respectively, under visible light irradiation, with the original VB2And UiO-66 has no catalytic activity for the oxidation of benzyl alcohol. In sharp contrast, VB2The conversion efficiency and selectivity of @ UiO-66-5/10/20/30 to benzaldehyde are very high. Specifically, at VB2In the presence of @ UiO-66-30, the conversion efficiency is as high as 94%, for VB2@ UiO-66-10/20/30, the selectivity of benzyl alcohol is close to 100%. And, especially when the catalyst is VB2@ UiO-66-30, after five cycles of photocatalytic oxidation reaction, the selectivity is still close to 100%, and the conversion efficiency is still at a high level, not lower than 91%, although the conversion efficiency is gradually reduced with the cycle number.
Compared with the prior art, the invention has the beneficial effects that:
(1) VB prepared by the invention2The @ UiO-66 composite photocatalyst shows excellent photocatalytic benzyl alcohol selective oxidation activity, and experimental research shows that the VB of the invention2@ UiO-66 composite photocatalystThe chemical material can be in visible light (>420nm) is irradiated for about 5 hours, wherein the optimal sample can lead 94 percent of benzyl alcohol (20 mu mol) to complete the conversion, and the selectivity of benzaldehyde reaches 100 percent. Original UiO-66 and VB under the same conditions2None of them showed benzyl alcohol oxidizing ability. Compared with the performance of other doping MOFs photocatalytic oxidation benzyl alcohol, except for some traditional MOFs doped with metal compound, VB2@ UiO-66 exhibits a higher number of conversions.
(2) VB synthesized by the invention2@ UiO-66 has its own advantages: (1) VB2Is a common vitamin in the nature, is cheaper and more environment-friendly than halogen organic compounds or metal complexes; (2) VB in the main system2The doping content of (a) (for example, the actual doping amount is 1.42%); (3) VB2@ UiO-66 has higher conversion efficiency, even VB2TOF value of @ UiO-66-30 is MR-MIL-125(Ti) [ methyl Red-MIL-125 (Ti)]36 times of the total weight of the powder.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention. Embodiments of the invention are described in detail below with reference to the attached drawing figures, wherein:
FIG. 1 is VB prepared in example 12@ UiO-66 photocatalyst, UiO-66 and VB2XRD (a), BET (b), TGA (c) and DTA (d) comparison patterns of (a).
FIG. 2 is VB prepared in example 12FT-IR (a) and Raman (b) spectra of the @ UiO-66 photocatalyst.
FIG. 3 is VB prepared in example 12The structure of the light absorption, valence band and energy band of the @ UiO-66 photocatalyst.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out according to conventional conditions or according to conditions recommended by the manufacturers.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. The reagents or starting materials used in the present invention can be purchased from conventional sources, and unless otherwise specified, the reagents or starting materials used in the present invention can be used in a conventional manner in the art or in accordance with the product specifications. In addition, any methods and materials similar or equivalent to those described herein can be used in the methods of the present invention. The preferred embodiments and materials described herein are intended to be exemplary only.
As introduced by the background, VB is currently utilized2There are many reports of selective oxidation of benzyl alcohol as a photocatalyst, but none of them can solve the problems of selectivity, recyclability and stability at the same time. Therefore, the invention proposes a method for converting VB2High-selectivity, high-stability and recyclable heterogeneous catalyst VB (vitamin B) is obtained by doping high-stability MOFs material UiO-66 through one step method2Preparation and use of @ UiO-66 and further anchoring of this to VB2The method of (a) extends to other common MOFs materials. The invention is further described with reference to the following figures and detailed description.
Example 1
Monomolecular VB2A preparation method of a doped UiO-66 photocatalyst material comprises the following steps:
(1) 0.212g of ZrCl4And 0.136g terephthalic acid in 80mL DMF;
(2) adding VB 5mg, 10mg, 20mg, 30mg and 40mg respectively2Fully stirring for 20 minutes, and then transferring into a polytetrafluoroethylene reaction kettle; placing the reaction kettle in a 120 ℃ oven for heat preservation for 48h for solvothermal reaction, naturally cooling to room temperature after the reaction is finished, carrying out vacuum filtration, washing with DMF and methanol, and drying at 60 ℃ for 12h to obtain different VB2VB of doping amount2@ UiO-66, respectively named VB according to the doping amount2@UiO-66-5、VB2@UiO-66-10、VB2@UiO-66-20、VB2@UiO-66-30、VB2@ UiO-66-40 as a convenient watchHereinafter, in the following experimental examples, these products doped in different amounts are also referred to as VB2@UiO-66-5/10/20/30/40。
Wherein, has different VB2VB of doping amount2@UiO-66(VB2@UiO-66-5、VB2@UiO-66-10、VB2@UiO-66-20、VB2@UiO-66-30、VB2@ UiO-66-40) and UiO-66, VB2The comparative XRD (a), BET (b), TGA (c) and DTA (d) patterns of (A) are shown in FIG. 1.
