CN106861626B - Adsorption-photocatalysis dual-function material, preparation method thereof and application thereof in volatile organic gas treatment process - Google Patents
Adsorption-photocatalysis dual-function material, preparation method thereof and application thereof in volatile organic gas treatment process Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 49
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- 229910052719 titanium Inorganic materials 0.000 claims description 9
- 229910052742 iron Inorganic materials 0.000 claims description 7
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical group [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 6
- 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 description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 4
- QDZRBIRIPNZRSG-UHFFFAOYSA-N titanium nitrate Chemical compound [O-][N+](=O)O[Ti](O[N+]([O-])=O)(O[N+]([O-])=O)O[N+]([O-])=O QDZRBIRIPNZRSG-UHFFFAOYSA-N 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical group [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 claims description 3
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
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- 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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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2213—At least two complexing oxygen atoms present in an at least bidentate or bridging ligand
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- B01D2255/80—Type of catalytic reaction
- B01D2255/802—Photocatalytic
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- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
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- B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
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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
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- B01J2531/84—Metals of the iron group
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Abstract
The invention discloses an adsorption-photocatalysis bifunctional material, a preparation method thereof and application thereof in a volatile organic gas treatment process. The preparation method comprises the following steps: dissolving 2-amino terephthalic acid and iron element precursor in N, N-dimethylformamide, adding methanol solvent, stirring uniformly, adding titanium element precursor, stirring, and carrying out hydrothermal synthesis reaction on the mixed solution; and after sequentially carrying out DMF washing and methanol washing on the product, centrifugally filtering and extracting the product, putting the product into a methanol solution for purification, finally centrifugally filtering and extracting the product, and drying to obtain the adsorption-photocatalysis dual-function material. The adsorption-photocatalytic dual-function material has high VOCs adsorption capacity selectivity and visible light photocatalytic degradation efficiency, can realize VOCs adsorption-photocatalytic degradation cyclic operation under normal temperature, normal pressure and visible light radiation, has simple process and low energy consumption, and can realize semi-continuous deep purification of waste gas containing VOCs.
Description
Technical Field
The invention belongs to the field of material preparation, and particularly relates to an adsorption-photocatalysis dual-functional material, a preparation method thereof and application thereof in a volatile organic gas treatment process.
Background
At present, thousands of factories in China still emit a large amount of Volatile Organic Compounds (VOCs) to the environment in an unorganized way, and the VOCs are one of the main sources of the current atmospheric pollution. The pollution of VOCs seriously threatens the health of human beings and destroys the ecological balance of the environment, restricts the sustainable development of society, and has attracted strong dissatisfaction of the public and great attention of governments. It is therefore imperative to effectively remediate pollution of VOCs. Therefore, the research and development of key materials and technologies for controlling the emission of VOCs have important national requirements and practical significance.
In order to effectively treat the pollution of VOCs in organic waste gas, catalytic combustion method, adsorption method, absorption method and the like are widely adopted at home and abroad, and treatment technologies researched in recent years comprise biofilm method, photocatalytic oxidation method, plasma method and the like [1 YUB.F.; hu z.b.; liu M.; yang H.L; kong Q.X.; liu Y.H., Review of research on air-conditioning systems and index air quality control for human health.International Journal of refinement.2009, 32,3-20 ]. Among them, the adsorption method is a treatment technique for large-air-volume low-concentration VOCs (several hundred ppm) which is considered to have the most potential development at present. Adsorption is a separation technique with a porous material as the core [2 old cold light; opening faithfully; wangtonghui, preparation of activated carbon module and study of adsorption property of activated carbon module on benzene, journal of university of chemical engineering (natural science edition) of Beijing, 2012,39, 26-30. The method can effectively adsorb volatile organic pollutants in the waste gas, and has been widely applied to the purification of organic waste gas and the recovery of VOCs. However, key bottleneck problems faced by current adsorption techniques for the remediation of VOCs include: (1) while adsorption is a spontaneous process, the adsorbent has limited adsorption capacity for VOCs; (2) regeneration is required when the adsorbent is near saturation for adsorption of VOCs, and is a process that requires external application of energy. Conventional adsorbent regeneration methods, such as thermal desorption, solvent elution [3 d of the pawn; (ii) a plum surface; plum wave, research and review of indoor air purification technology, research on trace elements and health, 2008,25,63-68 and the like inevitably cause secondary pollution, have high energy consumption or complex process, and directly determine the feasibility and the economical efficiency of the adsorption technology. Regeneration of the adsorbent is also a key point in the practical industry where adsorption technology can be applied, but is often overlooked during research. Meanwhile, the adsorption technology has high VOCs adsorption capacity and low energy consumption, and secondary pollution is not caused in the regeneration process of the adsorbent. Therefore, the research on the novel adsorbent with high VOCs adsorption capacity and the technology that the adsorbent does not cause secondary pollution in the regeneration process can play an important role in promoting the practical industrial application of the adsorption technology, and is worthy of important attack in the academic world and the industrial world.
