CN109012709B - Metal Fe modified black phosphorus alkene and preparation method and application thereof - Google Patents

Metal Fe modified black phosphorus alkene and preparation method and application thereof Download PDF

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CN109012709B
CN109012709B CN201810896168.3A CN201810896168A CN109012709B CN 109012709 B CN109012709 B CN 109012709B CN 201810896168 A CN201810896168 A CN 201810896168A CN 109012709 B CN109012709 B CN 109012709B
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dichloromethane
black phosphorus
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雷双瑛
孙小龙
陈洁
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Southeast University
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    • B01J27/00Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
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Abstract

The invention discloses a metal Fe modified black phosphorus alkene, which is a two-dimensional layered structure material prepared by taking red phosphorus as a raw material, wherein the number of layers is 10-25; wherein the load density of the metal Fe is 7.9-10%. The invention also discloses a preparation method of the metal Fe modified black phosphorus alkene and application of the metal Fe modified black phosphorus alkene as a catalyst in dichloromethane catalytic dissociation. When the sintering phenomenon of the catalyst is reduced, the high surface-to-volume ratio of the two-dimensional material improves the catalytic efficiency, and the high temperature resistance of the black phosphorus enables the catalytic process to be more reliable, so that the cost is greatly reduced compared with the method of using the noble metal as the catalyst.

Description

Metal Fe modified black phosphorus alkene and preparation method and application thereof
Technical Field
The invention belongs to a waste gas treatment technology, and particularly relates to a metal Fe modified black phosphorus alkene, and a preparation method and application thereof.
Background
As society develops, a large number of VOCs are released into the environment during production and life, and their kinds and numbers are increasingly expanding and complex. One of them is dichloromethane, which is used in large quantities for the manufacture of security cinematographic films, polycarbonates, the others as coating solvents, metal degreasers, aerosol propellants, polyurethane blowing agents, release agents, paint strippers. Methylene dichloride gas is emitted to the atmosphere globally every year by up to 120 million tons. More complex harmful substances are generated in the atmosphere and pose serious hazards to the atmospheric ozone layer and human health. Therefore, effective and rational purification and disposal of organic waste gases of methylene chloride are becoming increasingly of interest. The existing methods for treating and purifying methylene dichloride organic waste gas have many processes, and the catalytic combustion method is the most potential organic waste gas treatment method. Since 1988, there have been reports of treating low-concentration chlorine-containing organic waste gas by catalytic combustion at home and abroad, but the developed catalyst has the defects of high combustion temperature, high energy consumption, easy coking and inactivation and the like, and has a poor industrial application prospect. Therefore, there is an urgent need to develop a novel catalyst which can treat chlorine-containing exhaust gas at a low concentration with high efficiency and high selectivity at a relatively low temperature and is suitable for industrial applications.
2D materials with atomic layer thickness are widely studied due to their superior properties unlike other materials, such as graphene, MoS2, and the like. In recent years, a new 2D material, a few-layer black phosphorus (black phosphorus alkene), has been prepared by a mechanical stripping method under experimental conditions and has received much attention. Black phosphorus is a crystal with metallic luster, can be converted from white phosphorus or red phosphorus, and has direct semiconductorBand gap, and exhibits characteristics related to the number of layers, electron mobility of few-layer black phosphorus being 1000cm2/V-1s-1And the material also has very high leakage current modulation rate, so that the material has great potential in the application of future nano electronic devices. Moreover, as one of the two-dimensional materials, the large surface-to-volume ratio is also the excellent property of the material, which lays a foundation for the research of the black phosphorus alkene on the aspect of gas adsorption and is one of the hotspots of the research of the novel two-dimensional material at present. A great deal of research shows that the black phosphorus alkene has strong adsorbability to N-containing gas molecules such as NO2、NO、NH3Etc., which also limits the use of black phosphenes for other gas adsorption applications.
