CN114471467A - Truncated polyhedral MOFs @ rGO material and preparation method and application thereof - Google Patents
Truncated polyhedral MOFs @ rGO material and preparation method and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 12
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 48
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 55
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- 230000035484 reaction time Effects 0.000 claims description 2
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- 238000001816 cooling Methods 0.000 description 10
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 10
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- 125000004434 sulfur atom Chemical group 0.000 description 2
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- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 239000012917 MOF crystal Substances 0.000 description 1
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- 239000003795 chemical substances by application Substances 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
- 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]
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28066—Surface area, e.g. B.E.T specific surface area being more than 1000 m2/g
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
- C10G25/003—Specific sorbent material, not covered by C10G25/02 or C10G25/03
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4018—Spatial velocity, e.g. LHSV, WHSV
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- Chemical Kinetics & Catalysis (AREA)
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- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a truncated polyhedron MOFs @ rGO material as well as a preparation method and application thereof. The invention provides a truncated polyhedral MOFs @ rGO material which comprises reduced graphene oxide and a metal organic framework material, wherein the truncated polyhedral MOFs @ rGO material contains a hierarchical porous structure. The truncated polyhedral MOFs @ rGO material can be used as an adsorbent to effectively remove thiophene sulfides, has the characteristics of stable structure, high removal rate and high sulfur capacity, and is mild in reaction conditions, low in production cost and low in hydrogen consumption.
Description
Technical Field
The invention relates to the field of adsorption desulfurization, in particular to a truncated polyhedral MOFs @ rGO material, a preparation method and application thereof in adsorption desulfurization.
Background
In recent years, clean energy has been increasingly paid attention, and among them, fuel cells are the most promising energy conversion devices for vehicles and power plants, which not only can conveniently and cleanly convert chemical energy into electric energy, but also can be effectively used in the vehicles and the power plants. Fuel oil is an ideal energy source for fuel cells, however, sulfur compounds in fuel oil easily poison the reforming catalyst in fuel cells and the catalyst in the electrodes thereof. Therefore, the sulfur content of fuel oil used in fuel cells must be controlled to be extremely low.
The sulfur compounds in fuel oil such as finished gasoline mainly comprise mercaptan, thioether, disulfide, thiophene and derivatives thereof, and the thiophene sulfur compounds account for more than 85 percent of the total sulfur of the gasoline. Wherein the sulfur atoms of the mercaptan, thioether and disulfide have higher electron cloud density and weaker carbon-sulfur bond, and can be removed by the traditional hydrodesulfurization method. Thiophene and its derivatives can form a stable conjugated structure between the lone pair electrons on the sulfur atom and the pi electrons on the thiophene ring, and the carbon-sulfur bond is not easy to break, so the difficulty of removing thiophene by hydrodesulfurization is high.
Metal organic framework materials are increasingly used in adsorptive separation as porous materials in recent years. CN105561929B discloses a modified organic framework material for efficiently removing dibenzothiophene in fuel oil, which relates to a preparation method of bimetallic MOFs (metal organic framework materials), and a Zn @ PCN-10 material capable of effectively removing dibenzothiophene is obtained by coordination and connection of a proper ligand and bimetal. The sulfur content of the material is limited to a certain extent, raw materials are not fully utilized, the preparation period is long, and the industrial application in the later period is not facilitated.
Disclosure of Invention
The invention solves the technical problems of low removal rate of thiophene and derivatives thereof, small sulfur capacity and the like in the prior art, and also has the defects of harsh reaction conditions, high production cost, high hydrogen consumption and the like. The invention provides a truncated polyhedron MOFs @ rGO material, a preparation method and application thereof.
The invention provides a truncated polyhedral MOFs @ rGO material, which comprises reduced graphene oxide and a metal organic framework material, wherein the truncated polyhedral MOFs @ rGO material contains a hierarchical pore structure.
In the above technical solution, the metal source in the metal organic framework material is selected from one or more of Cu, Fe, Cr, V, Mn, Co, and Ni; preferably at least one of Cu and V.
In the above technical solution, the ligand of the metal organic framework is selected from one or more of trimesic acid, terephthalic acid, 4-bipyridine and 3,4, 5-biphenyltricarboxylic acid.
In the technical scheme, the reduced graphene oxide can be obtained by Brodie, Staudenmai or Hummer methods to obtain graphite oxide/graphite oxide, and then reduced to obtain the reduced graphene oxide.
In the above technical scheme, the mass ratio of the metal in the metal organic framework to the reduced graphene oxide is 1: (0.01-1).
In the technical scheme, the metal organic framework material is a truncated polyhedron, the edge length of the polyhedron is 3-10 mu m, the side length of a section polygon is 0.5-5 mu m, and the section polygon can be a triangle, a quadrangle, a pentagon or a hexagon.
