CN109647540A - A kind of novel porous titanium-organic framework materials and preparation method thereof producing hydrogen for visible light photocatalysis - Google Patents
A kind of novel porous titanium-organic framework materials and preparation method thereof producing hydrogen for visible light photocatalysis Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 42
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 21
- 239000001257 hydrogen Substances 0.000 title claims abstract description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 239000013384 organic framework Substances 0.000 title claims abstract description 16
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 16
- 238000007146 photocatalysis Methods 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000013110 organic ligand Substances 0.000 claims abstract description 49
- 239000010936 titanium Substances 0.000 claims abstract description 21
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 12
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 80
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 48
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 34
- 150000003628 tricarboxylic acids Chemical class 0.000 claims description 19
- 238000010992 reflux Methods 0.000 claims description 16
- 239000000725 suspension Substances 0.000 claims description 16
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 12
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 12
- 239000013086 titanium-based metal-organic framework Substances 0.000 claims description 12
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 10
- 238000004140 cleaning Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 238000010668 complexation reaction Methods 0.000 claims description 8
- 238000006462 rearrangement reaction Methods 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000002604 ultrasonography Methods 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- -1 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000002178 crystalline material Substances 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 3
- SATWKVZGMWCXOJ-UHFFFAOYSA-N 4-[3,5-bis(4-carboxyphenyl)phenyl]benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC(C=2C=CC(=CC=2)C(O)=O)=CC(C=2C=CC(=CC=2)C(O)=O)=C1 SATWKVZGMWCXOJ-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052719 titanium Inorganic materials 0.000 abstract description 9
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 238000000354 decomposition reaction Methods 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 230000008707 rearrangement Effects 0.000 abstract description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract 1
- 239000004615 ingredient Substances 0.000 abstract 1
- 150000003627 tricarboxylic acid derivatives Chemical class 0.000 abstract 1
- 239000012621 metal-organic framework Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 3
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 3
- 239000013132 MOF-5 Substances 0.000 description 2
- 229910003077 Ti−O Inorganic materials 0.000 description 2
- 230000009102 absorption Effects 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000007540 photo-reduction reaction Methods 0.000 description 1
- 238000005381 potential energy Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
-
- B01J35/39—
-
- B01J35/60—
-
- B01J35/617—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
Abstract
The invention discloses a kind of novel porous titanium-organic framework materials and preparation method thereof that hydrogen is produced for visible light photocatalysis, it is characterized in that using a series of tricarboxylic acid organic ligand as Organic Ingredients, using isopropyl titanate as metal titanium source, pass through solvent thermal reaction, titanium ion is with carboxyl coordination and rearrangement forms titanyl cluster, carries out hexa-coordinate with organic ligand and obtains titanium-organic framework materials.The present invention is simple using solvothermal preparation method, and yield is higher, products pure, crystallinity is preferable, obtained titanium-organic framework materials specific surface area is larger, has excellent absorbability to visible light and can have important environmental benefit and energy source use to be worth with photocatalysis Decomposition aquatic products hydrogen.
Description
Technical field
It is the present invention relates to a kind of metal-organic framework materials, in particular to a kind of to produce the new of hydrogen for visible light photocatalysis
Type Porous titanium-organic framework materials and preparation method thereof, belong to organic material technical field.
