CN106064101A - A kind of iron-based MOFs catalysis material and preparation and application thereof - Google Patents

A kind of iron-based MOFs catalysis material and preparation and application thereof Download PDF

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CN106064101A
CN106064101A CN201610451108.1A CN201610451108A CN106064101A CN 106064101 A CN106064101 A CN 106064101A CN 201610451108 A CN201610451108 A CN 201610451108A CN 106064101 A CN106064101 A CN 106064101A
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catalysis material
iron
based mofs
preparation
vocs
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刘宏利
安太成
陈江耀
李桂英
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Guangdong University of Technology
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Guangdong University of Technology
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    • B01J35/39
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/74General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86Catalytic processes
    • B01D53/8668Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/74General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86Catalytic processes
    • B01D53/8678Removing components of undefined structure
    • B01D53/8687Organic components
    • 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
    • B01J31/22Organic complexes
    • B01J31/2204Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208Oxygen, e.g. acetylacetonates
    • B01J31/2226Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
    • B01J31/223At least two oxygen atoms present in one at least bidentate or bridging ligand
    • B01J31/2239Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2255/00Catalysts
    • B01D2255/70Non-metallic catalysts, additives or dopants
    • B01D2255/705Ligands for metal-organic catalysts
    • 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
    • B01J2531/02Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0213Complexes without C-metal linkages
    • 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
    • B01J2531/80Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84Metals of the iron group
    • B01J2531/842Iron
    • 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
    • Y02ATECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters

Abstract

The invention discloses a kind of ferrous metals organic backbone (MOFs) catalysis material and preparation method and application.Described iron-based MOFs catalysis material is by FeCl3·6H2After O and p-phthalic acid are dissolved in DMF solution, under temperature programmed control, carry out hydro-thermal reaction, the solid of precipitation is carried out successively alcohol and washes, filter, be vacuum dried and obtain.This catalysis material not only has absorption and the accumulation ability of excellence to Organic substance volatility (VOCs), and can degrade efficiently VOCs under visible ray drives, and can be used for the reaction system of VOCs light catalytic purifying in air.Preparation method of the present invention has that technique is simple, environmental friendliness, reaction condition gentle, catalytic efficiency is high, do not produce the features such as secondary pollution, it is easy to large-scale promotion in field of environment protection.