In the technical scheme, the truncated polyhedron-shaped MOFs @ rGO material is a hierarchical porous material and comprises micropores and mesopores; the total pore volume is 0.40-0.90cm3The mesoporous volume is 0.01-0.40cm3The pore volume of the micropores is 0.10-0.85cm3The specific surface area is 1000-1500m2/g。
In the above technical scheme, preferably, the truncated polyhedral MOFs @ rGO material is a hierarchical porous material, and the total pore volume is 0.60-0.80cm3The mesoporous volume is 0.12-0.40cm3The pore volume of the micropores is 0.40-0.58cm3The specific surface area is 1000-2/g。
In the technical scheme, the truncated polyhedral MOFs @ rGO material is in a crystal structure that a metal organic framework material grows on a reduced graphene oxide sheet layer or the metal organic framework material is wrapped by the reduced graphene oxide sheet layer.
The invention provides a preparation method of a truncated polyhedral MOFs @ rGO material, which comprises the following steps:
s1: adding graphite oxide and an anionic surfactant into a first solvent, and ultrasonically stripping and dispersing to obtain graphene oxide dispersion liquid;
s2: dissolving metal salt and a ligand in a second solvent to form a reaction solution, mixing the reaction solution with the graphene oxide dispersion liquid obtained in S1, and reacting to obtain the truncated polyhedral MOFs @ rGO material;
wherein the first solvent or/and the second solvent comprises an alcohol solvent.
In the above technical solution, the anionic surfactant in step S1 includes one or more of alkyl benzene sulfonate, α -olefin sulfonate, alkyl sulfonate, α -sulfomonocarboxylic acid and its derivatives, and fatty acid sulfoalkyl ester.
In the above technical solution, the first solvent in step S1 includes one or more of monohydric alcohol, dihydric alcohol, polyhydric alcohol, and deionized water.
In the above technical solution, the concentration of the graphene oxide dispersion in step S1 is 0.05-2 mg/mL.
In the above technical solution, the mass ratio of the graphite oxide to the anionic surfactant in step S1 is 1: (0.1-5).
In the above technical solution, the ultrasound in step S1 may be performed by performing water bath ultrasound on the mixture in step S1, the ultrasound power is 200-.
In the above technical solution, the metal salt in step S2 includes one or more of inorganic salts of Cu, Fe, Cr, V, Mn, Co, and Ni; preferably at least one of Cu and V metal salts.
In the above technical solution, the ligand in step S2 is selected from one or more of trimesic acid, terephthalic acid, 4-bipyridine and 3,4, 5-biphenyltricarboxylic acid.
In the technical scheme, the molar ratio of the metal salt to the ligand in the S2 is 1 (0.2-5).
In the above technical solution, the second solvent in step S2 includes one or more of N, N-dimethylformamide, N-dimethylacetamide, triethylamine, hydrofluoric acid, tetrahydrofuran, monohydric alcohol, dihydric alcohol, polyhydric alcohol, and deionized water.
In the above technical solution, the first solvent in the step S1 and the second solvent in the step S2 may be the same or different.
In the above technical solution, the dosage ratio of the second solvent to the metal salt in step S2 is 5-500mL of solvent per 1.0g of metal salt.
In the above technical solution, the mass ratio of the metal in the metal-organic framework in step S2 to the graphene oxide obtained in step S1 is 1: (0.01-1).
In the above technical solution, the reaction conditions of step S2: the reaction temperature is 30-150 ℃, preferably 80-110 ℃, and the reaction time is 3-24h, preferably 16-20 h.
In the technical scheme, the reduced graphene oxide (rGO) in the truncated polyhedral MOFs @ rGO material is obtained by reducing the graphene oxide dispersion liquid in the step S2 in the reaction process.
In the present invention, the apparatus for mixing and reacting the raw materials is not limited, and may be any apparatus capable of achieving mixing or reaction existing in the art, for example, the apparatus for mixing and reacting may be a reactor or a reaction kettle.
In the present invention, before the reaction in step S2, there may be a stirring and ultrasonic process to promote the reaction. After the reaction, there may be filtration, washing and drying steps, and such steps are not particularly limited except for the drying process, and may be any means capable of achieving filtration and washing. In step S2, washing may be performed or may not be performed, and the washing is preferably performed. In the present invention, the washing in step S2 is not limited as long as the purpose of washing can be achieved.
In the above technical solution, the step S2 further includes drying after the reaction, the drying is performed in two stages, preferably, the temperature of the first stage is 50-100 ℃ and the time is 1-24h, and the drying temperature of the second stage is 100-200 ℃ and the time is 1-24 h.