Metal-Organic Frameworks (MOFs) are porous Organic-inorganic hybrid crystalline materials with periodic wireless network structures formed by Metal ions or Metal clusters and Organic ligands through a self-assembly process. MOFs materials have rich and regular pore structures, ultrahigh specific surface area and ultrahigh pore volume, adjustable pore diameter and surface chemical properties, contain unsaturated metal sites and the like, and have great application prospects in sustainable energy and environmental management. In terms of adsorption of VOCs, Ponkun et al reported that the adsorption of VOCs by MIL-101(Cr) material reached 11.91mmol/g of toluene adsorption capacity at 25 ℃. [4Yang K.; sun q.; xue R; LinD.H., the introduction of volatile compounds by metal-organic frames MIL-101. the influence of molecular and shape. the journal of Hazardous materials.2011,195,124-131]Our earlier studies also found that the adsorption capacity of HKUST-1 to benzene at 298K and 8kPa was 6.90 mmol/g-1. [5 Li Yujie, Miao Jinpun, Sunjujiao, Xiaojing, Xixia, Xihongxia, Li fain, mechanochemical method for synthesizing metal organic frame material HKUST-1 and its benzene adsorption performance 2015,66,793-]However, the adsorption-photocatalysis dual-function metal organic framework material with high VOCs adsorption capacity and high VOCs photocatalysis degradation activity and the VOCs adsorption-photocatalysis coupling treatment process based on the material are not reported.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention mainly aims to invent an adsorption-photocatalysis dual-function material and a novel volatile organic gas treatment process. The adsorption-photocatalysis dual-function material has high VOCs adsorption capacity and high VOCs photocatalytic degradation activity; the VOCs treatment technology based on the adsorption-photocatalysis dual-function material can realize the regeneration process of the material while realizing the semi-continuous adsorption purification-photocatalysis degradation, and the regeneration process of the material does not cause secondary pollution and has low energy consumption.
The purpose of the invention is realized by the following technical scheme:
an adsorption-photocatalysis bifunctional material and a preparation method thereof, comprising the following steps:
(1) dissolving 2-amino terephthalic acid and iron element precursors in N, N-Dimethylformamide (DMF), adding a methanol solvent, uniformly stirring, adding a titanium element precursor, continuously uniformly stirring, and carrying out hydrothermal synthesis reaction on the mixed solution;
(2) and after sequentially carrying out DMF washing and methanol washing on the product, centrifugally filtering and extracting the product, putting the product into a methanol solution for purification, periodically replacing the solvent during the purification, finally centrifugally filtering and extracting the product, and drying to prepare the iron-titanium bimetal organic framework material, namely the adsorption-photocatalysis dual-functional material.
In the method, the iron element precursor is ferric nitrate, ferric chloride, ferric sulfate or ferric oxide; the titanium element precursor is tetrabutyl titanate, tetraisopropyl titanate, titanyl sulfate, titanium tetrachloride or titanium nitrate; the iron element precursor and the titanium element precursor meet the condition that the molar ratio of titanium to iron is 0.5-2; the molar ratio of the 2-amino terephthalic acid to the iron element precursor is 0.5-3; the temperature of the hydro-thermal synthesis reaction solution is 120-180 ℃; the hydrothermal synthesis reaction time is 48-72 h; the centrifugal rotating speed is 6000 to 9000 r/min; the drying temperature is 80-150 ℃.
