CN110354901A - A kind of preparation method and application of the monatomic porphyryl MOF material of metal - Google Patents
A kind of preparation method and application of the monatomic porphyryl MOF material of metal Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 45
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 37
- 239000002184 metal Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000005406 washing Methods 0.000 claims abstract description 29
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 25
- 239000001257 hydrogen Substances 0.000 claims abstract description 25
- 238000010438 heat treatment Methods 0.000 claims abstract description 20
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 239000005711 Benzoic acid Substances 0.000 claims abstract description 9
- 235000010233 benzoic acid Nutrition 0.000 claims abstract description 9
- 239000007787 solid Substances 0.000 claims abstract description 8
- 229910007932 ZrCl4 Inorganic materials 0.000 claims abstract description 7
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims abstract description 7
- 229910003594 H2PtCl6.6H2O Inorganic materials 0.000 claims abstract description 5
- 229910021638 Iridium(III) chloride Inorganic materials 0.000 claims abstract description 5
- -1 porphyrin carboxylic acid Chemical class 0.000 claims abstract description 5
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 claims abstract description 5
- 229910009112 xH2O Inorganic materials 0.000 claims abstract description 5
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 3
- 238000001035 drying Methods 0.000 claims abstract description 3
- 238000007789 sealing Methods 0.000 claims abstract description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 238000004519 manufacturing process Methods 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 5
- 238000005119 centrifugation Methods 0.000 claims description 4
- 229910007926 ZrCl Inorganic materials 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 5
- 239000012621 metal-organic framework Substances 0.000 description 33
- 239000013078 crystal Substances 0.000 description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 9
- 238000004090 dissolution Methods 0.000 description 8
- 238000006555 catalytic reaction Methods 0.000 description 7
- 235000019441 ethanol Nutrition 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- 229960004756 ethanol Drugs 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 150000004032 porphyrins Chemical class 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 230000001699 photocatalysis Effects 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 229910002621 H2PtCl6 Inorganic materials 0.000 description 2
- 229910010068 TiCl2 Inorganic materials 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 239000003426 co-catalyst Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000003504 photosensitizing agent Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 229910015189 FeOx Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 239000012924 metal-organic framework composite Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-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
- 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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- 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
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
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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
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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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
- B01J2531/46—Titanium
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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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
- C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The invention discloses a kind of preparation method and applications of the monatomic porphyryl MOF material of metal.The preparation method of the porphyryl MOF material, comprising the following steps: (1) weigh ZrCl4, porphyrin carboxylic acid and benzoic acid be dissolved in DMF reagent, transfer them in reaction kettle, heating reaction, then washed, it is dry, obtain PCN-224；(2) by PCN-224 and TiCp obtained by step (1)2Cl2It is blended in DMF solvent, mixture is transferred in reaction kettle, heating reaction, then washing drying is carried out, obtain PCN-224 (Zr/Ti)；(3) by step (2) obtained solid PCN-224 (Zr/Ti), IrCl3.xH2O、H2PtCl6.6H2O is dispersed in DMF, sealing heating reaction in a kettle, then is washed, dry to get the porphyryl MOF material for limiting single metal atom.The monatomic porphyryl MOF material of metal prepared by the present invention can be used as producing hydrogen catalyst, and hydrogen output is high.
Description
Technical field
The present invention relates to catalyst fields, and in particular to a kind of preparation method of the monatomic porphyryl MOF material of metal and
Using.
Background technique
From 2011, the Dalian Chemistry and Physics Institute, the Chinese Academy of Sciences great waves academician and its space flight catalysis were successfully synthesized with new material research team
Monatomic platinum catalyst Pt1/ FeOx, after proposing " monatomic catalysis " concept, monatomic catalysis is by the fervent of researcher
Concern.In recent years, monatomic catalysis is even more winsome, yields unusually brilliant results.It is monatomic catalysis (Single-Atom Catalysis,
SAC), it can be achieved that the maximization of metallic atom utilization rate, reduces catalyst cost, thus has important meaning.It is monatomic to urge
Agent is provided simultaneously with homogeneous catalyst " isolated site ", heterogeneous catalyst stable structure, segregative advantage, possesses bridging multiphase
It is catalyzed, the great potential of homogeneous catalysis.