In the technical scheme, the metal organic framework material in the prepared truncated polyhedron MOFs @ rGO material is a truncated polyhedron, the edge length of the polyhedron is 3-10 mu m, the side length of a section polygon is 0.5-5 mu m, and the section polygon can be a triangle, a quadrangle, a pentagon or a hexagon.
In the technical scheme, the prepared truncated polyhedron-shaped MOFs @ rGO material is a hierarchical porous material and comprises micropores and mesopores; the total pore volume is 0.40-0.90cm3The mesoporous volume is 0.01-0.40cm3The pore volume of the micropores is 0.10-0.85cm3The specific surface area is 1000-1500m2(ii) in terms of/g. Preferably, the truncated polyhedral MOFs @ rGO material is a hierarchical porous material, and the total pore volume is 0.60-0.80cm3The mesoporous volume is 0.12-0.40cm3The pore volume of the micropores is 0.40-0.58cm3The specific surface area is 1000-2/g。
In the technical scheme, the prepared truncated polyhedral MOFs @ rGO material is in a crystal structure that a metal organic framework material grows on a reduced graphene oxide sheet layer or the metal organic framework material is wrapped by the reduced graphene oxide sheet layer.
The third aspect of the invention provides a method for removing thiophene sulfides, which comprises the step of contacting the truncated polyhedron MOFs @ rGO material provided by the first aspect or the truncated polyhedron MOFs @ rGO material prepared by the preparation method provided by the second aspect with a material containing thiophene.
In the technical scheme, the concentration of the thiophene in the material containing the thiophene is 0.5-5mgS/g, and the airspeed is 0.1-5h-1。
The invention has the following beneficial effects:
1. the truncated polyhedral MOFs @ rGO material provided by the invention has rich pore channel structures and a large number of defect sites, and is a multi-level pore material with mesopores and micropores, so that the adsorption of sulfides with larger molecular weight, such as thiophene, and the like is facilitated. And because the reduced graphene oxide sheet layer causes a segmentation effect on the MOF, a truncated polyhedron shape is formed, so that sulfides can enter pore channels more easily.
2. The preparation method of the desulfurization material disclosed by the invention fully realizes the integration of steps, so that the added modification material fully exerts various effects, and the material cost and the time cost are greatly saved. The addition of the anionic surfactant can not only promote the stripping of the graphite oxide in the early stage and prevent the graphite oxide from being aggregated after the stripping in the later stage, but also be used as a template agent to construct mesopores, macropores and structures in the microporous MOFs. The addition of the alcohol solvent in the mixed solvent can promote the dispersion of graphite oxide, can also serve as a weak reducing agent in a later-stage high-temperature environment to enable part of graphene oxide to become a reduced graphene oxide sheet layer, and enable defect sites which are beneficial to S adsorption to appear in MOFs, and the defect sites which appear also contribute to the segmentation effect of the reduced graphene oxide sheet layer on the MOFs to form a truncated polyhedron shape. The integration of all steps in the preparation method flexibly regulates the properties of MOF crystal structures and the sizes of apertures, so that the desulfurization performance of the MOFs @ rGO composite material is greatly improved.
Drawings
FIG. 1 is an SEM image of the MOFs @ rGO-1 material prepared in example 1;
FIG. 2 is an SEM image of the MOFs @ rGO-2 material prepared in example 2;
FIG. 3 is an SEM image of the MOFs @ rGO-4 material prepared in example 4;
FIG. 4 is an SEM image of the MOFs @ rGO-5 material prepared in example 5;
FIG. 5 is an SEM image of a MOF-d1 material prepared in comparative example 1;
FIG. 6 is an SEM image of a MOFs @ rGO-d2 material prepared in comparative example 2;
FIG. 7 is an SEM image of the MOFs @ rGO-d3 material prepared in comparative example 3;
FIG. 8 is an SEM image of a MOFs @ rGO-d4 material prepared in comparative example 4;
FIG. 9 is a TEM image of the MOFs @ rGO-1 material of example 1(a) and the MOF-d1 material of comparative example 1 (b);
FIG. 10 is an XRD pattern of the MOFs @ rGO-1 material of example 1 and the MOF-d1 material of comparative example 1 (b).
Detailed Description
The technical solution of the present invention is further illustrated by the following examples, but the scope of the present invention is not limited by the examples. In the present invention, wt% is a mass fraction.
The pore size property analysis of the samples in the present invention was obtained by testing the nitrogen adsorption-desorption isotherm of the material at 77K by ASAP2020 (Micrometrics). The specific surface area of the sample is calculated by a Brunauer-Emmett-Teller (BET) equation, and the micropore volume (V) of the material is obtained by using a T-plot micropore analysis methodmicro) Obtaining the total pore volume (V) of the material by a single point adsorption branch of the adsorption isothermtotal)。
Scanning Electron Microscope (SEM) photographs of the samples of the present invention were taken on a Hitachi S-4800 type II scanning electron microscope. The accelerating voltage of the instrument is 15kV, and the samples are subjected to chromium plating treatment before analysis.
