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 PDF

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CN110354901A
CN110354901A CN201910709206.4A CN201910709206A CN110354901A CN 110354901 A CN110354901 A CN 110354901A CN 201910709206 A CN201910709206 A CN 201910709206A CN 110354901 A CN110354901 A CN 110354901A
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pcn
porphyryl
mof material
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dmf
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贺有周
冯欢
姜光镁
夏济和
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Chongqing Technology and Business University
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    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/1691Coordination polymers, e.g. metal-organic frameworks [MOF]
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18Catalysts 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
    • B01J31/1805Catalysts 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
    • B01J31/181Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1815Cyclic 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/30Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39Photocatalytic properties
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/60Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61Surface area
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    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/04Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
    • C01B3/042Decomposition of water
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/40Complexes comprising metals of Group IV (IVA or IVB) as the central metal
    • B01J2531/46Titanium
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2531/00Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/40Complexes comprising metals of Group IV (IVA or IVB) as the central metal
    • B01J2531/48Zirconium
    • CCHEMISTRY; METALLURGY
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    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02Processes for making hydrogen or synthesis gas
    • C01B2203/0266Processes for making hydrogen or synthesis gas containing a decomposition step
    • C01B2203/0277Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/36Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

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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

A kind of preparation method and application of the monatomic porphyryl MOF material of metal
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.
CN201910709206.4A 2019-08-01 2019-08-01 A kind of preparation method and application of the monatomic porphyryl MOF material of metal Pending CN110354901A (en)

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CN111804341B (en) * 2020-07-29 2022-12-23 重庆工商大学 Preparation method and application of porphyrin-metal organic framework material
CN112871216B (en) * 2021-01-18 2022-03-04 山东大学 CO2Bismuth-based MOFs photocatalyst for cycloaddition reaction and preparation method and application thereof
CN112871216A (en) * 2021-01-18 2021-06-01 山东大学 CO2Bismuth-based MOFs photocatalyst for cycloaddition reaction and preparation method and application thereof
CN113398997A (en) * 2021-07-01 2021-09-17 辽宁大学 Platinum-doped ultrathin Zr-MOFs nano thin-layer composite photocatalyst and preparation method and application thereof
CN113398997B (en) * 2021-07-01 2023-11-10 辽宁大学 Platinum doped ultrathin Zr-MOFs nano thin layer composite photocatalyst and preparation method and application thereof
CN113713772A (en) * 2021-08-16 2021-11-30 西安交通大学 Application of PCN-222 as adsorbent in adsorption of PFOS pollutants in water body
CN113755877A (en) * 2021-10-14 2021-12-07 重庆工商大学 Monoatomic Pt electrocatalytic material and preparation method and application thereof
CN114588947A (en) * 2022-03-10 2022-06-07 招商局重庆交通科研设计院有限公司 Preparation method and application of Zr-MOF-s (Pt) (Zr/Ti) -R photocatalyst

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