Disclosure of Invention
The purpose of the invention is as follows: aiming at the technical problems in the prior art, the invention provides a catalyst metal Fe modified black phosphorus alkene which is formed by metal modification of two-dimensional material black phosphorus alkene, a preparation method and application of the catalyst, and a catalyst loaded with the catalyst.
The technical scheme is as follows: the preparation method of the metal Fe modified black phosphorus alkene comprises the following steps:
(1) taking red phosphorus, heating the red phosphorus and the Si substrate to 600-650 ℃ in a vacuum environment, keeping the temperature for 30-35 minutes, and then cooling to room temperature to obtain the Si substrate coated with the red phosphorus film;
(2) taking the Si substrate coated with the red phosphorus film obtained in the step (1), heating the Si substrate, Sn and SnI to 900-940 ℃ in a protective atmosphere of 26-27.8atm, keeping the temperature for 30-32 minutes, and then gradually cooling to room temperature to obtain the Si substrate coated with the black phosphorus film;
(3) and (3) putting the Si substrate coated with the black phosphorus film obtained in the step (2) into an Fe ion solution, fishing out the Si substrate after reaction, roasting the Si substrate in a protective atmosphere, cooling, and stripping the black phosphorus on the Si substrate under an electron microscope by a probe stripping method to obtain the Fe-loaded few-layer black phosphorus.
The method can prepare the black phosphorus alkene film with better quality, more stable performance and larger area compared with a mechanical stripping method, a liquid phase stripping method and other methods.
In the step (1), the red phosphorus is purified and dried, namely the red phosphorus is taken and put into deionized water for purification for 15 to 19 minutes and then is purified under the vacuum degree of 10-2-10-3Drying in an oven under Pa for 20-27 minutes.
In the step (2), the mass ratio of Sn to SnI is 1.14-2: 1. Wherein, SnI mainly plays the role of a mineralizer in the growth process of black phosphorus, and the mineralizer can improve and promote the solubility of phosphorus vapor in metal Sn.
Preferably, the mass ratio of Sn to SnI of the red phosphorus film is 1 (2.28-4) to 2.
In the step (2), the protective atmosphere is inert gas, preferably argon.
In the step (2), the gradual cooling to the room temperature means that the temperature is gradually reduced to the room temperature by 50-52.2 ℃ every 30-32 minutes.
In the step (3), the Fe ion solution is Fe (NO)3)3The concentration of the solution is 0.04-0.1 g/mL; and putting the Si substrate coated with the black phosphorus film into the Fe ion solution for reacting for 15-30 minutes. Fe (NO) in comparison with other Fe ion solutions3)3The efficiency of forming Fe modified black phosphorus alkene is highest. In addition, the concentration of the Fe ion solution influences the modification density of the metal Fe, and the modification density which can be obtained under the condition of 0.04-0.1g/mL is 2.70% -10%.
Further preferably, the Fe (NO) is3)3The concentration of the solution was 0.0827 g/mL.
In the step (3), the calcination refers to calcination in a quartz tube at 700-720 ℃ for 10-15 minutes under the protection of nitrogen.
The metallic Fe modified black phosphenes prepared according to the above method are also within the scope of the present invention.
Further, the prepared metal Fe modified black phosphorus alkene is a two-dimensional layered structure material prepared by taking red phosphorus as a raw material, and the number of layers is 10-25; wherein the load density of the metal Fe is 7.9-10%.
The application of the metal Fe modified black phosphorus alkene as a catalyst in dichloromethane catalytic dissociation is also within the protection scope of the invention. Wherein the adsorption energy of the metal Fe modified black phosphorus alkene on dichloromethane can reach 1.008-1.034eV, and the dissociation energy of dichloromethane is 0.648-0.720 eV.