Description

A kind of iron-based MOFs catalysis material and preparation and application thereof
Technical field
The invention belongs to photocatalysis technology field, particularly to ferrous metals organic backbone (MOFs) catalysis material and system Preparation Method, and the application in control atmosphere pollution volatile organic matter.
Background technology
Along with quickly propelling of industrialization and urbanization, the air pollution of China is on the rise.Various air pollutants In, volatile organic matter (Volatile organic compounds, VOCs) as an important polluter of atmospheric pollution, There is low concentration, highly toxic feature, seriously threaten human health and the sustainable development of society, caused the Chinese government, The public and the extensive concern of researcher.
The most emerging photocatalysis oxidation technique, is expected to directly utilize sunlight by VOCs under the effect of photocatalyst Finally it is oxidized to CO2And H2O, have simultaneously can the advantages such as Oxidation at room temperature, energy consumption be low, easy to operate it is considered to be most before application The VOCs Treatment process of scape.And the research and development of high efficiency low cost photocatalyst are core and the keys realizing the application of this technology.At present The semiconductor light-catalyst developed generally utilizes only to account in sunlight and lives less than just showing to be catalyzed under the ultraviolet excitation of 5% Property;Further, since most of semiconductor catalysts have less specific surface area so that it is can not effectively adsorb in real atmosphere The VOCs pollutant (generally ppbv to ppmv level) of low concentration, thus cause photochemical catalytic oxidation efficiency to be substantially reduced.The tightest Heavily limit semi-conducting material to directly utilize sunlight and carry out the application of photocatalytic degradation VOCs.Therefore, semi-conducting material is widened Photoresponse scope, improve its photocatalytic activity and become focus and the difficult point of this area research.
Fe2O3Can (about 2.2eV) photocatalysis as a kind of narrow band gap nontoxic, cheap, that chemical stability is good Agent, the maximum absorption wave of its photoresponse is up to about 600nm, it is possible to directly utilize the visible ray in solar spectrum as exciting light Drive redox reaction, and have been used for the aspect such as the visible light photocatalytic degradation of organic pollution, photodissociation Aquatic product hydrogen.So And, due to Fe2O3The problem such as have that photo-generated carrier recombination rate is high and conduction band positions is relatively low so that it is typically exhibit relatively low can See photocatalytic activity.But can be by reducing Fe2O3Particle diameter, improve high dispersive type and the specific surface area of catalysis material simultaneously, With reduce electron-hole compound, improve catalyst and to mass transfer and the absorbability of substrate molecule thus increase photo-generated carrier With the contact probability of adsorbed substrate, it is expected to obviously improve Fe2O3Visible light catalysis activity.But, how to prepare small particle, High dispersive and the efficient Fe of Large ratio surface2O3Catalysis material remains a challenge.
Summary of the invention
It is an object of the invention to the deficiency overcoming prior art to exist, primary and foremost purpose is to provide and a kind of has both excellent suction The preparation method of attached ferrous metals organic backbone (MOFs) catalysis material with photocatalysis performance.
It is a further object of the present invention to provide the iron-based MOFs catalysis material that said method prepares.
Another object of the present invention is to provide above-mentioned iron-based MOFs catalysis material at visible light photocatalytic degradation low concentration Application in VOCs.
Above-mentioned purpose of the present invention is achieved by the following technical programs:
The preparation method of a kind of iron-based MOFs catalysis material, comprises the steps:
S1. by FeCl3·6H2Join in DMF solution after O and p-phthalic acid mixing, be stirred at room temperature, obtain mixing molten Liquid A;
S2. the mixed solution A of step S1 gained is loaded in the polytetrafluoroethyllining lining hydrothermal reaction kettle of 5~200mL, React 10~100h, after being cooled to room temperature at 80~180 DEG C, collect precipitate, obtain the crude product of iron-based MOFs catalysis material;
S3. the crude product of the iron-based MOFs catalysis material of step S2 gained is joined in ethanol solution, at 30~100 DEG C Soak, the pressed powder vacuum dried 10~20h obtained after filtration, i.e. obtain the iron-based MOFs catalysis material of activation.
Preferably, the FeCl described in step S13·6H2The mol ratio of O: p-phthalic acid: DMF is 1:(0.1~20): (20 ~500).
Preferably, the time that is stirred at room temperature described in step S1 is 0.5~3h.
Preferably, the cooldown rate described in step S2 is 0.05~3 DEG C/min.
Preferably, the soak time described in step S3 is 8~24h.
Preferably, the vacuum drying temperature described in step S3 is 60~180 DEG C.
It addition, the iron-based MOFs catalysis material prepared of said method and volatility in visible light catalytic Cleaning Air thereof Organic application is also within protection scope of the present invention.
Preferably, styrene is had the absorption of highly significant and efficient photocatalysis to live by this iron-based MOFs catalysis material Property.
The iron-based MOFs material of the present invention possessed can high efficiency photocatalysis degraded low concentration VOCs three essential condition: its One, this iron-based MOFs material has absorption and the richness of the highest specific surface area and bigger porosity, beneficially low concentration VOCs Collection, carries out providing favourable microenvironment for light-catalyzed reaction;Its two, this iron-based MOFs is by Fe3+With in p-phthalic acid Oxygen atom ligand assembles, the confinement a large amount of extra small Fe in iron-based MOFs framework33-oxo(Fe2O3) bunch be remarkably improved Expose avtive spot;Its three, pore passage structure that iron-based MOFs is orderly and built the pi-electron confession bulk effect that part is formed by it, have It is beneficial to the migration of light induced electron, the separation efficiency of photo-generate electron-hole can be effectively improved, may advantageously facilitate entering of light-catalyzed reaction OK.