Background technique
In face of serious environmental problem and energy crisis, the demand of cleaning and sustainable energy is very necessary for the whole world
, but still be a significant challenge, with solar energy photocatalytic decompose aquatic products hydrogen be to provide cleaning and high performance energy most and have it is uncommon
One of solution of prestige.Since visible light accounts for about the 43% of solar energy, and ultraviolet light (UV) only contributes about 4%, therefore visible
The photocatalysis of optical drive is most important for effective use solar energy.Metal-organic framework materials (MOFs) are as a kind of novel
Porous crystalline material has good application prospect in many fields.For MOFs because of its large surface area, aperture is adjustable and adjustable
Optoelectronic architecture becomes ideal catalysis material.Report that MOFs has Photocatalyzed Hydrogen Production effect for the first time from Mori seminar
Since, existing 23 kinds of MOFs show effective Photocatalyzed Hydrogen Production activity.But the major defect of MOFs Photocatalyzed Hydrogen Production is most
Number MOF is unstable in water.Because Ti-O bonding action has good water stability, bloom compared with other low-valent metals
Learn response and the photoreduction performance from feature Ti-O key.Ti-MOFs has bigger surface area, has in visible light region
More light absorptions, and the TiO with the photochemical catalyst as most study2It compares, it is easier to adjust photoelectric properties, Ti-
MOFs is one of most promising photocatalysis MOFs.However, due to the high response and harsh synthesis condition of titanium precursors,
The synthesis of Ti-MOFs is still a challenge.The Ti-MOFs being synthesized at present, only MIL-125 can be applied to visible light
The Photocatalyzed Hydrogen Production of driving.The research of Ti-MOFs still in early stage, meanwhile, triphenylamine and its derivative are good due to it
Stability, strong electron behavior and high open-work ability and be widely used in organic semiconductor, organic solar batteries and
DSSC, this is conducive to electric charge transfer and carries out redox reaction into metal cluster.However it is captured in seldom report MOFs for light
Application, therefore prepare a kind of novel Ti-MOFs for producing hydrogen with high efficiency photocatalysis and be necessary, this is also following energy
Material opens a new idea.
Summary of the invention
The Novel Titanium metal-organic framework materials prepared by the present invention for producing hydrogen for visible light photocatalysis are with regular hole
The two-dimensional layer infinite network crystalline material in road, the crystalline material are configured to titanyl cluster and three by titanium ion and oxygen atom rearrangement
First carboxylic acid organic ligand forms three-dimensional network frame structure by hexa-coordinate, which is
Ti-MOF-1:Ti6(μ3-O)6(OH)6(TCA)2(H2O)(DMF)2；
Ti-MOF-2:Ti6(μ3-O)6(OH)6(BTB)2(DMF)2,Ti-MOF-3:Ti6(μ3-O)6(OH)6(BTCA)2
(DMF)2。
The object of the present invention is to provide a kind of novel porous titanium-organic frame materials that hydrogen is produced for visible light photocatalysis
Material and preparation method thereof.Simple with preparation method, wherein Ti-MOF-1 specific surface area is 560m2The ratio table of/g, Ti-MOF-2
Area is 628m2The specific surface area of/g Ti-MOF-3 is 655m2/g.Wherein Ti-MOF-1 and Ti-MOF-3 is to visible absorption energy
Power is strong, has excellent Photocatalyzed Hydrogen Production performance in triethanolamine/acetonitrile/water system (wherein triethanolamine does sacrifice agent).
The technical scheme adopted by the invention is that: tricarboxylic acid organic ligand is added in DMF, is filled in hydrothermal reaction kettle
Divide dissolution, isopropyl titanate hydro-thermal single step reaction is then added and prepares Ti-MOF-1, Ti-MOF-2, Ti-MOF-3, Ti-MOF-
4, Ti-MOF-5 and Ti-MOF-6.
To achieve the above object, technical solution of the present invention comprising the following steps:
(1) required tricarboxylic acid organic ligand is added in the polytetrafluoroethylene (PTFE) hydrothermal reaction kettle of 25mL, 5mL is added
N,N-Dimethylformamide (hereinafter referred to as DMF), ultrasound dissolves it sufficiently, obtains clear solution；
(2) isopropyl titanate is added into the resulting clear solution of step (1), stirs, in constant temperature oven
180 DEG C of 18~30h of reaction, the carboxylic acid oxygen of organic ligand and titanium ion rearrangement reaction become Ti in hydrothermal reaction process6O6Metal
Cluster, and complexation reaction is carried out with organic ligand, the suspension after obtaining hydro-thermal reaction；
(3) suspension after hydro-thermal reaction that step (2) obtains is naturally cooled into room temperature, centrifuge separation cleaning, respectively
It is cleaned 3~5 times with DMF and methanol, then with DMF in 120 DEG C of 7~9h of reflux, with methanol in 80 DEG C of 7~9h of reflux, centrifugation is produced
Object, 120 DEG C of 10~12h of vacuum drying of vacuum, obtains titanium-based metal-organic frame material of titanyl cluster Yu organic ligand hexa-coordinate
Material.