TEM photographs of the samples in the present invention were taken on a transmission electron microscope of JEM-2100HR, JEOL. The lattice resolution was 0.14nm, the dot resolution was 0.23nm, and the maximum voltage was 200 kV.
The XRD pattern of the sample in the invention is obtained by a Rigaku-Ultima type X-ray diffractometer in Japan and MOFs crystal phase analysis is carried out. CuK α radiation, wavelength λ 0.15432 nm. The scanning range 2 theta of the X-ray diffraction pattern is 3-75 degrees, the scanning speed is 5 degrees/min, and the step length is 0.02 degrees.
Example 1
Weighing 50mg of graphite oxide and 50mg of sodium benzenesulfonate, dispersing into 100mL of ethanol, and performing ultrasonic treatment for 8h to fully strip the graphite oxide and the sodium benzenesulfonate to obtain graphene oxide dispersion A with a uniform system.
Mesoxybenzoic acid (700 mg) was weighed and added to a mixture of 40mL absolute ethanol and 20mL N, N-dimethylformamide, and stirred thoroughly for 30 min. 1400mg of copper nitrate trihydrate was weighed and dissolved in 20mL of deionized water, and then the two solutions were stirred well for 60min to obtain MOF-199 mother liquor. Slowly adding the graphene oxide dispersion liquid A into MOF-199 mother liquor, and carrying out ultrasonic treatment for 60 min. Then the mixture is put into a reaction kettle at the temperature of 95 ℃ for reaction for 20 hours. And after the reaction is finished, naturally cooling to room temperature, centrifuging, washing for 3 times by using absolute ethyl alcohol, drying for 6h at 60 ℃, and drying for 8h at 130 ℃ to obtain the MOFs @ rGO-1 material. Wherein the mass ratio of the metal in the metal-organic framework to the reduced graphene oxide is about 25: 1.
The data of the specific surface area, the pore property and the like of the MOFs @ rGO-1 material are shown in Table 1. The SEM image of the material is shown in figure 1, wherein in figure 1, a plurality of crystals are stacked, the edge length of a polyhedron is 3-10 mu m, the cross section of the crystal is a polygon with 1-2 mu m crystals on the side, and pores are distributed on the surface. In the TEM image, as shown in fig. 9(a), the periphery of the black polygon is wrapped with a thin amorphous material, which should be a reduced graphene oxide sheet layer, and the crystal has lattice defects inside, which should be a mesoporous structure. The XRD pattern is shown in FIG. 10, it can be seen that there is not much difference between the peaks of the MOFs @ rGO and the MOFs material of comparative example 1 in the XRD, because the reduced graphene oxide is in an amorphous state, and the XRD represents the long-range order of the crystal, so that only a very wide peak with very low peak intensity is obtained, and the MOFs crystal is in an ordered state, so that the peak of the reduced graphene oxide cannot be seen in the XRD pattern of the composite product. However, as can be seen from the figure, the base line of MOFs @ rGO has some arched bulges indicating that there is an amorphous morphology but no sharp carbon peaks indicating that the dispersed graphene lamellae do not aggregate.
The MOFs @ rGO-1 material is subjected to desulfurization performance evaluation by a fixed bed thiophene adsorption device. The concentration of the thiophene of the raw material is 2mgS/g, and the airspeed is set to be 4h-1The dynamic adsorption sulfur capacity was found to be 38.33 mg-S/g.
Example 2
Weighing 50mg of graphite oxide and 50mg of sodium dodecyl benzene sulfonate, dispersing into 100mL of ethanol, and performing ultrasonic treatment for 8 hours to fully strip the graphite oxide and the sodium dodecyl benzene sulfonate to obtain the graphene oxide dispersion liquid A with a uniform system.
Mesoxybenzoic acid (700 mg) was weighed and added to a mixture of 40mL absolute ethanol and 20mL N, N-dimethylformamide, and stirred thoroughly for 30 min. 1400mg of copper nitrate trihydrate was weighed and dissolved in 20mL of deionized water, and then the two solutions were stirred well for 60min to obtain MOF-199 mother liquor. Slowly adding the graphene oxide dispersion liquid A into MOF-199 mother liquor, and carrying out ultrasonic treatment for 60 min. Then the mixture is put into a reaction kettle at the temperature of 95 ℃ for reaction for 20 hours. And after the reaction is finished, naturally cooling to room temperature, centrifuging, washing for 3 times by using absolute ethyl alcohol, drying for 6h at 60 ℃, and drying for 8h at 130 ℃ to obtain the MOFs @ rGO-2 material. Wherein the mass ratio of the metal in the metal-organic framework to the reduced graphene oxide is about 23: 1.