The dichloromethane dissociation catalyst comprises a central shaft, wherein a plurality of interlayers are distributed outwards along the central shaft, a catalyst filling layer is arranged between every two adjacent interlayers, an outer shell is wrapped outside the interlayer positioned at the outermost layer, and the central shaft, the interlayers and the outer shell are in cross connection through supporting layers; and the catalyst filling layer is filled with metal Fe modified black phosphorus alkene as a dichloromethane dissociation catalyst.
Preferably, the methylene chloride dissociation catalyst is cylindrical. The cylindrical shape can reduce the overall manufacturing cost and leave enough construction space for the catalyst. In contrast, if the housing is a rectangular housing with the same length as the design, about 75cm more housing volume is needed to achieve the design2The housing material of (1).
The middle shaft, the interlayer, the shell and the supporting layer are made of stainless steel; wherein the middle shaft is cylindrical, and the thickness of the shell is greater than that of the support isolation layer and that of the isolation layer.
Furthermore, the middle shaft is a stainless steel cylinder with the diameter of 5mm and the height of 150 mm; the interlayer is made of stainless steel with the thickness of 0.1mm, the height is 150mm, and the interlayer is manufactured by bending according to different lengths of the different layers of the interlayer; the shell is made of stainless steel with the thickness of 2mm, the length of the shell is 377mm, the height of the shell is 150mm, and a circular ring with the diameter of 60mm is manufactured by bending along the long edge to serve as the shell; the supporting layer is a rectangular stainless steel metal plate with the height of 150mm, the length of 25.5mm and the thickness of 1 mm. Wherein, (1) the parameters of the shell and the middle shaft can be amplified or reduced in the same proportion, and the height ratio is 1: 1, radius ratio of 12: 1; (2) the thickness of the interlayer is smaller than the interlayer spacing, and each interlayer spacing is generally controlled to be 1.8-2.5mm so as to facilitate the filling of the catalyst and the passing of the dichloromethane-containing gas; (3) the width of the interlayer is equal to the radius of the hollow cylinder of the shell minus the radius of the central axis.
The methylene chloride dissociation catalyst is prepared by the following method: the middle shaft, the interlayer, the shell and the supporting layer are sequentially coated and assembled, wherein the middle shaft and the supporting layer are connected in an argon gas shielded welding mode, the interlayer and the supporting layer are welded in an argon arc welding mode, the connected parts and the shell are welded in the argon arc welding mode, and finally a catalyst filling layer formed between every two adjacent interlayers is filled with a catalyst.
The activity of the black phosphorus alkene surface is activated by modifying the black phosphorus alkene surface, and common surface modification comprises adsorption of metal atoms and substitutional doping of the metal atoms, wherein the substitutional doping has a large influence on the structure of the black phosphorus alkene material, so the surface modification in a metal adsorption mode is adopted. Theoretical calculation proves that for the modification of the metal Fe atom, the black phosphorus alkene has the adsorption energy of 3.03eV for the Fe atom, so that the metal Fe can be well adsorbed on the surface of the black phosphorus alkene to form a stable cluster structure. The black phosphorus alkene modified by Fe atom has the adsorption energy of 1.034eV (which is far larger than the adsorption energy of pure black phosphorus to dichloromethane molecule by 0.315 eV), and the whole catalytic dissociation process has a potential barrier of 0.674eV and is a very favorable exothermic process.
Has the advantages that: compared with the prior art, the invention has the following beneficial effects: (1) the black phosphorus alkene used in the invention is one of two-dimensional materials, a stable 2D layer can be well formed on the surface of the Fe atom, and the formed Fe modified black phosphorus alkene (Fe-BP) system greatly improves the adsorption capacity to dichloromethane. (2) The two-dimensional material black phosphorus selected in the invention can make the catalyst layer very thin, thereby enabling the whole device to be more miniaturized and the volume to be reduced by 13% to the maximum. (3) The modified metal Fe adopted by the invention ensures that the potential barrier value of the dissociation of the C-Cl bond of the dichloromethane is only 0.674eV, so that the dichloromethane can be efficiently dissociated at the approximate normal temperature, and the efficiency is greatly improved. In summary, the high surface-to-volume ratio of the two-dimensional material improves the catalytic efficiency while reducing the sintering phenomenon of the catalyst, and the high temperature resistance of the black phosphorus enables the catalytic process to be more reliable, so that the cost is greatly reduced compared with the method of using noble metal as the catalyst.