The tricarboxylic acid organic ligand is 4,4 ', 4 "-tricarboxylic acids triphenylamine (H3TCA), 1,3,5- tri- (4- carboxyl benzene
Base) benzene (H3BTB), H3One of BTCA, TPT, BBC or BTE.
The molar ratio of the isopropyl titanate and tricarboxylic acid organic ligand is 1:1~2.
Compared with the background art, the invention has the advantages that:
1, titanium of the invention-organic framework materials preparation method is hydro-thermal method, and the synthetic method craft is simple, condition
Mild and environmental-friendly, yield is up to 60%~71%.A series of titaniums-organic framework materials structure novel obtained belongs to
In hexagonal crystal system, space group P63/MCM, cell parameter isα=β=90 °,
γ=120 °, the material are by Ti6O6The carboxylic acid oxygen of metal cluster and organic ligand is coordinated to be formed, then passes through organic ligand forming layer
Shape porous structure constitutes three-dimensional network frame structure by Van der Waals force and hydrogen bond action between layers；
2, titanium-organic framework materials of the invention have good absorption to visible light, and can be in triethanolamine/second
There is good Photocatalyzed Hydrogen Production effect in nitrile/water, there is potential energy value；
3, titanium of the invention-organic framework materials crystallization degree is high, stability is good, can keep in water for a long time
Stable structure, after salt acid soak 2 days for impregnating that 7 days and PH are 0 in water, x-ray diffractogram of powder spectrum still can be with
With it is good corresponding before no immersion, it was demonstrated that it is with preferable water stability and acid resistance.
Detailed description of the invention
Fig. 1 is the crystal structure schematic diagram of titanium-organic framework materials of the present invention, a) is coordinated for TCA and titanium cluster
Structural schematic diagram, b) be BTB and titanium cluster coordination structure schematic diagram, c) it is BTCA and titanium cluster coordination structure schematic diagram.
Fig. 2 is the XRD diagram of titanium-organic framework materials of the present invention.
Fig. 3 is that the FTIR of titanium-organic framework materials of the present invention schemes.
Fig. 4 is titanium of the present invention-organic framework materials Ti-MOF-1, Ti-MOF-2 and Ti-MOF-3 SEM/TEM figure.
Fig. 5 is the photocatalysis Decomposition aquatic products hydrogen effect picture of titanium-organic framework materials of the present invention.
Specific embodiment
Embodiment 1:
(1) by the required "-tricarboxylic acids triphenylamine (H of tricarboxylic acid organic ligand 4,4 ', 43TCA poly- the four of 25mL) are added to
In vinyl fluoride hydrothermal reaction kettle, it is added 5mL n,N-Dimethylformamide (hereinafter referred to as DMF), ultrasound dissolves it sufficiently, obtains
To clear solution；
(2) mole of isopropyl titanate and tricarboxylic acid organic ligand 1:1 is pressed into the resulting clear solution of step (1)
Than isopropyl titanate is added, stirs, reacted at 180 DEG C of constant temperature oven for 24 hours, organic ligand in hydrothermal reaction process
Carboxylic acid oxygen and titanium ion rearrangement reaction become Ti6O6Metal cluster, and complexation reaction is carried out with organic ligand, after obtaining hydro-thermal reaction
Suspension；
(3) suspension after hydro-thermal reaction that step (2) obtains is naturally cooled into room temperature, centrifuge separation cleaning, respectively
It is cleaned 4 times with DMF and methanol, is then centrifuged product, vacuum 120 with methanol in 80 DEG C of reflux 8h in 120 DEG C of reflux 7h with DMF
DEG C vacuum drying 12h, obtain titanium-based metal-organic framework materials Ti-MOF-1 of titanyl cluster Yu organic ligand hexa-coordinate.