The data of the specific surface area, the pore property and the like of the MOFs @ rGO-2 material are shown in Table 1. The SEM image of the material is shown in figure 2, the edge length of the polyhedron is 3-10 μm, the crystal section is a triangle with the side length of about 1-3 μm, and floccules are gathered on the crystal surface.
And the MOFs @ rGO-2 material is subjected to desulfurization performance evaluation by a fixed bed thiophene adsorption device. The concentration of the thiophene of the raw material is 2mgS/g, and the airspeed is set to be 4h-1The dynamic adsorption sulfur capacity was found to be 36.77 mg-S/g.
Example 3
Weighing 140mg of graphite oxide and 50mg of sodium benzenesulfonate, dispersing into 100mL of ethanol, and performing ultrasonic treatment for 8h to fully strip the graphite oxide and the sodium benzenesulfonate to obtain graphene oxide dispersion A with a uniform system.
Mesoxybenzoic acid (700 mg) was weighed and added to a mixture of 40mL absolute ethanol and 20mL N, N-dimethylformamide, and stirred thoroughly for 30 min. 1400mg of copper nitrate trihydrate was weighed and dissolved in 20mL of deionized water, and then the two solutions were stirred well for 60min to obtain MOF-199 mother liquor. Slowly adding the graphene oxide dispersion liquid A into MOF-199 mother liquor, and carrying out ultrasonic treatment for 60 min. Then the mixture is put into a reaction kettle at the temperature of 95 ℃ for reaction for 20 hours. And after the reaction is finished, naturally cooling to room temperature, centrifuging, washing for 3 times by using absolute ethyl alcohol, drying for 6h at 60 ℃, and drying for 8h at 130 ℃ to obtain the MOFs @ rGO-3 material. Wherein the mass ratio of the metal in the metal-organic framework to the reduced graphene oxide is about 16: 1.
The data of the specific surface area and pore properties of the MOFs @ rGO-3 material are shown in Table 1, and the SEM image of the material is similar to that of example 1. The edge length of the polyhedron is 3-10 μm, and the cross section of the crystal is a polygon with edge length of 1-3 μm.
And the MOFs @ rGO-3 material is subjected to desulfurization performance evaluation by a fixed bed thiophene adsorption device. The concentration of the thiophene of the raw material is 2mgS/g, and the airspeed is set to be 4h-1The dynamic adsorption sulfur capacity was found to be 33.15 mg-S/g.
Example 4
Weighing 20mg of graphite oxide and 50mg of sodium benzenesulfonate, dispersing into 100mL of ethanol, and performing ultrasonic treatment for 8h to fully strip the graphite oxide and the sodium benzenesulfonate to obtain graphene oxide dispersion A with a uniform system.
Mesoxybenzoic acid (700 mg) was weighed and added to a mixture of 40mL absolute ethanol and 20mL N, N-dimethylformamide, and stirred thoroughly for 30 min. 1400mg of copper nitrate trihydrate was weighed and dissolved in 20mL of deionized water, and then the two solutions were stirred well for 60min to obtain MOF-199 mother liquor. Slowly adding the graphene oxide dispersion liquid A into MOF-199 mother liquor, and carrying out ultrasonic treatment for 60 min. Then the mixture is put into a reaction kettle at the temperature of 95 ℃ for reaction for 20 hours. And naturally cooling to room temperature after the reaction is finished, centrifuging, washing for 3 times by using absolute ethyl alcohol, drying for 6 hours at 60 ℃, and drying for 8 hours at 130 ℃ to obtain the MOFs @ rGO-4 material. Wherein the mass ratio of the metal in the metal-organic framework to the reduced graphene oxide is about 56: 1.
The data of the specific surface area, the pore property and the like of the MOFs @ rGO-4 material are shown in Table 1. The SEM image of the material is shown in FIG. 3, the crystal is truncated octahedron, the cross section is a quadrangle with the side length of 1, and the surface is provided with pores. The edge length of the polyhedron is 3-10 μm, and the crystal section is a polygon with side length of about 0.5-2 μm.
And the MOFs @ rGO-4 material is subjected to desulfurization performance evaluation by a fixed bed thiophene adsorption device. The concentration of the thiophene of the raw material is 2mgS/g, and the airspeed is set to be 4h-1The dynamic adsorption sulfur capacity was found to be 31.43 mg-S/g.