In the method, the mass percent of Ti in the iron-titanium bimetallic metal organic framework dual-function catalytic adsorption material is 0.5-3.0 wt%; the light absorption side band is 700-800 nm, the crystal size is 500-800 nm in length and 100-600 nm in width.
A process for treating volatile organic gas by using an adsorption-photocatalysis dual-function material comprises the following steps:
(1) introducing air containing VOCs into a packed adsorption-photocatalysis dual-function material bed layer, and adsorbing the VOCs by the adsorption-photocatalysis dual-function material bed layer so as to obtain clean air;
(2) adsorption-photocatalysisWhen the bed layer of the dual-function material is close to adsorption saturation, a light source is started, so that VOCs enriched on the surface of the adsorption-photocatalysis dual-function material are subjected to photocatalytic degradation to generate CO2And H2And O, secondary pollution and energy consumption caused by desorption of VOCs in the regeneration process are effectively avoided, and meanwhile, the adsorption-photocatalysis dual-function material bed layer is regenerated and enters the next adsorption-photocatalysis cycle.
In the treatment process of the adsorption-photocatalysis dual-function material in volatile organic gas, in the step (1), the VOCs are toluene, benzene, formaldehyde or isopropanol; the content of the VOCs in the air is 50-300 ppm; the gas flow rate is 5-20 ml/min; in the step (2), the regeneration environment is room temperature; the photocatalytic regeneration light source is 100-300 mW/cm2(ii) a The regeneration time is 2-6 h.
In the process for treating the volatile organic gases by using the adsorption-photocatalysis dual-function material, the adsorption rate of VOCs is over 95 percent; the adsorption performance of VOCs of the material after photocatalytic regeneration is kept above 90 percent of the original adsorption performance. The working principle of the invention is as follows:
the adsorption-photocatalysis dual-function material has two functions of adsorption and photocatalysis. The traditional material often has only one function, such as molecular sieve, activated carbon and the like, and has a certain specific surface area so as to have the function of a catalyst, but has limited potential as a photocatalyst; and metal oxide TiO2And CdS, etc., which have photocatalytic activity but have limited specific surface area and thus limited potential as an adsorbent. The metal organic framework material is an organic-inorganic hybrid material with an ultrahigh specific surface area and ordered pore structure, has high specific surface area and semiconductor characteristics, and has the potential of being designed into an adsorption-photocatalysis dual-function material. The iron-titanium bimetallic organic frame material adsorption-photocatalysis dual-functional material has a metal-organic hybrid frame structure, so that the adsorption capacity of VOCs is strong; because titanium element is doped in the organic-inorganic hybrid material, the position of a conduction band of a semiconductor is improved, and the reduction capability of the material is improved, so that the material has the capability of generating photogenerated electrons under the illumination condition and combining with oxygen to generate superoxide anions so as to oxidize VOCs (volatile organic compounds)。
The new VOCs treatment process principle based on the adsorption-photocatalysis bifunctional metal organic framework material is as follows: the surface of the bifunctional material is provided with VOCs adsorption sites and photocatalysis sites at the same time, and when VOCs-containing waste gas passes through a material bed layer, the adsorption sites on the surface of the material can selectively adsorb VOCs, so that clean air is obtained; when the bed layer approaches to adsorption saturation, under the radiation of a light source, VOCs enriched on the surface of the material can be degraded to generate CO through photocatalysis site2And H2And O, secondary pollution and energy consumption caused by desorption of VOCs in the regeneration process are effectively avoided, and meanwhile, the adsorption-photocatalysis dual-function material bed layer is regenerated and enters the next adsorption-photocatalysis cycle.