Drawings
FIG. 1 is a top view of a metallic Fe modified black phosphene;
FIG. 2 is a side view of a metallic Fe-modified black phospholene;
FIG. 3 is a top view of an adsorption structure of metal Fe modified black phosphorus alkene on dichloromethane;
FIG. 4 is a side view of an adsorption structure of metal Fe modified black phosphorus alkene on dichloromethane;
FIG. 5 is a graph of dissociation barrier of metal Fe modified black phosphorus alkene to dichloromethane;
FIG. 6 is a cross-sectional view of the catalyst;
FIG. 7 is a side view of the catalyst;
FIG. 8 is a graph of the dissociation barrier of metal Pt-modified black phosphene to dichloromethane.
Wherein the abscissa in fig. 5 and 8 is the dissociation process structure (the three structural diagrams in the figures are respectively the initial state structure, the transition state structure and the final state structure from left to right), and the ordinate is the energy.
Detailed Description
The present application will be described in detail with reference to specific examples.
Example 1
The preparation method of the metal Fe modified black phosphorus alkene catalyst comprises the following steps:
A) weighing red phosphorus, purifying in deionized water for 15 min, taking out, and vacuum-pumping (vacuum degree of 10)-2-10-3Pa) drying in a drying box for 20 minutes, and putting the treated product into a dryer for use;
B) putting the dried red phosphorus into a tube furnace, putting a silicon substrate into the tube furnace, vacuumizing the tube furnace, heating to 630 ℃, keeping for 30 minutes, closing the tube furnace, and cooling at room temperature to obtain a Si substrate coated with a red phosphorus film;
C) transferring the obtained Si substrate coated with the red phosphorus film into a conical-bottom glass centrifugal tube containing Sn/SnI (red phosphorus film: Sn: SnI is 1:4:2), then putting the centrifugal tube into a pressure container reactor, filling argon into the reactor to reach 26atm, fixing the reactor in a tube furnace, heating to 920 ℃, and then cooling to 51 ℃ every 31 minutes until the reactor is completely closed to obtain the Si substrate coated with the black phosphorus film;
D) the treated Si substrate was placed at room temperature in a 0.0827g/mL Fe (NO) solution3)3The solution is added for 15 to 30 minutes;
E) and fishing out the Si substrate, drying the Si substrate on a heating table at 80-90 ℃, roasting the Si substrate in a quartz tube at 700 ℃ for 10-15 minutes under the protection of nitrogen, taking out the Si substrate after cooling, and stripping the black phosphorus alkene on the Si substrate under an electron microscope by a probe stripping method to obtain the Fe-loaded few-layer black phosphorus alkene.
Results testing
The structure of the metallic Fe modified black phosphorus alkene obtained by the method is shown in figures 1 and 2.
The adsorption experiment simulation is carried out by utilizing a VASP software package, and the specific process is as follows: firstly, establishing a single-layer black phosphorus model and carrying out structural optimization to obtain the energy E of stable black phosphorus alkenebPAdding Fe atoms into the black phosphorus alkene and carrying out structural optimization to obtain energy E of the stable metal Fe modified black phosphorus alkene systemFe-bP,Finally, adding optimized dichloromethane molecules (the energy of dichloromethane is E) on the metal Fe modified black phosphorus alkene systemCH2Cl2) And carrying out structure optimization to obtain stable energy E of the metal Fe modified black phosphorus alkene adsorbing dichloromethane systemFe-bP-CH2Cl2The adsorption structure of the metal Fe modified black phosphorus alkene on dichloromethane is shown in figures 3 and 4: the Fe modified black phosphorus alkene adsorbs dichloromethane, and a chemical bond is formed between a Cl atom of the dichloromethane and metal Fe, so that a stable chemical adsorption structure is shown. The adsorption energy of dichloromethane on the metal Fe modified black phosphorus alkene is calculated to be 1.034eV by using the formula (1), which shows that the Fe modified black phosphorus alkene has strong adsorption capacity on dichloromethane.