Example 5
Weighing 50mg of graphite oxide and 10mg of sodium benzenesulfonate, dispersing into 100mL of ethanol, and performing ultrasonic treatment for 8h to fully strip the graphite oxide and the sodium benzenesulfonate to obtain graphene oxide dispersion A with a uniform system.
Mesoxybenzoic acid (700 mg) was weighed and added to a mixture of 40mL absolute ethanol and 20mL N, N-dimethylformamide, and stirred thoroughly for 30 min. 1400mg of copper nitrate trihydrate was weighed and dissolved in 20mL of deionized water, and then the two solutions were stirred well for 60min to obtain MOF-199 mother liquor. Slowly adding the graphene oxide dispersion liquid A into MOF-199 mother liquor, and carrying out ultrasonic treatment for 60 min. Then the mixture is put into a reaction kettle at the temperature of 95 ℃ for reaction for 20 hours. And after the reaction is finished, naturally cooling to room temperature, centrifuging, washing for 3 times by using absolute ethyl alcohol, drying for 6h at 60 ℃, and drying for 8h at 130 ℃ to obtain the MOFs @ rGO-5 material. Wherein the mass ratio of the metal in the metal-organic framework to the reduced graphene oxide is about 21: 1.
The data of the specific surface area, the pore property and the like of the MOFs @ rGO-5 material are shown in Table 1. The SEM image of the material is shown in figure 4, the crystal is a truncated octahedron, the cross section is a quadrangle with the edge length of 3, and the surface hole is not obvious. The edge length of the polyhedron is 3-10 μm, and the crystal section is a triangle with the side length of 2-5 μm.
And the MOFs @ rGO-5 material is subjected to desulfurization performance evaluation by a fixed bed thiophene adsorption device. The concentration of the thiophene of the raw material is 2mgS/g, and the airspeed is set to be 4h-1The dynamic adsorption sulfur capacity was found to be 27.07 mg-S/g.
Example 6
Weighing 50mg of graphite oxide and 140mg of sodium benzenesulfonate, dispersing into 100mL of ethanol, and performing ultrasonic treatment for 8h to fully strip the graphite oxide and the sodium benzenesulfonate to obtain graphene oxide dispersion A with a uniform system.
Mesoxybenzoic acid (700 mg) was weighed and added to a mixture of 40mL absolute ethanol and 20mL N, N-dimethylformamide, and stirred thoroughly for 30 min. 1400mg of copper nitrate trihydrate was weighed and dissolved in 20mL of deionized water, and then the two solutions were stirred well for 60min to obtain MOF-199 mother liquor. Slowly adding the graphene oxide dispersion liquid A into MOF-199 mother liquor, and carrying out ultrasonic treatment for 60 min. Then the mixture is put into a reaction kettle at the temperature of 95 ℃ for reaction for 20 hours. And after the reaction is finished, naturally cooling to room temperature, centrifuging, washing for 3 times by using absolute ethyl alcohol, drying for 6h at 60 ℃, and drying for 8h at 130 ℃ to obtain the MOFs @ rGO-6 material. Wherein the mass ratio of the metal in the metal-organic framework to the reduced graphene oxide is about 26: 1.
The data of the specific surface area and pore properties of the MOFs @ rGO-6 material are shown in Table 1, and the SEM image of the material is similar to that of example 1. The edge length of the polyhedron is 3-10 μm, and the crystal section is a polygon with the side length of 1-3 μm.
And the MOFs @ rGO-6 material is subjected to desulfurization performance evaluation by a fixed bed thiophene adsorption device. The concentration of the thiophene of the raw material is 2mgS/g, and the airspeed is set to be 4h-1The dynamic adsorption sulfur capacity was found to be 34.39 mg-S/g.
Comparative example 1
Mesoxybenzoic acid (700 mg) was weighed and added to a mixture of 40mL absolute ethanol and 20mL N, N-dimethylformamide, and stirred thoroughly for 30 min. 1400mg of copper nitrate trihydrate was weighed and dissolved in 20mL of deionized water, and then the two solutions were stirred well for 60min to obtain MOF-199 mother liquor. Putting the mixture into a reaction kettle at the temperature of 95 ℃ for reaction for 20 hours. And after the reaction is finished, naturally cooling to room temperature, centrifuging, washing for 3 times by using absolute ethyl alcohol, drying for 6h at 60 ℃, and drying for 8h at 130 ℃ to obtain the MOF-d1 material.
The specific surface area and pore properties of the MOF-d1 material are shown in Table 1. The SEM image of the material is shown in FIG. 5, with the crystal edge length of 3-10 μm and no truncated angle. The TEM image of the material is shown in fig. 9(b), and unlike comparative example 1, no amorphous material was wrapped around the polygon and no light source penetrated inside the crystal, indicating that the pore size inside the crystal was fine.