Embodiment 2:
(1) by required tricarboxylic acid organic ligand 1,3,5- tri- (4- carboxyl phenyl) benzene (H3BTB) it is added to the poly- of 25mL
In tetrafluoroethene hydrothermal reaction kettle, it is added 5mL n,N-Dimethylformamide (hereinafter referred to as DMF), ultrasound dissolves it sufficiently,
Obtain clear solution；
(2) the rubbing by isopropyl titanate and tricarboxylic acid organic ligand 1:1.5 into the resulting clear solution of step (1)
You stir, the organic ligand in 180 DEG C of reaction 18h of constant temperature oven, hydrothermal reaction process than isopropyl titanate is added
Carboxylic acid oxygen and titanium ion rearrangement reaction become Ti6O6 metal cluster, and with organic ligand carry out complexation reaction, obtain hydro-thermal reaction
Suspension afterwards；
(3) suspension after hydro-thermal reaction that step (2) obtains is naturally cooled into room temperature, centrifuge separation cleaning, respectively
It is cleaned 3 times with DMF and methanol, is then centrifuged product, vacuum 120 with methanol in 80 DEG C of reflux 9h in 120 DEG C of reflux 8h with DMF
DEG C vacuum drying 12h, obtain titanium-based metal-organic framework materials Ti-MOF-2 of titanyl cluster Yu organic ligand hexa-coordinate.
Embodiment 3:
(1) by required tricarboxylic acid organic ligand H3BTCA is added in the polytetrafluoroethylene (PTFE) hydrothermal reaction kettle of 25mL, is added
Enter 5mL n,N-Dimethylformamide (hereinafter referred to as DMF), ultrasound dissolves it sufficiently, obtains clear solution；
(2) mole of isopropyl titanate and tricarboxylic acid organic ligand 1:2 is pressed into the resulting clear solution of step (1)
Than isopropyl titanate is added, stir, the organic ligand in 180 DEG C of reaction 30h of constant temperature oven, hydrothermal reaction process
Carboxylic acid oxygen and titanium ion rearrangement reaction become Ti6O6Metal cluster, and complexation reaction is carried out with organic ligand, after obtaining hydro-thermal reaction
Suspension；
(3) suspension after hydro-thermal reaction that step (2) obtains is naturally cooled into room temperature, centrifuge separation cleaning, respectively
It is cleaned 5 times with DMF and methanol, is then centrifuged product, vacuum 120 with methanol in 80 DEG C of reflux 7h in 120 DEG C of reflux 9h with DMF
DEG C vacuum drying 10h, obtain titanium-based metal-organic framework materials Ti-MOF-3 of titanyl cluster Yu organic ligand hexa-coordinate.
Embodiment 4:
(1) required tricarboxylic acid organic ligand TPT is added in the polytetrafluoroethylene (PTFE) hydrothermal reaction kettle of 25mL, is added
5mL n,N-Dimethylformamide (hereinafter referred to as DMF), ultrasound dissolves it sufficiently, obtains clear solution；
(2) the rubbing by isopropyl titanate and tricarboxylic acid organic ligand 1:1.5 into the resulting clear solution of step (1)
You stir, react at 180 DEG C of constant temperature oven for 24 hours, organic ligand in hydrothermal reaction process than isopropyl titanate is added
Carboxylic acid oxygen and titanium ion rearrangement reaction become Ti6O6Metal cluster, and complexation reaction is carried out with organic ligand, obtain hydro-thermal reaction
Suspension afterwards；
(3) suspension after hydro-thermal reaction that step (2) obtains is naturally cooled into room temperature, centrifuge separation cleaning, respectively
It is cleaned 4 times with DMF and methanol, is then centrifuged product, vacuum 120 with methanol in 80 DEG C of reflux 8h in 120 DEG C of reflux 7h with DMF
DEG C vacuum drying 12h, obtain titanium-based metal-organic framework materials Ti-MOF-4 of titanyl cluster Yu organic ligand hexa-coordinate.