Ead=EFe-bp-CH2Cl2-(ECH2Cl2+EFe-bp) (1)
The metallic Fe modified black phosphorus alkene prepared in the example 1 is applied to the catalytic dissociation of dichloromethane.
In order to verify the catalytic effect of the metal Fe modified black phosphorus alkene on dichloromethane dissociation, we performed transition state search (in which a vacuum layer is set to be 15 angstroms) on dichloromethane in the metal Fe modified black phosphorus alkene dissociation process by using the CI-NEB method and using the structure in FIG. 1 as an initial state, and the final result is shown in FIG. 5. As can be seen from FIG. 5, methylene chloride is decomposed into Cl atom and CH on Fe-modified black phosphene2Cl structure in methylene chlorideThe dissociation barrier on the reagent is only 0.674eV, and the whole process is an exothermic process with favorable dissociation, thus improving dissociation efficiency.
Comparative example 1
Pt modified black phosphene and catalytic dissociation effect thereof.
This comparative example was compared with example 1, except that the Fe ion solution in step D) in the catalyst preparation was changed to a Pt ion solution, and the remaining conditions were the same, to prepare Pt-modified black phosphene.
Similarly, the catalytic effect of the metal Pt-modified black phosphene on the dissociation of dichloromethane was verified by the CI-NEB method described in example 1, and as a result, as shown in fig. 8, the decomposition barrier of dichloromethane on the catalyst supporting the Pt-modified black phosphene as a catalyst was 1.040 eV. Therefore, compared with the black phosphorus alkene modified by the noble metal Pt, the black phosphorus alkene modified by Fe is used as a dissociation catalyst of dichloromethane, the dissociation barrier is lower, and compared with the noble metal material, the black phosphorus alkene modified by Fe greatly reduces the cost.
Example 2
A preparation method of a metal Fe modified black phosphorus alkene catalyst comprises the following steps:
A) weighing red phosphorus, purifying in deionized water for 17 min, taking out, and vacuum-pumping (vacuum degree of 10)-2-10-3Pa) drying in a drying box for 23 minutes, and putting the treated product into a dryer for use;
B) putting the dried red phosphorus into a tubular furnace, putting a silicon substrate into the tubular furnace, vacuumizing the tubular furnace, heating to 600 ℃, keeping for 35 minutes, closing the tubular furnace, and cooling at room temperature to obtain a Si substrate coated with a red phosphorus film;
C) transferring the obtained Si substrate coated with the red phosphorus film into a conical-bottom glass centrifugal tube containing Sn/SnI (the red phosphorus film is Sn: SnI is 1:4:2), then putting the centrifugal tube into a pressure container reactor, filling argon into the reactor to reach 26.5atm, fixing the reactor in a tube furnace, heating to 900 ℃, and then cooling to 50 ℃ every 30 minutes until the reactor is completely closed to obtain the Si substrate coated with the black phosphorus film;
D) will processThe Si substrate after that was charged with Fe (NO) at a concentration of 0.04g/mL under room temperature conditions3)3The solution is added for 15 to 30 minutes;
E) and fishing out the Si substrate, drying the Si substrate on a heating table at 80-90 ℃, roasting the Si substrate in a quartz tube at 700 ℃ for 10-15 minutes under the protection of nitrogen, taking out the Si substrate after cooling, and stripping the black phosphorus alkene on the Si substrate under an electron microscope by a probe stripping method to obtain the Fe-loaded few-layer black phosphorus alkene.