And carrying out desulfurization performance evaluation on the MOF-d1 material by a fixed bed thiophene adsorption device. The concentration of the thiophene of the raw material is 2mgS/g, and the airspeed is set to be 4h-1The dynamic adsorption sulfur capacity was found to be 18.01 mg-S/g.
Comparative example 2
Weighing 50mg of graphite oxide, dispersing into 100mL of ethanol, and carrying out ultrasonic treatment for 8 hours to fully strip the graphite oxide to obtain graphene oxide dispersion liquid A with a uniform system.
Trimesic acid 700mg was weighed and added to a mixture of 40mL of absolute ethanol and 20mL of N, N-dimethylformamide, and stirred thoroughly for 30 min. 1400mg of copper nitrate trihydrate was weighed and dissolved in 20mL of deionized water, and then the two solutions were stirred well for 60min to obtain MOF-199 mother liquor. Slowly adding the graphene oxide dispersion liquid A into MOF-199 mother liquor, and carrying out ultrasonic treatment for 60 min. Then the mixture is put into a reaction kettle at the temperature of 95 ℃ for reaction for 20 hours. And after the reaction is finished, naturally cooling to room temperature, centrifuging, washing for 3 times by using absolute ethyl alcohol, drying for 6h at 60 ℃, and drying for 8h at 130 ℃ to obtain the MOFs @ rGO-d2 material. Wherein the mass ratio of the metal in the metal-organic framework to the reduced graphene oxide is about 17: 1.
The data of the specific surface area, the pore property and the like of the MOFs @ rGO-d2 material are shown in Table 1. The SEM image of the material is shown in figure 6, the crystal is a truncated octahedron, the edge length of the octahedron is 3-10 μm, the cross section is a quadrangle with the side length of 0.5-2, and the surface is smooth.
The MOFs @ rGO-d2 material is subjected to desulfurization performance evaluation by a fixed bed thiophene adsorption device. The concentration of the thiophene of the raw material is 2mgS/g, and the airspeed is set to be 4h-1The dynamic adsorption sulfur capacity was found to be 23.43 mg-S/g.
Comparative example 3
50mg of sodium benzenesulfonate is weighed and dispersed into 100mL of ethanol to obtain graphene oxide dispersion liquid A with a uniform system. Mesoxybenzoic acid (700 mg) was weighed and added to a mixture of 40mL absolute ethanol and 20mL N, N-dimethylformamide, and stirred thoroughly for 30 min. 1400mg of copper nitrate trihydrate was weighed and dissolved in 20mL of deionized water, and then the two solutions were stirred well for 60min to obtain MOF-199 mother liquor. Slowly adding the graphene oxide dispersion liquid A into MOF-199 mother liquor, and carrying out ultrasonic treatment for 60 min. Then the mixture is put into a reaction kettle at the temperature of 95 ℃ for reaction for 20 hours. And naturally cooling to room temperature after the reaction is finished, centrifuging, washing for 3 times by using absolute ethyl alcohol, drying for 6 hours at 60 ℃, and drying for 8 hours at 130 ℃ to obtain the MOFs @ rGO-d3 material.
The data of the specific surface area, the pore property and the like of the MOFs @ rGO-d3 material are shown in Table 1. The SEM image of the material is shown in FIG. 7, the crystal is octahedron, the edge length of the octahedron is 3-10 μm, and a small amount of aggregates are on the surface.
The MOFs @ rGO-d3 material is subjected to desulfurization performance evaluation by a fixed bed thiophene adsorption device. The concentration of the thiophene of the raw material is 2mgS/g, and the airspeed is set to be 4h-1The dynamic adsorption sulfur capacity was found to be 24.11 mg-S/g.
Comparative example 4
Trimesic acid 700mg was weighed and added to a mixture of 40mL of absolute ethanol and 20mL of N, N-dimethylformamide, and stirred thoroughly for 30 min. 1400mg of copper nitrate trihydrate is weighed and dissolved in 20mL of deionized water, then the two solutions are fully stirred for 60min to obtain MOF-199 mother liquor, and then 50mg of graphite oxide and 50mg of sodium benzenesulfonate are weighed and subjected to ultrasound for 60 min. Then the mixture is put into a reaction kettle at the temperature of 95 ℃ for reaction for 20 hours. And after the reaction is finished, naturally cooling to room temperature, centrifuging, washing for 3 times by using absolute ethyl alcohol, drying for 6h at 60 ℃, and drying for 8h at 130 ℃ to obtain the MOFs @ rGO-d4 material. Wherein the mass ratio of the metal in the metal-organic framework to the reduced graphene oxide is about 16: 1.