Compared with the prior art, the invention has the following advantages and effects:
1. the adsorption-photocatalysis dual-function material has high VOCs adsorption capacity selectivity and visible light photocatalysis degradation efficiency;
2. the process can realize cyclic operation of VOCs adsorption-photocatalytic degradation (regeneration) under normal temperature, normal pressure and visible light radiation, has simple process and low energy consumption, and can realize semi-continuous deep purification of the waste gas containing the VOCs.
Drawings
FIG. 1 is a process diagram of VOCs treatment based on adsorption-photocatalysis dual-function material;
FIG. 2 is an XRD spectrum of examples 1 to 4 of the present invention;
FIG. 3a is a TEM-EDS picture of example 2 of the present invention;
FIG. 3b is the element distribution of example 2;
FIG. 4 is a UV-Vis spectrum of examples 1 to 4 of the present invention;
FIG. 5 is a valence band XPS spectrum of example 2 of the present invention;
FIG. 6 is a graph showing the adsorption performance of examples 1 to 4 of the present invention on formaldehyde, toluene, isopropanol and benzene;
FIG. 7 is a graph showing the visible light degradation properties of formaldehyde, toluene, isopropanol and benzene in examples 1 to 4 of the present invention.
Detailed Description
The invention is further described below with reference to the figures and examples, but the scope of the invention as claimed is not limited to the scope of the examples.
Example 1
1. Preparation of bifunctional adsorption-photocatalysis metal organic framework material
(1) 1.054g of 2-amino terephthalic acid and 5.16g of iron element precursor iron oxide are dissolved in N, N-Dimethylformamide (DMF), methanol solvent is added, the mixture is stirred uniformly, then 0.26ml of titanium tetrachloride is added, the mixture is stirred uniformly, and the mixture is subjected to hydrothermal synthesis reaction for 72 hours at 120 ℃.
(2) Washing the product with DMF and methanol in sequence, centrifugally filtering to extract the product, purifying the product in methanol solution, periodically replacing the solvent during the purification, centrifugally filtering to extract the product, and drying at 150 ℃ to obtain the Fe-Ti bimetallic organic framework material.
2. Novel VOCs treatment process based on dual-function adsorption-photocatalysis metal organic framework material
(1) Introducing air with the formaldehyde content of 300ppm into the filled adsorption-photocatalysis dual-function material bed layer at the flow rate of 5ml/min, wherein the adsorption-photocatalysis dual-function material bed layer can selectively adsorb formaldehyde, so as to obtain clean air;
(2) when the adsorption-photocatalysis dual-function material bed layer is close to adsorption saturation, starting 100mW/cm2The light source is illuminated for 6 hours, so that the VOCs enriched on the surface of the adsorption-photocatalysis dual-function material are subjected to photocatalytic degradation to generate CO2And H2And O, secondary pollution and energy consumption caused by desorption of VOCs in the regeneration process are effectively avoided, and meanwhile, the adsorption-photocatalysis dual-function material bed layer is regenerated and enters the next adsorption-photocatalysis cycle.
Example 2
1. Preparation of bifunctional adsorption-photocatalysis metal organic framework material
(1) 1.054g of 2-amino terephthalic acid and 3.18g of iron precursor ferric sulfate are dissolved in N, N-Dimethylformamide (DMF), methanol solvent is added, 0.52ml of titanyl sulfate is added after uniform stirring, the mixture is continuously stirred uniformly, and the mixture is subjected to hydrothermal synthesis reaction for 60 hours at 160 ℃.
(2) Washing the product with DMF and methanol in sequence, centrifugally filtering to extract the product, purifying the product in methanol solution, periodically replacing the solvent during the purification, centrifugally filtering to extract the product, and drying at 120 ℃ to obtain the Fe-Ti bimetallic organic framework material.
2. Novel VOCs treatment process based on dual-function adsorption-photocatalysis metal organic framework material
(1) Introducing air with the toluene content of 200ppm into the filled adsorption-photocatalysis dual-function material bed layer at the flow rate of 10ml/min, wherein the adsorption-photocatalysis dual-function material bed layer can selectively adsorb toluene, so as to obtain clean air;
(2) when the adsorption-photocatalysis dual-function material bed layer is close to adsorption saturation, starting 200mW/cm2The strong light source illuminates for 5 hours, so that the toluene enriched on the surface of the adsorption-photocatalysis dual-function material is subjected to photocatalytic degradation to generate CO2And H2And O, secondary pollution and energy consumption caused by toluene desorption in the regeneration process are effectively avoided, and meanwhile, the adsorption-photocatalysis dual-function material bed layer is regenerated and enters the next adsorption-photocatalysis cycle.