Embodiment 5:
(1) required tricarboxylic acid organic ligand BBC is added in the polytetrafluoroethylene (PTFE) hydrothermal reaction kettle of 25mL, is added
5mL n,N-Dimethylformamide (hereinafter referred to as DMF), ultrasound dissolves it sufficiently, obtains clear solution；
(2) mole of isopropyl titanate and tricarboxylic acid organic ligand 1:1 is pressed into the resulting clear solution of step (1)
Than isopropyl titanate is added, stir, the organic ligand in 180 DEG C of reaction 18h of constant temperature oven, hydrothermal reaction process
Carboxylic acid oxygen and titanium ion rearrangement reaction become Ti6O6 metal cluster, and carry out complexation reaction with organic ligand, after obtaining hydro-thermal reaction
Suspension；
(3) suspension after hydro-thermal reaction that step (2) obtains is naturally cooled into room temperature, centrifuge separation cleaning, respectively
It is cleaned 3 times with DMF and methanol, is then centrifuged product, vacuum 120 with methanol in 80 DEG C of reflux 9h in 120 DEG C of reflux 8h with DMF
DEG C vacuum drying 11h, obtain titanium-based metal-organic framework materials Ti-MOF-5 of titanyl cluster Yu organic ligand hexa-coordinate.
Embodiment 6:
(1) required tricarboxylic acid organic ligand BTE is added in the polytetrafluoroethylene (PTFE) hydrothermal reaction kettle of 25mL, is added
5mL n,N-Dimethylformamide (hereinafter referred to as DMF), ultrasound dissolves it sufficiently, obtains clear solution；
(2) mole of isopropyl titanate and tricarboxylic acid organic ligand 1:2 is pressed into the resulting clear solution of step (1)
Than isopropyl titanate is added, stir, the organic ligand in 180 DEG C of reaction 30h of constant temperature oven, hydrothermal reaction process
Carboxylic acid oxygen and titanium ion rearrangement reaction become Ti6O6Metal cluster, and complexation reaction is carried out with organic ligand, after obtaining hydro-thermal reaction
Suspension；
(3) suspension after hydro-thermal reaction that step (2) obtains is naturally cooled into room temperature, centrifuge separation cleaning, respectively
It is cleaned 5 times with DMF and methanol, is then centrifuged product, vacuum 120 with methanol in 80 DEG C of reflux 7h in 120 DEG C of reflux 9h with DMF
DEG C vacuum drying 10h, obtain titanium-based metal-organic framework materials Ti-MOF-6 of titanyl cluster Yu organic ligand hexa-coordinate.
It is sub that the above enumerated are only specific embodiments of the present invention.It is clear that the invention is not restricted to which above embodiment, may be used also
With there are many deformations.All changes that those skilled in the art directly can export or associate from present disclosure
Shape is considered as protection scope of the present invention.
Claims (4)
1. a kind of novel porous titanium-organic framework materials and preparation method thereof for producing hydrogen for visible light photocatalysis, special
Sign is: the titanium-organic framework materials are prepared by one step of solvent method, and the crystalline material of generation has unprecedented
Ti6O6The crystal structure of cluster and long-range order, Ti in the material6O6Cluster by being interconnected to form chain structure, then with organic ligand
It connects to form three-dimensional network frame structure by hexa-coordinate.