Metal-organic framework material (metal organic frameworks, MOFs) is as a kind of novel porous material
Material, because the specific surface area of its superelevation, pore structure abundant and high dispersive metal center the features such as, it is considered to be a kind of ideal
The presoma for preparing nanometer oxide material, porous carbon materials and composite material.Metal organic framework is by metal ion/cluster
It is formed with functionalization organic linker, due to specific molecular structure unit, adjustable functional group and effective coordination
Point, therefore have become the promising support for preparing SAC.In view of this, it is presumed that, it is equipped with square planar four-coordination porphyrin list
The MOF of member may be the monoatomic ideal supporter of fixed noble metal.
Here, we show the monatomic porphyryl MOF of metal.Since porphyrin unit has clearly defined monatomic side
The fact that shape planar anchoring site, a series of metals (Ir, Pt, Ru, Au, Pd) are monatomic can to pass through easy method success
Ground is fixed in porphyryl MOF structure.Isolated single atom utilizes unique structure, monatomic catalytic center and photonic absorption
Ability shows highly reinforcing catalytic performance during the liberation of hydrogen of visible optical drive.
Summary of the invention
In view of the above shortcomings of the prior art, the purpose of the present invention is to provide a kind of monatomic porphyryls of metal
The preparation method of MOF material can be used as producing hydrogen catalyst using porphyryl MOF material prepared by the preparation method, and produce hydrogen
It measures higher than pure porphyryl MOF material.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is that it is such:
A kind of preparation method of the monatomic porphyryl MOF material of metal, comprising the following steps:
(1) ZrCl is weighed4, porphyrin carboxylic acid and benzoic acid be dissolved in DMF reagent, transfer them in reaction kettle, heating reaction,
It is washed again, it is dry, obtain PCN-224；Wherein, the ZrCl4, porphyrin carboxylic acid and benzoic acid mass ratio be 10 ~ 30:10
~ 20:250 ~ 400；
(2) by PCN-224 and TiCp obtained by step (1)2Cl2It is blended in DMF solvent, mixture is transferred in reaction kettle,
Heating reaction, then washing drying is carried out, obtain PCN-224 (Zr/Ti)；Wherein, solid PCN-224 and TiCp2Cl2Molar ratio
For 1 ~ 3:1；
(3) by step (2) obtained solid PCN-224 (Zr/Ti), IrCl3.xH2O、H2PtCl6.6H2O is dispersed in DMF, sealing
Heating reaction in a kettle, then washed, it is dry to get the porphyryl MOF material for limiting single metal atom.Wherein,
PCN-224(Zr/Ti)、IrCl3.xH2O、H2PtCl6.6H2O molar ratio is 50 ~ 100:1 ~ 5:1 ~ 5.
Wherein, in the step (1), the heating is carried out at 120 DEG C；The time of the heating is 24 ~ 26 hours.
In the step (2), the heating is carried out at 120 DEG C；The time of the heating is 24 ~ 80 hours.
In the step (3), the heating is carried out at 80 DEG C；The time of the heating is 2 ~ 4 hours.
Washing described in the step (1) is washed respectively using DMF and anhydrous ethanol solvent, first uses DMF centrifuge washing 3
It is secondary, then with dehydrated alcohol centrifuge washing 3 times.
Washing described in the step (2) is washed respectively using DMF and anhydrous ethanol solvent, first uses DMF centrifuge washing 3
It is secondary, again with methanol centrifuge washing 3 times.
Washing described in the step (3) uses anhydrous ethanol solvent centrifuge washing 3 times.
Invention additionally discloses a kind of application of the monatomic porphyryl MOF material of metal in Photocatalyzed Hydrogen Production.