Example 3
A preparation method of a metal Fe modified black phosphorus alkene catalyst comprises the following steps:
A) weighing red phosphorus, purifying in deionized water for 19 min, taking out, and vacuum-pumping (vacuum degree of 10)-2-10-3Pa) drying in a drying box for 27 minutes, and putting the treated product into a dryer for use;
B) putting the dried red phosphorus into a tubular furnace, putting a silicon substrate into the tubular furnace, pumping the tubular furnace to vacuum, heating to 650 ℃, keeping for 32 minutes, closing the tubular furnace, and cooling at room temperature to obtain a Si substrate coated with a red phosphorus film;
C) transferring the obtained Si substrate coated with the red phosphorus film into a conical-bottom glass centrifugal tube containing Sn/SnI (the red phosphorus film is Sn: SnI is 1:4:2), then putting the centrifugal tube into a pressure container reactor, filling argon into the reactor to reach 27.8atm, fixing the reactor in a tube furnace, heating to 940 ℃, and then cooling to 52.2 ℃ every 32 minutes until the reactor is completely closed to obtain the Si substrate coated with the black phosphorus film;
D) the treated Si substrate was charged with Fe (NO) at a concentration of 0.1g/mL at room temperature3)3The solution is added for 15 to 30 minutes;
E) and fishing out the Si substrate, drying the Si substrate on a heating table at 80-90 ℃, roasting the Si substrate in a quartz tube at 700 ℃ for 10-15 minutes under the protection of nitrogen, taking out the Si substrate after cooling, and stripping the black phosphorus alkene on the Si substrate under an electron microscope by a probe stripping method to obtain the Fe-loaded few-layer black phosphorus alkene.
Some characteristics of the metallic Fe-modified black phosphenes prepared in examples 1, 2 and 3 were compared and tested for adsorption and desorption by the simulation method in example 1, and the results are shown in the following table:
Figure BDA0001758215100000071
according to the test results, it can be seen that: as the pressure in the pressure vessel reactor increases, the number of layers of the prepared few-layer black phosphorus gradually increases, but is basically maintained at 10-25 layers. For the density of the metal modified black phosphorus alkene, the modification density of about 2.7-10% can be achieved within the concentration range of 0.04-0.1 g/mL. The adsorption energy of the Fe modified black phosphorus alkene on dichloromethane can reach more than 1.0eV, so that the catalyst can well capture dichloromethane. In addition, the dissociation barrier can be maintained at about 0.70eV, which ensures that the dichloromethane can be dissociated at a temperature close to normal temperature.
Example 5
A dichloromethane dissociation catalyst is cylindrical, as shown in figures 6 and 7, the diameter of the dichloromethane dissociation catalyst is 60mm, the height of the dichloromethane dissociation catalyst is 150mm, the dichloromethane dissociation catalyst is formed by wrapping and assembling a central shaft 1, interlayer 2, a shell 3 supporting layer 4 and a catalyst filling layer 5, wherein the interlayer 2 comprises a plurality of annular catalyst filling layers 5 which are distributed along the central shaft 1 in an outward diffusion mode, the catalyst filling layer 5 is arranged between every two adjacent interlayer 2, the shell 3 is wrapped outside the outermost interlayer 2, the central shaft 1, the interlayer 2 and the shell 3 are connected through the supporting layer 4, and the supporting layer 4 is distributed in a cross mode; the catalyst-packed layer 5 is packed with a methylene chloride dissociation catalyst. The middle shaft 1, the interlayer 2, the shell 3 and the supporting layer 4 are made of stainless steel; the thickness of the shell > the thickness of the support isolation layer > the thickness of the isolation layer; the distance between the adjacent interlayer 2 is 1-2mm, which is slightly less than the thickness of the shell. The dichloromethane dissociation catalyst is the metallic Fe modified black phosphene prepared in example 1.