The data of the specific surface area, the pore property and the like of the MOFs @ rGO-d4 material are shown in Table 1. The SEM image of the material is shown in FIG. 8, where the crystal shape is not evident and there are a large number of aggregates on the surface.
The MOFs @ rGO-d4 material is subjected to desulfurization performance evaluation by a fixed bed thiophene adsorption device. The concentration of the thiophene of the raw material is 2mgS/g, and the airspeed is set to be 4h-1And the dynamic adsorption sulfur capacity is measured to be 25.99 mg-S/g.
TABLE 1 parameters of specific surface area and pore Properties for examples 1-6 and comparative examples 1-4
Note: [ a ] A]SBETRepresents the BET specific surface area calculated from the formula Brunauer-Emmett-Teller (BET); [ b ] a]VtRepresents the total pore volume; [ c ] is]VmicroRepresents the pore volume of the micropores; [ d]VmesoRepresents the mesoporous volume.
Claims (14)
1. The truncated polyhedron-shaped MOFs @ rGO material comprises reduced graphene oxide and a metal organic framework material, and the truncated polyhedron-shaped MOFs @ rGO material contains a hierarchical pore structure.
2. The truncated polyhedral MOFs @ rGO material according to claim 1, wherein the metal source in the metal organic framework material is selected from one or more of Cu, Fe, Cr, V, Mn, Co, Ni; preferably at least one of Cu and V.
3. The truncated polyhedral MOFs @ rGO material according to claim 1, wherein the ligands of the metal-organic framework are selected from one or more of trimesic acid, terephthalic acid, 4-bipyridine and 3,4, 5-biphenyltricarboxylic acid.
4. The truncated polyhedral MOFs @ rGO material of claim 1, wherein the mass ratio of metal to reduced graphene oxide in the metal organic framework is 1: (0.01-1).
5. The truncated polyhedral MOFs @ rGO material of claim 1, wherein said metal organic framework material is a truncated polyhedron with a length of the polyhedron of 3-10 μm, a length of the side of the cross-sectional polygon of 0.5-5 μm, and a triangle, a quadrilateral, a pentagon or a hexagon in cross-sectional polygon.
6. The truncated polyhedral MOFs @ rGO material of claim 1, wherein the truncated polyhedral MOFs @ rGO material is a hierarchical porous material comprising micropores and mesopores; the total pore volume is 0.40-0.90cm3The mesoporous volume is 0.01-0.40cm3The pore volume of the micropores is 0.10-0.85cm3The specific surface area is 1000-1500m2/g。
7. A preparation method of a truncated polyhedral MOFs @ rGO material comprises the following steps:
s1: adding graphite oxide and an anionic surfactant into a first solvent, and ultrasonically stripping and dispersing to obtain graphene oxide dispersion liquid;
s2: dissolving metal salt and a ligand in a second solvent to form a reaction solution, mixing the reaction solution with the graphene oxide dispersion liquid obtained in S1, and reacting to obtain the truncated polyhedral MOFs @ rGO material;
wherein the first solvent or/and the second solvent comprises an alcohol solvent.
8. The method of claim 7, wherein the anionic surfactant of step S1 comprises one or more of alkyl benzene sulfonate, alpha-olefin sulfonate, alkyl sulfonate, alpha-sulfomonocarboxylic acid and its derivatives, and fatty acid sulfoalkyl ester.
9. The method of claim 7, wherein the first solvent in step S1 includes one or more of monohydric alcohol, dihydric alcohol, polyhydric alcohol, and deionized water.
10. The production method according to claim 7, wherein the mass ratio of the graphite oxide to the anionic surfactant in step S1 is 1: (0.1-5). The molar ratio of the metal salt to the ligand in step S2 is 1: (0.2-5).
11. The method according to claim 7, wherein the second solvent in step S2 includes one or more of N, N-dimethylformamide, N-dimethylacetamide, triethylamine, hydrofluoric acid, tetrahydrofuran, a monohydric alcohol, a dihydric alcohol, a polyhydric alcohol, and deionized water; the ligand is one or more selected from trimesic acid, terephthalic acid, 4-bipyridine and 3,4, 5-biphenyltricarboxylic acid.
12. The method according to claim 7, wherein the reaction conditions of step S2 are as follows: the reaction temperature is 30-150 ℃, preferably 80-110 ℃, and the reaction time is 3-24h, preferably 16-20 h.
13. A method for removing thiophenic sulfides comprising contacting the truncated polyhedral MOFs @ rGO material of any one of claims 1 to 6 or prepared by the method of any one of claims 7 to 12 with a thiophene containing material.
14. The method according to claim 13, wherein the concentration of thiophene in the thiophene-containing feed is from 0.5 to 5mgS/g, and the space velocity is from 0.1 to 5h-1。
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