Compared with prior art, the method have the advantages that
1. the iron-based MOFs catalysis material that the present invention prepares has both the advantage that excellent absorption is collaborative with photocatalysis. This photocatalyst is by p-phthalic acid and Fe3+A kind of porous material assembled, it not only has bigger serface and height The feature of porosity, beneficially low concentration VOCs absorption and enrichment, and its construction unit Fe33-oxo(Fe2O3) bunch it is light Catalytic reaction provides substantial amounts of avtive spot, increases the contact probability of photo-generated carrier and adsorbed substrate, favorably In significantly improving visible light catalysis activity.
2., under visible ray drives, this iron-based MOFs catalysis material VOCs capable of being fast degraded, is that efficient photocatalysis is anti- Answer system.Test result indicate that, iron-based MOFs catalysis material to typical case VOCs gas-phase benzene ethylene show good absorption and Photocatalytic activity, in 10min, styrene has 96.1% to be adsorbed onto rapidly on catalysis material, just inhales through about 900min Attached penetrate;After adsorption desorption balances, under the irradiation of visible ray, in 35min, iron-based MOFs catalysis material is to cinnamic Degradation rate reaches 95.8%.
3. to have that power consumption is low, operation safety, response speed soon, do not produce secondary pollution etc. excellent for the preparation method of the present invention Point, it is easy to accomplish industrialization.
Accompanying drawing explanation
Fig. 1 is iron-based MOFs catalysis material adsorption curve cinnamic to gas phase.
Fig. 2 is iron-based MOFs catalysis material kinetics of photocatalytic degradation cinnamic to gas phase curve.
Detailed description of the invention
Further illustrate present disclosure below in conjunction with Figure of description and specific embodiment, but should not be construed as this The restriction of invention.If not specializing, the conventional hands that technological means used in embodiment is well known to those skilled in the art Section.Unless stated otherwise, the present invention uses reagent, method and apparatus are the art conventional reagent, method and apparatus.
Embodiment 1
S1. it is the FeCl of 2:1 by mol ratio3·6H2O and p-phthalic acid join in 30mL DMF solution, are stirred at room temperature 1h, obtains orange-yellow clear solution.
S2. the clear solution of step S1 gained is loaded in the hydrothermal reaction kettle of 100mL, at 110 DEG C, react 24h;With After the rate of temperature fall of 0.1 DEG C/min is cooled to room temperature, collects precipitate, obtain the crude product of iron-based MOFs catalysis material.
S3. being immersed in ethanol solution by the precipitate of step S2 gained, 60 DEG C are soaked 15h, by being filtrated to get solution In pressed powder;150 DEG C of vacuum drying 12h, i.e. can obtain the iron-based MOFs catalysis material of activation.
Embodiment 2
S1. it is the FeCl of 1:1 by mol ratio3·6H2O and p-phthalic acid join in 30mL DMF solution, are stirred at room temperature 2h, obtains orange-yellow clear solution.
S2. the clear solution of step S1 gained is loaded in the hydrothermal reaction kettle of 100mL, at 150 DEG C, react 20h;With After the rate of temperature fall of 0.5 DEG C/min is cooled to room temperature, collects precipitate, obtain the crude product of iron-based MOFs catalysis material;
S3. being immersed in ethanol solution by the precipitate of step S2. gained, 60 DEG C are soaked 15h, by being filtrated to get solution In pressed powder;120 DEG C of vacuum drying 15h, i.e. can obtain the iron-based MOFs catalysis material of activation.
Embodiment 3
S1. it is the FeCl of 2:1 by mol ratio3·6H2O and p-phthalic acid join in 30mL DMF solution, are stirred at room temperature 1.5h, obtains orange-yellow clear solution.
S2. the clear solution of step S1 gained is loaded in the hydrothermal reaction kettle of 100mL, at 150 DEG C, react 24h;With After the rate of temperature fall of 1.0 DEG C/min is cooled to room temperature, collects precipitate, obtain the crude product of iron-based MOFs catalysis material.
S3. being immersed in ethanol solution by the precipitate of step S2. gained, 80 DEG C are soaked 12h, by being filtrated to get solution In pressed powder;150 DEG C of vacuum drying 12h, i.e. can obtain the iron-based MOFs catalysis material of activation.
Embodiment 4
S1. it is the FeCl of 1:10 by mol ratio3·6H2O and p-phthalic acid join in 40mL DMF solution, and room temperature is stirred Mix 1.5h, obtain orange-yellow clear solution.
S2. the clear solution of step S1 gained is loaded in the hydrothermal reaction kettle of 100mL, at 140 DEG C, react 80h;With After the rate of temperature fall of 0.05 DEG C/min is cooled to room temperature, collects precipitate, obtain the crude product of iron-based MOFs catalysis material.
S3. being immersed in ethanol solution by the precipitate of step S2. gained, 80 DEG C are soaked 12h, by being filtrated to get solution In pressed powder;130 DEG C of vacuum drying 15h, i.e. can obtain the iron-based MOFs catalysis material of activation.
Fig. 1 is iron-based MOFs catalysis material adsorption curve cinnamic to gas phase.As seen from Figure 1, iron-based MOFs Catalysis material shows good absorption and photocatalytic activity to typical case's VOCs gas-phase benzene ethylene, and the styrene of 96.1% exists Quickly adsorbed on catalysis material in 10min, just reached complete adsorption penetration through about 900min;Fig. 2 is iron-based MOFs light The kinetic curve of catalysis material photocatalytic degradation cinnamic to gas phase.Figure it is seen that after adsorption desorption balances, Under the irradiation of visible ray, in 35min, iron-based MOFs material reaches 95.8% to cinnamic degradation rate.The above results shows, should Catalysis material is a kind of efficient surrounding purifying material, has good absorption-photocatalysis cooperative effect.
Above-described embodiment is the present invention preferably embodiment, but embodiments of the present invention are not by above-described embodiment Limit, the change made under other any spirit without departing from the present invention and principle, modify, substitute, combine, simplify, All should be the substitute mode of equivalence, within being included in protection scope of the present invention.