Compared with prior art, the present invention has the advantage that
1, the monatomic porphyryl MOF material of metal prepared by the present invention has high porosity, low-density, bigger serface, duct
Rule, aperture is adjustable and topological structure diversity and the advantages that Scalability.Wherein, using Ti aliquot replacement Zr as center atom
Porphyryl MOF material production hydrogen effect be higher than using Zr as the production hydrogen effect of the pure MOF material of center atom, reach 1180.864
µL。
2, single metal atom is fixed in porphyrin ring, exposes more metal active sites, saves metal
Dosage, and effectively raise hydrogen output.
3, preparation method requirement provided by the invention is low, easy to operate, equipment is simple, reproducible, has biggish push away
Wide value.
Detailed description of the invention
Fig. 1 is the porphyryl of metal monatomic porphyryl MOF material and Ti aliquot replacement Zr made from the embodiment of the present invention 1
The XRD diagram of MOF material and pure Zr base porphyrin MOF material.
Fig. 2 is the hydrogen output figure of the monatomic porphyryl MOF material of metal made from 1-4 of the embodiment of the present invention.
Specific embodiment
Below in conjunction with embodiment, the invention will be further described.
One, the preparation of the monatomic porphyryl MOF material of metal
Embodiment 1
(1) by ZrCl4(900mg), H2TCPP(300mg) and 12g benzoic acid ultrasonic dissolution is in 60mLDMF solution.It will mixing
Object heats 24 hours in 120 DEG C of baking ovens.After being cooled to room temperature, cube darkviolet crystal is harvested by filtering.Obtain PCN-
224。
(2) by 415mgPCN-224 crystal and 375mgTiCl2Cl2It is mixed in 60mLDMF.By gained mixture 120
DEG C keep 3 day time, then cool to room temperature.By the way that crystal PCN-224(Zr/Ti obtained is collected by centrifugation), and use DMF(3
× 20mL) and ethyl alcohol (3 × 20mL) thoroughly washing, then it is dried in vacuo 24 hours at 80 DEG C.Obtain PCN-224 (Zr/Ti).
(3) by 200mgPCN-224 (Zr/Ti) and 2mLIrCl3Aqueous solution is added in 40mLDMF.Mixture is transferred to
In reaction kettle, after ultrasonic dissolution 10min, heated 4 hours at 80 DEG C.It is cooled to room temperature, then, with ethyl alcohol centrifuge washing number
Secondary, 80 DEG C of dry 6h obtain PCN-224 (Zr/Ti)-Ir.
Embodiment 2
(1) by ZrCl4(900mg), H2TCPP(300mg) and 12g benzoic acid ultrasonic dissolution is in 60mL DMF solution.It will mixing
Object heats 24 hours in 120 DEG C of baking ovens.After being cooled to room temperature, cube darkviolet crystal is harvested by filtering.Obtain PCN-
224。
(2) by 415mg PCN-224 crystal and 375mg TiCl2Cl2It is mixed in 60mL DMF.Gained mixture is existed
It 120 DEG C of 3 day times of holding, then cools to room temperature.By the way that crystal PCN-224(Zr/Ti obtained is collected by centrifugation), it is used in combination
DMF(3 × 20mL) and ethyl alcohol (3 × 20mL) thoroughly washing, then it is dried in vacuo 24 hours at 80 DEG C.Obtain PCN-224
(Zr/Ti)。
(3) by 200mg PCN-224 (Zr/Ti) and 2mLH2PtCl6Aqueous solution is added in 40mLDMF.Mixture is shifted
Into reaction kettle, after ultrasonic dissolution 10min, heated 4 hours at 80 DEG C.It is cooled to room temperature, then, with ethyl alcohol centrifuge washing number
Secondary, 80 DEG C of dry 6h obtain PCN-224 (Zr/Ti)-Pt.