2. a kind of novel porous titanium-organic frame material for producing hydrogen for visible light photocatalysis according to claim 1
Material and preparation method thereof, which comprises the following steps:
(1) required tricarboxylic acid organic ligand is added in the polytetrafluoroethylene (PTFE) hydrothermal reaction kettle of 25mL, 5mL N, N- is added
Dimethylformamide (hereinafter referred to as DMF), ultrasound dissolves it sufficiently, obtains clear solution；
(2) isopropyl titanate is added into the resulting clear solution of step (1), stirs, at 180 DEG C of constant temperature oven
18~30h is reacted, the carboxylic acid oxygen of organic ligand and titanium ion rearrangement reaction become Ti in hydrothermal reaction process6O6Metal cluster, and with
Organic ligand carries out complexation reaction, the suspension after obtaining hydro-thermal reaction；
(3) suspension after hydro-thermal reaction that step (2) obtains is naturally cooled into room temperature, DMF is used in centrifuge separation cleaning respectively
It is cleaned 3~5 times with methanol, is then centrifuged product, very with methanol in 80 DEG C of 7~9h of reflux in 120 DEG C of 7~9h of reflux with DMF
120 DEG C of 10~12h of vacuum drying of sky, obtain titanium-based metal-organic framework materials of titanyl cluster Yu organic ligand hexa-coordinate.
3. a kind of novel porous titanium-organic frame material for producing hydrogen for visible light photocatalysis according to claim 2
Material and preparation method thereof, it is characterised in that: the tricarboxylic acid organic ligand is 4,4 ', 4 "-tricarboxylic acids triphenylamines
(H3TCA), 1,3,5- tri- (4- carboxyl phenyl) benzene (H3BTB), H3One of BTCA, TPT, BBC or BTE.
4. a kind of novel porous titanium-organic frame material for producing hydrogen for visible light photocatalysis according to claim 2
Material and preparation method thereof, it is characterised in that: the molar ratio of the isopropyl titanate and tricarboxylic acid organic ligand is 1:1~2.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111889145A (en) * | 2020-07-20 | 2020-11-06 | 齐鲁工业大学 | Iron-doped titanium-oxygen cluster material and synthesis method and application thereof |
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| CN111889145A (en) * | 2020-07-20 | 2020-11-06 | 齐鲁工业大学 | Iron-doped titanium-oxygen cluster material and synthesis method and application thereof |
| CN111889145B (en) * | 2020-07-20 | 2022-08-30 | 齐鲁工业大学 | Iron-doped titanium-oxygen cluster material and synthesis method and application thereof |
| CN113443954A (en) * | 2021-06-25 | 2021-09-28 | 太原理工大学 | Efficient separation method for ethane in mixed gas |
| CN113443954B (en) * | 2021-06-25 | 2022-07-08 | 太原理工大学 | Efficient separation method for ethane in mixed gas |
| CN114130431A (en) * | 2021-11-23 | 2022-03-04 | 中国科学院大连化学物理研究所 | Preparation method and application of P-type pyrenyl metal organic framework single crystal material and nanobelt |
| CN114471727A (en) * | 2022-02-10 | 2022-05-13 | 重庆工商大学 | Au @ NH2-MIL-125(Cu/Ti) photocatalyst and preparation method and application thereof |
| CN114471727B (en) * | 2022-02-10 | 2023-11-17 | 重庆工商大学 | Au@NH 2 MIL-125 (Cu/Ti) photocatalyst, and preparation method and application thereof |
| CN115245764A (en) * | 2022-03-14 | 2022-10-28 | 大连理工大学 | Method for preparing titanium-based metal organic framework film by titanium-oxygen cluster |
| CN115245764B (en) * | 2022-03-14 | 2023-11-21 | 大连理工大学 | Method for preparing titanium-based metal organic framework film by using titanium oxide clusters |
| CN114685808A (en) * | 2022-04-22 | 2022-07-01 | 浙江工业大学 | Hydrogen bond associated pseudo three-dimensional titanium-carbon-based micro complex with one-dimensional pores opened, and preparation method and application thereof |
| CN115582148A (en) * | 2022-10-28 | 2023-01-10 | 浙江大学 | Preparation method and application of titanium ion doped cerium-based metal organic framework photocatalyst |
| CN115582148B (en) * | 2022-10-28 | 2023-08-18 | 浙江大学 | Preparation method and application of titanium ion doped cerium-based metal organic framework photocatalyst |
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