Example 3
1. Preparation of bifunctional adsorption-photocatalysis metal organic framework material
(1) 1.054g of 2-amino terephthalic acid and 2.58g of iron element precursor ferric nitrate are dissolved in N, N-Dimethylformamide (DMF), methanol solvent is added, after uniform stirring, 0.78ml of tetraisopropyl titanate is added, after uniform stirring, the mixed solution is subjected to hydrothermal synthesis reaction for 48 hours at 120 ℃.
(2) Washing the product with DMF and methanol in sequence, centrifugally filtering to extract the product, purifying the product in methanol solution, periodically replacing the solvent during the purification, centrifugally filtering to extract the product, and drying at 100 ℃ to obtain the Fe-Ti bimetallic organic framework material.
2. Novel VOCs treatment process based on dual-function adsorption-photocatalysis metal organic framework material
(1) Introducing air with the isopropanol content of 100ppm into the filled adsorption-photocatalysis dual-function material bed layer at the flow rate of 15ml/min, wherein the adsorption-photocatalysis dual-function material bed layer can selectively adsorb the isopropanol, so as to obtain clean air;
(2) when the adsorption-photocatalysis dual-function material bed layer is close to adsorption saturation, the bed layer is opened with 150mW/cm2The isopropanol enriched on the surface of the adsorption-photocatalysis dual-function material is subjected to photocatalytic degradation to generate CO after being illuminated for 4 hours by an intense light source2And H2And O, secondary pollution and energy consumption caused by isopropanol desorption in the regeneration process are effectively avoided, and meanwhile, the adsorption-photocatalysis dual-function material bed layer is regenerated and enters the next adsorption-photocatalysis cycle.
Example 4
1. Preparation of bifunctional adsorption-photocatalysis metal organic framework material
(1) 1.054g of 2-amino terephthalic acid and 1.29g of iron element precursor ferric chloride are dissolved in N, N-Dimethylformamide (DMF), methanol solvent is added, 1.04ml of tetrabutyl titanate is added after uniform stirring, and the mixed solution is subjected to hydrothermal synthesis reaction for 72 hours at 150 ℃ after continuous uniform stirring.
(2) Washing the product with DMF and methanol in sequence, centrifugally filtering to extract the product, purifying the product in methanol solution, periodically replacing the solvent during the purification, centrifugally filtering to extract the product, and drying at 80 ℃ to obtain the Fe-Ti bimetallic organic framework material.
2. Novel VOCs treatment process based on dual-function adsorption-photocatalysis metal organic framework material
(1) Introducing air with the benzene content of 50ppm into the filled adsorption-photocatalysis dual-function material bed layer at the flow rate of 20ml/min, wherein the adsorption-photocatalysis dual-function material bed layer can selectively adsorb benzene, so as to obtain clean air;
(2) when the adsorption-photocatalysis dual-function material bed layer is close to adsorption saturation, 300mW/cm is started2The strong light source illuminates for 5 hours, so that benzene enriched on the surface of the adsorption-photocatalysis dual-function material is subjected to photocatalytic degradation to generate CO2And H2O, effectively avoids secondary pollution and energy consumption caused by benzene desorption in the regeneration process, and meanwhile, the adsorption-photocatalysis dual-function material bed layer is regenerated and enters the next adsorption-photocatalysis cycle。
The invention provides a bifunctional adsorption-photocatalytic metal organic framework material and a novel VOCs treatment process thereof, wherein the titanium content, the crystal structure, the light absorption range, the VOCs adsorption performance and the VOCs photocatalytic degradation performance are as follows:
(1) titanium content of ferrotitanium bimetallic organic framework material
The contents of iron and titanium in examples 1 to 4 of the present invention were analyzed by a Varian 715-ES plasma emission spectrometer, and the results are shown in Table 1.