Embodiment 3
(1) by ZrCl4(900mg), H2TCPP(300mg) and 12g benzoic acid ultrasonic dissolution is in 60mL DMF solution.It will mixing
Object heats 24 hours in 120 DEG C of baking ovens.After being cooled to room temperature, cube darkviolet crystal is harvested by filtering.Obtain PCN-
224。
(2) by 415mg PCN-224 crystal and 375mg TiCl2Cl2It is mixed in 60mL DMF.Gained mixture is existed
It 120 DEG C of 3 day times of holding, then cools to room temperature.By the way that crystal PCN-224(Zr/Ti obtained is collected by centrifugation), it is used in combination
DMF(3 × 20mL) and ethyl alcohol (3 × 20mL) thoroughly washing, then it is dried in vacuo 24 hours at 80 DEG C.Obtain PCN-224
(Zr/Ti)。
(3) by 200mg PCN-224 (Zr/Ti) and 1mLIrCl3Aqueous solution and 500 μ L H2PtCl6Aqueous solution is added
In 40mLDMF.Mixture is transferred in reaction kettle, after ultrasonic dissolution 10min, is heated 4 hours at 80 DEG C.It is cooled to room
Temperature, then, for several times with ethyl alcohol centrifuge washing, 80 DEG C of dry 6h obtain PCN-224 (Zr/Ti)-Ir/Pt.
Embodiment 4
(1) by ZrCl4(900mg), H2TCPP(300mg) and 12g benzoic acid ultrasonic dissolution is in 60mL DMF solution.It will mixing
Object heats 24 hours in 120 DEG C of baking ovens.After being cooled to room temperature, cube darkviolet crystal is harvested by filtering.Obtain PCN-
224。
(2) by 200mg PCN-224 and 1mLIrCl3Aqueous solution and 500 μ L H2PtCl6Aqueous solution is added in 40mLDMF.
Mixture is transferred in reaction kettle, after ultrasonic dissolution 10min, is heated 4 hours at 80 DEG C.It is cooled to room temperature, then, uses second
For several times, 80 DEG C of dry 6h obtain PCN-224-Ir/Pt to alcohol centrifuge washing.
Two, catalysis characteristics measure
1mL TEOA(triethanolamine is separately added into quartz reactor) as in the embodiment 1-4 for sacrificing reducing agent, 10mg
The monatomic porphyryl MOF material of gained noble metal, 1mL H2O is as proton source, 18mL acetonitrile as solvent；Then it is accessed
It produces in hydrogen photocatalytic system, circulating condensing water is kept for 10 DEG C.The production hydrogen photocatalytic system for being connected to quartz reactor is vacuumized.?
Xenon source is placed at the 5cm of quartz reactor top, the wavelength of optical filter is 380nm, takes a sample to pass through production within each one hour
Hydrogen photocatalytic system enters in gas-chromatography, detects the amount of hydrogen.Hydrogen output such as 1 institute of table of MOF material prepared by embodiment 1 ~ 4
Show.
The hydrogen output of the MOF material of 1 embodiment 1 ~ 4 of table preparation
| Hydrogen output/(μ L/g) | |
| Embodiment 1 | 222.3241 |
| Embodiment 2 | 811.19851 |
| Embodiment 3 | 1180.864 |
| Embodiment 4 | 284.83826 |
Referring to fig. 2, it is the restriction monoatomic MOF material of metal after Ti aliquot replacement Zr that embodiment 1,2,3, which is central metal,
In, embodiment 4 is that center metal is that Zr limits the monoatomic MOF material of metal, and Examples 1 and 2 are to limit a kind of metal list
The MOF material of atom, and embodiment 3 is to limit the monoatomic MOF material of two kinds of metals, as can be seen from Figure 2, embodiment 1,2,3
Hydrogen output is respectively as follows: 222.3241 μ L, 811.19851 μ L and 1180.864 μ L, hydrogen output gradually increase.This is because Ir is always
It is incorporated by the MOF structure of photosensitizer.Pt is always used as the co-catalyst of the Photocatalyzed Hydrogen Production in MOF composite material.Cause
This, the porphyrin-Ir unit as photosensitizer and the porphyrin-Pt unit as co-catalyst generate synergistic effect to improve catalytic
Energy.