Claims (8)

1. the preparation method of an iron-based MOFs catalysis material, it is characterised in that comprise the steps:
S1. by FeCl3·6H2Join in DMF solution after O and p-phthalic acid mixing, be stirred at room temperature, obtain mixed solution A;
S2. the mixed solution A of step S1 gained is loaded in the polytetrafluoroethyllining lining hydrothermal reaction kettle of 5~200mL, 80~ React 10~100h, after being cooled to room temperature at 180 DEG C, collect precipitate, obtain the crude product of iron-based MOFs catalysis material;
S3. the crude product of the iron-based MOFs catalysis material of step S2 gained is joined in ethanol solution, 30~100 DEG C of immersions 8~24h, the pressed powder vacuum dried 10~20h obtained after filtration, i.e. obtain the iron-based MOFs catalysis material of activation.
Preparation method the most according to claim 1, it is characterised in that the FeCl described in step S13·6H2O: terephthaldehyde Acid: the mol ratio of DMF is 1:(0.1~20): (20~500).
Preparation method the most according to claim 1, it is characterised in that the time that is stirred at room temperature described in step S1 be 0.5~ 3h。
Preparation method the most according to claim 1, it is characterised in that the cooldown rate described in step S2 is 0.05~3 DEG C/ min。
Preparation method the most according to claim 1, it is characterised in that the vacuum drying temperature described in step S3 be 60~ 180℃。
6. the iron-based MOFs catalysis material that a kind is prepared by method described in any one of Claims 1 to 5.
7. the iron-based MOFs catalysis material described in claim 6 in visible light catalytic Cleaning Air volatile organic matter should With.
Apply the most according to claim 7, it is characterised in that described volatile organic matter is styrene.
CN201610451108.1A 2016-06-20 2016-06-20 A kind of iron-based MOFs catalysis material and preparation and application thereof Pending CN106064101A (en)

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