As can be seen from Table 1, the content ratio of Fe and Ti in the Fe-Ti bimetallic organic framework material prepared by the invention is consistent with the change trend of the feeding amount, and finally the content of Ti is increased along with the increase of the molar ratio of Ti in the precursor.
(2) Crystal structure property of iron-titanium bimetal organic framework material
The crystal structures of example 1(Fe-Ti-1), example 2(Fe-Ti-2), example 3(Fe-Ti-3) and example 4(Fe-Ti-4) according to the invention were characterized by means of an X-ray diffractometer, model D8-ADVANCE, Bruker, Germany, under the operating conditions: cu target Kalpha light source, 40mA current in radiant tube, 40kv voltage, continuous scanning mode, 5-40 degree of scanning angle, 0.1 second/step of scanning speed and 0.02 degree of scanning step length.
XRD spectra of example 1(Fe-Ti-1), example 2(Fe-Ti-2), example 3(Fe-Ti-3) and example 4(Fe-Ti-4) of the present invention and pure iron-based MOF are shown in FIG. 2, and it can be seen from FIG. 2 that as the Ti content increases, the main peak around 8 ° has a phenomenon of gradually shifting to the left, which indicates that Ti enters the lattice to replace the position of Fe, and as the radius of Ti ion is larger than the ionic radius of Fe, the distortion of the crystal framework increases, and the peak position shifts to the left.
(3) Crystal morphology and element distribution of iron-titanium bimetal organic framework material
And analyzing the crystal morphology and element distribution of the ferrotitanium bimetallic organic framework material by using a JEM-2100 transmission electron microscope. FIG. 3a shows the morphology of example 2 of the present invention under an electron microscope, and FIG. 3b shows the element distribution of example 2 of the present invention. As can be seen from FIG. 3a, the material is in the shape of an ellipsoid 900nm long and 200nm wide. In addition, according to the electron spectrum analysis, the representative element Fe and the element Ti can be distributed throughout the whole crystal, and the fact that the elements Fe and Ti can be uniformly distributed on the whole frame is proved.
(4) Ultraviolet-visible absorption spectrum analysis of iron-titanium bimetal organic framework material
The UV-Vis spectrometer of Shimadzu Japan was used to analyze the UV-visible absorption of the FeTi bimetallic organic framework material. FIG. 4 shows the UV absorption spectra of example 1(Fe-Ti-1), example 2(Fe-Ti-2), example 3(Fe-Ti-3) and example 4(Fe-Ti-4) of the present invention and pure iron-based MOF, and it can be seen that the absorption sidebands appear blue-shifted with increasing Ti content, indicating that the forbidden band width is continuously increased.
(5) Valence band XPS spectrum of iron-titanium bimetal organic framework material
The valence band of the Fe-Ti bimetallic organic framework material is measured by ESCALB 250Xi X-ray photoelectron spectroscopy. Figure 5 shows a comparison of the valence band of example 2 of the invention with the valence band of a pure iron-based MOF. As can be seen from FIG. 5, the valence band of the material can be raised by introducing Ti, the valence band value of Fe-Ti-2 is 2.38eV, and the valence band value of Fe-MOF is 2.64eV, and the ultraviolet absorption spectrum shows that the conduction band is higher than that of pure iron-based MOF, and the reduction capability of the sample is also enhanced.
(6) Adsorption performance of iron-titanium bimetallic organic framework material on formaldehyde, toluene, isopropanol and benzene
The saturated adsorption amount of VOC was measured in example 2(Fe-Ti-2) of the present invention using an AUTOSORB-1 gas adsorber (Quantachrome, Inc., USA). As can be seen from FIG. 6, Fe-Ti-2 has high adsorption capacity for formaldehyde, toluene, isopropanol and benzene, which indicates that the material has the capacity of adsorbing VOC.