Having a different VB2VB of doping amount2FT-IR (a) and Raman (b) spectra of @ UiO-66 are shown in FIG. 2.
Example 2
Monomolecular VB2The preparation method of the doped ZIF-8 photocatalyst material comprises the following steps:
(1) 0.717g of Zn (NO)3)2·6H2O and 0.180g 2-methylimidazole in 50mL DMF;
(2) 30mg of VB were continuously added2Fully stirring for 20 minutes, and then transferring into a polytetrafluoroethylene reaction kettle; putting the reaction kettle into a drying oven at 140 ℃ for heat preservation for 24 hours to carry out solvothermal reaction, naturally cooling to room temperature after the reaction is finished, carrying out vacuum filtration, washing with DMF and methanol, and drying at 60 ℃ for 12 hours to obtain light yellow powder, namely VB2@ZIF-8。
Example 3
Monomolecular VB2The preparation method of the doped MIL-125 photocatalyst material comprises the following steps:
(1) 0.3mL of Ti (OiPr)4And a mixed solution of 250mg of terephthalic acid in 9mL of DMF and 1mL of methanol;
(2) 30mg of VB were continuously added2Fully stirring for 5 minutes, and then transferring into a polytetrafluoroethylene reaction kettle with the volume of 20 mL; placing the reaction kettle in a drying oven at 150 ℃ for heat preservation for 48h for solvothermal reaction, naturally cooling to room temperature after the reaction is finished, performing vacuum filtration, washing with DMF and methanol, and drying in a fume hood overnight to obtain yellow powder, namely VB2@MIL-125。
Example 4
Monomolecular VB2The preparation method of the doped Bi-BTC photocatalyst material comprises the following steps:
(1) 0.236g of Bi (NO)3)3·5H2O and 0.193g trimesic acid were dissolved in the mixture DMF/MeOH (5mL,1: 3);
(2) 30mg of VB were continuously added2Fully stirring for 20 minutes, and then transferring into a 100mL polytetrafluoroethylene reaction kettle; placing the reaction kettle in a programmed air-temperature oven, heating to 120 deg.C for 45 hr, maintaining for 12 hr, cooling to room temperature at 2 deg.C/min, vacuum filtering, washing with DMF and methanol, and drying at 60 deg.C overnight to obtain VB2@Bi-BTC。
Examples of the experiments
Phase testing:
VB prepared in example 12The X-ray diffraction pattern of @ UiO-66 is shown in FIG. 1, and it can be seen from FIG. 1(a) that VB is doped2The sample after that still maintains the structure of UiO-66, and no other impurity peaks appear. Following VB2The initial amount was increased and the intensity of the two main peaks was somewhat reduced, but still maintaining the framework structure of UiO-66. For sample VB2@ UiO-66-40, the two main peaks are greatly reduced in intensity, and excessive VB can be presumed2The addition caused collapse of the frame structure, so only VB was considered in the subsequent studies2@UiO-66-5、VB2@UiO-66-10、VB2@UiO-66-20、VB2@UiO-66-30。
Specific surface area test:
VB prepared in example 12The BET test pattern of @ UiO-66 is shown in FIG. 1(b), from which it can be seen that the specific surface area of UiO-66 varies with VB2The amount of addition is increasing and decreasing.
Thermogravimetric and differential thermal testing:
VB prepared in example 12@ UiO-66 and UiO-66, VB2The thermogravimetry and differential heat of (c) are shown in FIGS. 1(c) and (d). As can be seen, the original UiO-66 ligand weight loss is below theoretical, i.e., UiO-66 has available ligand defects. Meanwhile, the actual VB can be calculated from the ligand weight loss results of different samples2The doping amount follows the initial VB2The amount of addition increases. At the same time, VB at 300 DEG C2@ UiO-66 does not appear similar to VB2Significant weight loss, and a shift in decomposition temperature compared to simple UiO-66, all demonstrate VB2And UiO-66 may have chemical bond interactions.