Embodiment 3 compared with Example 4, the difference is that the central metal of embodiment 3 is Ti aliquot replacement Zr, and real
The central metal for applying example 4 is Zr.As shown in Figure 2, the hydrogen output of embodiment 3 is 1180.864 μ L, and the hydrogen output of embodiment 4
For 284.83826 μ L, it follows that being the production hydrogen effect ratio of the MOF material of center metal ion with pure using Ti aliquot replacement Zr
Zr is that the MOF material production hydrogen effect of center metal ion is good.
Finally, it should be noted that technical side the above examples are only used to illustrate the technical scheme of the present invention and are not limiting
Case, those skilled in the art should understand that, modification or equivalent replacement of the technical solution of the present invention are made for those, and
The objective and range for not departing from the technical program, are intended to be within the scope of the claims of the invention.
Claims (9)
1. a kind of preparation method of the monatomic porphyryl MOF material of metal, which comprises the following steps:
(1) ZrCl is weighed4, porphyrin carboxylic acid and benzoic acid be dissolved in DMF reagent, transfer them in reaction kettle, heating reaction,
It is washed again, it is dry, obtain PCN-224；Wherein, the ZrCl4, porphyrin carboxylic acid and benzoic acid mass ratio be 10 ~ 30:10
~ 20:250 ~ 400；
(2) by PCN-224 and TiCp obtained by step (1)2Cl2It is blended in DMF solvent, mixture is transferred in reaction kettle, add
Thermal response, then washing drying is carried out, obtain PCN-224 (Zr/Ti)；Wherein, solid PCN-224 and TiCp2Cl2Molar ratio be 1
~ 3:1；
(3) by step (2) obtained solid PCN-224 (Zr/Ti), IrCl3.xH2O、H2PtCl6.6H2O is dispersed in DMF, sealing
Heating reaction in a kettle, then washed, it is dry to get the porphyryl MOF material for limiting single metal atom.
2. wherein, PCN-224 (Zr/Ti), IrCl3.xH2O、H2PtCl6.6H2O molar ratio is 50 ~ 100:1 ~ 5:1 ~ 5.
3. the preparation method of the monatomic porphyryl MOF material of metal according to claim 1, which is characterized in that the step
Suddenly in (1), the heating is carried out at 120 DEG C；The time of the heating is 24 ~ 26 hours.
4. the preparation method of the monatomic porphyryl MOF material of metal according to claim 1, which is characterized in that the step
Suddenly in (2), the heating is carried out at 120 DEG C；The time of the heating is 24 ~ 80 hours.
5. the preparation method of the monatomic porphyryl MOF material of metal according to claim 1, which is characterized in that the step
Suddenly in (3), the heating is carried out at 80 DEG C；The time of the heating is 2 ~ 4 hours.
6. the preparation method of the monatomic porphyryl MOF material of metal according to claim 1, which is characterized in that the step
Suddenly washing described in (1) is washed respectively using DMF and anhydrous ethanol solvent, is first used DMF centrifuge washing 3 times, then use dehydrated alcohol
Centrifuge washing 3 times；Every time when washing, the ratio of DMF and solid PCN-224 are 30 ~ 50ml:100mg, dehydrated alcohol and solid
The ratio of PCN-224 is 30 ~ 50ml:100mg.
7. the preparation method of the monatomic porphyryl MOF material of metal according to claim 1, which is characterized in that the step
Suddenly washing described in (2) is washed respectively using DMF and anhydrous ethanol solvent, is first used DMF centrifuge washing 3 times, again with methanol centrifugation
Washing 3 times；Every time when washing, the ratio of DMF and solid PCN-224 (Zr/Ti) is 30 ~ 50ml:100mg, dehydrated alcohol with admittedly
The ratio of body PCN-224 (Zr/Ti) is 30 ~ 50ml:100mg.
8. the preparation method of the monatomic porphyryl MOF material of metal according to claim 1, which is characterized in that the step
Suddenly washing described in (3) uses anhydrous ethanol solvent centrifuge washing 3 times, every time when washing, the ratio of dehydrated alcohol and MOF material
For 30 ~ 50ml:100mg.
9. a kind of application of monatomic porphyryl MOF material of metal in Photocatalyzed Hydrogen Production.
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