(7) Visible light degradation performance of iron-titanium bimetal organic framework material to formaldehyde, toluene, isopropanol and benzene
A PLS-SXE300 xenon lamp of Beijing Pofele company is used as a light source, and a 420nm filter is used as the light source. The VOC content was measured by GC9560 gas chromatograph and hydrogen flame ionization detector. The reaction vessel is 100ml, dry air with VOC (formaldehyde, toluene, isopropanol or benzene) concentration of 300ppm is introduced, after adsorption equilibrium is reached, illumination is carried out for 6h, and sampling is carried out to test the residual VOC content.
FIG. 7 shows the photocatalytic degradation rate of VOC, which is 98%, 90%, 95% and 86% for formaldehyde, toluene, isopropanol and benzene, respectively, in example 2(Fe-Ti-2) of the present invention, which indicates that the sample has a higher photocatalytic reaction capability.
TABLE 1 Fe and Ti contents of the Fe-Ti bimetallic MOORGANIC FRAME Material of the invention
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (3)
1. The preparation method of the adsorption-photocatalysis dual-function material is characterized by comprising the following steps of:
(1) dissolving 2-amino terephthalic acid and iron element precursors in N, N-Dimethylformamide (DMF), adding a methanol solvent, uniformly stirring, adding a titanium element precursor, continuously uniformly stirring, and carrying out hydrothermal synthesis reaction on the mixed solution;
(2) performing DMF washing and methanol washing on the product in sequence, performing centrifugal filtration to extract the product, purifying the product in a methanol solution, periodically replacing the solvent during the purification, finally performing centrifugal filtration to extract the product, and drying to prepare the iron-titanium bimetal organic framework material, namely the adsorption-photocatalysis dual-functional material;
the iron element precursor is ferric nitrate, ferric chloride, ferric sulfate or ferric oxide, the titanium element precursor is tetrabutyl titanate, tetraisopropyl titanate, titanyl sulfate, titanium tetrachloride or titanium nitrate, the molar ratio of titanium to iron of the iron element precursor is 0.5 ~ 2, the molar ratio of 2-aminoterephthalic acid to the iron element precursor is 0.5 ~ 3, the temperature of a hydrothermal synthesis reaction solution is 120 ~ 180 ℃, the hydrothermal synthesis reaction time is 48 ~ 72h, the centrifugal rotation speed is 6000 ~ 9000r/min, and the drying temperature is 80 ~ 150 ℃;
the mass percentage of Ti of the iron-titanium bimetal organic framework dual-function catalytic adsorption material is 0.5 ~ 3.0.0 wt%, the light absorption side band is 700 ~ 800nm, and the crystal size of the iron-titanium bimetal organic framework dual-function catalytic adsorption material is 500 ~ 800nm and 100 ~ 600 nm;
the application of the adsorption-photocatalysis dual-function material in the treatment process of volatile organic gases comprises the following steps:
(1) introducing air containing VOCs into a packed adsorption-photocatalysis dual-function material bed layer, and adsorbing the VOCs by the adsorption-photocatalysis dual-function material bed layer so as to obtain clean air;
(2) when the adsorption-photocatalysis dual-function material bed layer is close to adsorption saturation, the light source is started, so that VOCs enriched on the surface of the adsorption-photocatalysis dual-function material are subjected to photocatalytic degradation to generate CO2And H2And O, meanwhile, regenerating the adsorption-photocatalysis dual-function material bed layer, and entering the next adsorption-photocatalysis cycle.
2. The method for preparing the adsorption-photocatalytic dual-function material according to claim 1, wherein in the step (1), the VOCs are toluene, benzene, formaldehyde or isopropanol, the content of the VOCs in the air is 50 ~ 300ppm, the gas flow rate is 5 ~ 20mL/min, in the step (2), the regeneration environment is room temperature, and the light source for photocatalytic regeneration is 100 ~ 300mW/cm2The regeneration time is 2 ~ 6 h.
3. The method for preparing the adsorption-photocatalysis dual-function material according to claim 2, wherein the adsorption rate of VOCs is more than 95%; the adsorption performance of VOCs of the material after photocatalytic regeneration is kept above 90 percent of the original adsorption performance.
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