Infrared and raman testing:
VB prepared in example 12@ UiO-66 and UiO-66, VB2The infrared and raman contrast plots of (a) and (b) of fig. 2 are shown. In the UiO-66, the longitudinal and transverse vibration modes of Zr-O were 682.96, 554.97 and 475.74cm-1The triplet of (2). VB2@ UiO-66 Medium, 682.96cm-1The peak value at (A) is shifted to 662.06cm-1554.97 and 475.74cm-1The peak intensity decreases with VB2At 538.86cm-1Gradually a new broad peak appears, which means that a new Zr-O/Zr-N bond is generated. The peak of carboxylic acid group is gradually changed from 1586.56 to 1547.01cm-1The shift is caused by a change in the adjacent O-Zr-O-Zr bond. In Raman spectrum FIG. 2(b), VB2@ UiO-66-30 at 1610.2cm-1There is a new significant raman peak nearby, similar to the reported signal of carbonyl compounds binding to metal ions.
Testing the photophysical properties:
VB prepared in example 12@ UiO-66, UiO-66 and VB2The ultraviolet-visible diffuse reflection absorption spectrum of (A) is shown in FIG. 3(a), and it can be seen from FIG. 3(a) that VB2The addition of (2) greatly improves the absorption of UiO-66 in the visible light region. As can be seen from the valence band spectrum of FIG. 3(b), the valence band of UiO-66 is 2.58eV, which follows VB2Increase in content, VB2The valence band of @ UiO-66 moves from 2.66eV to 2.49 eV. Meanwhile, the band diagrams of all samples are shown in fig. 3 (c). Thermodynamically, VB of light excitation2Can transfer electrons to O2Generating O2 ·-And the like. However, VB after bonding to UiO-662@ UiO-66 to O2 ·-Generation ofIs no longer feasible. This means VB2The introduction of (2) can adjust the energy band position of the material, thereby reducing the types of active oxygen. It may serve as an advantage to increase the selectivity of certain organic oxidation reactions.
Photocatalytic activity test
1. The test method comprises the following steps:
the photocatalytic oxidation test was carried out in a system with a closed quartz glass vessel attached. A300W xenon lamp is selected as a light source for top irradiation, a filter is 420nm, and the photocatalytic activity of the sample is evaluated by the selective oxidation performance of benzyl alcohol.
20mg of catalyst, 20. mu. mol of benzyl alcohol, 20mL of n-hexane were placed in a two-port quartz reactor. Under the irradiation of a 300w xenon lamp (ps-sxe300, Beijing Perfectlight Technology Co., LTD., China), a 420nm filter, oxygen bubbling, and catalytic oxidation reaction were carried out at a constant temperature (10 ℃). The product was analyzed for yield and type by GC-MS chromatography (GC-MS-qp2010, SH-Rtx-Wax column).
2. And (3) test results:
different VB prepared in example 12VB of doping amount2The performance profiles of the @ UiO-66 photocatalyst for oxidizing benzyl alcohol are shown in Table 1.
TABLE 1 UiO-66, VB2And VB2Results of benzyl alcohol oxidation of @ UiO-66-5/10/20/30
Note: n.d. indicates not detected, -indicates that no product was detected and therefore cannot be calculated.
As can be seen from Table 1, the original VB was observed under visible light irradiation2And UiO-66 has no catalytic activity for the oxidation of benzyl alcohol. In sharp contrast, VB2The conversion efficiency and selectivity of @ UiO-66-5/10/20/30 to benzaldehyde are very high. Specifically, at VB2In the presence of @ UiO-66-30, the conversion efficiency is as high as 94%, for VB2@ UiO-66-10/20/30, the selectivity of benzyl alcohol is close to 100%.
To go intoOne step verification of stability, this experimental example is to VB2The photocatalytic oxidation reaction was carried out for five cycles on @ UiO-66-30 (prepared in example 1), and the results of the photocatalytic oxidation benzyl alcohol stability test are shown in Table 2.
TABLE 2 VB2Test of oxidative stability of benzyl alcohol of @ UiO-66-30
As shown in table 2, after 5 cycles, the selectivity was still close to 100%, and the conversion efficiency was still at a higher level, at least higher than 91%, although there was a decrease.
VB prepared in examples 2 to 42@ZIF-8、VB2@ MIL-125 and VB2The photocatalytic oxidation performance of benzyl alcohol of @ Bi-BTC is shown in Table 3.
TABLE 3 benzyl alcohol Oxidation Performance of different MOFs materials
Note: n.d. indicates not detected, -indicates that no product was detected and therefore cannot be calculated.
As shown in Table 3, VB2@ MIL-125 and VB2@ Bi-BTC exhibits good photooxidation ability and selectivity. This result may be related to VB2Is related to the actual doping amount. Ti has good affinity with oxygen, such as Zr, which results in more VB2Is introduced into MIL-125. Meanwhile, Bi-based MOFs have been demonstrated to have a significant heavy metal effect due to the ability to generate more triplet excitons. These results provide valuable experience in selecting highly efficient MOFs materials as substrates for labile coenzymes.
Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (14)
1. The photocatalyst for selectively catalyzing benzyl alcohol into benzaldehyde is characterized in that the photocatalyst is VB2@ Zr-MOFs consisting of a single molecule VB2Obtained by doping in Zr-MOFs, the VB2Is vitamin B2。
2. The photocatalyst for selectively catalyzing benzyl alcohol to benzaldehyde according to claim 1, wherein the Zr-MOFs is UiO-66 (Zr)6O4(OH)4(BDC)12And the BDC is terephthalic acid.
3. The photocatalyst for selectively catalyzing benzyl alcohol to benzaldehyde according to claim 1 or 2, wherein VB is higher than VB2The doping amount of the catalyst is 5-30 mg.
4. The photocatalyst for selectively catalyzing benzyl alcohol to benzaldehyde according to claim 3, wherein VB is higher than VB2The doping amount of the catalyst is 10-30 mg.
5. The photocatalyst for selectively catalyzing benzyl alcohol to benzaldehyde according to claim 2, wherein VB is contained in the photocatalyst2The mol percentage of the ligand BDC is 0.69-1.42%.
6. The preparation method of the photocatalyst for selectively catalyzing benzyl alcohol to benzaldehyde according to claim 1 or 2, wherein the preparation method comprises the steps of preparing a Zr-MOFs solution, and then adding VB2Adding the mixture into a Zr-MOFs solution to carry out hydrothermal reaction.
7. The method of claim 6, wherein the photocatalyst is selected from the group consisting of methanol, and benzaldehydeWherein the Zr-MOFs is UiO-66, and the method comprises mixing zirconium chloride and terephthalic acid in N, N-dimethylformamide and mixing VB2Adding the mixture into the mixed solution for hydrothermal reaction.
8. The method for preparing the photocatalyst for selectively catalyzing benzyl alcohol to benzaldehyde according to claim 7, wherein the molar ratio of zirconium chloride to terephthalic acid is 1: 0.5-2, the adding amount of N, N-dimethylformamide is 50-120 ml.
9. The method as claimed in claim 7, wherein VB is higher than VB in the presence of the photocatalyst2The doping amount of the catalyst is 5-30 mg.
10. The method as claimed in claim 7, wherein VB is higher than VB in the presence of the photocatalyst2The doping amount of the catalyst is 10-30 mg.
11. The method for preparing the photocatalyst for selectively catalyzing benzyl alcohol to benzaldehyde according to any one of claims 6 to 10, wherein the temperature of the hydrothermal reaction is 80-130 ℃ and the reaction time is 20-50 h.
12. The method for preparing the photocatalyst for selectively catalyzing benzyl alcohol to benzaldehyde according to any one of claims 6 to 10, wherein the method further comprises the steps of cooling to room temperature after the hydrothermal reaction is finished, washing with N, N-dimethylformamide and methanol in sequence, and drying.
13. The method for preparing the photocatalyst for selectively catalyzing benzyl alcohol to benzaldehyde according to claim 12, wherein the drying condition is 60-80 ℃ and the drying time is 10-12 h.
14. The selective catalytic benzylalcohol of claim 7 being benzaldehydeThe method for preparing a photocatalyst according to (1), characterized in that the method comprises subjecting zirconium chloride and terephthalic acid to a reaction in a molar ratio of 1: 0.5-2 is mixed in 50-120ml of N, N-dimethylformamide and evenly stirred; mixing 5-40mg of VB2Adding into the above mixed solution, and stirring at room temperature for 10-30 min; will be added with VB2Carrying out hydrothermal reaction on the mixed solution at the temperature of 80-130 ℃, cooling to room temperature after reacting for 20-50h, washing with N, N-dimethylformamide and methanol in sequence, and then drying for 10-12h at the temperature of 60-80 ℃ to obtain the catalyst.
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