The preparation method of the dichloromethane dissociation catalyst comprises the following steps:
1) manufacturing a middle shaft: the middle shaft is of a stainless steel cylindrical structure with the diameter of 5mm and the height of 150 mm;
2) manufacturing the interlayer: the interlayer is made of stainless steel with the thickness of 0.1mm, the height of the interlayer is 150mm, different lengths are selected according to different layers of the interlayer, 1/4 circular rings with different radiuses are manufactured by bending along the length edge and are used as the interlayer, and the distance between every two interlayers is controlled to be 1.8-2.5 mm;
3) manufacturing the shell: the shell is made of stainless steel with the thickness of 2mm, the length of the shell is 377mm, the height of the shell is 150mm, and the shell is made into a hollow cylinder with the radius of about 60mm by bending along the long edge;
4) manufacturing a support layer: the supporting layer is made of a rectangular stainless steel metal plate with the height of 150mm, the length of 25.5mm and the thickness of 1 mm;
5) catalyst filling layer: the catalyst filled in the catalyst filling layer is black phosphorus alkene modified by metal Fe;
6) sequentially coating and assembling the middle shaft, the interlayer, the shell, the supporting layer and the catalyst filling layer prepared in the steps 1) -5) to obtain the dichloromethane dissociation catalyst, wherein the maximum diameter of the dichloromethane dissociation catalyst reaches 60 mm. The specific connection mode is as follows: the middle shaft and the supporting layer are connected in an argon gas shielded welding mode, then argon arc welding is carried out between the 1/4 circular ring-shaped isolation layer and the supporting layer, then the connected part and the shell are welded in the argon arc welding mode, and finally the catalyst is filled.
The use of a two-dimensional material as support for the metal Fe allows the catalytic layer to be made sufficiently thin that the overall catalyst (fig. 6 and 7) is reduced in volume by up to 13%.

Claims (4)

1.一种用于催化离解二氯甲烷的金属Fe修饰的黑磷烯,其特征在于,通过以下方法制备:1. a kind of black phosphorene that is used for the modification of the metal Fe of catalysis dissociation methylene dichloride, it is characterised in that, prepared by the following method: (1)取红磷,将其与Si衬底在真空环境下升温至600-650℃,保持30-35分钟,然后冷却至室温,得到覆有红磷薄膜的Si衬底;(1) get red phosphorus, heat it and Si substrate to 600-650 ℃ under vacuum environment, keep 30-35 minutes, then cool to room temperature, obtain Si substrate covered with red phosphorus film; (2)取步骤(1)所得覆有红磷薄膜的Si衬底,与Sn和SnI4在26-27.8atm的保护性气氛下,升温至900-940℃保持30-32分钟,然后逐渐降至室温,得到覆有黑磷薄膜的Si衬底;(2) Take the Si substrate covered with the red phosphorus film obtained in step (1), and with Sn and SnI 4 in a protective atmosphere of 26-27.8 atm, heat up to 900-940 ° C for 30-32 minutes, and then gradually decrease to room temperature to obtain a Si substrate covered with a black phosphorus film; (3)将步骤(2)所得覆有黑磷薄膜的Si衬底放入Fe离子溶液中,室温条件下反应后捞出Si衬底置于保护性气氛下焙烧后冷却,将Si衬底上的黑磷烯在电子显微镜下通过探针剥离的方法剥离得到负载Fe的少层黑磷烯;(3) Put the Si substrate covered with the black phosphorus film obtained in step (2) into the Fe ion solution, remove the Si substrate after the reaction at room temperature, place it in a protective atmosphere, bake it, and cool it, and place the Si substrate on the Si substrate. Fe-loaded black phosphorene was exfoliated by probe exfoliation under an electron microscope; 步骤(1)中,所述红磷先纯化并干燥,即取红磷,置于去离子水中纯化15-19分钟,然后在真空度10-2-10-3Pa的烘箱中干燥20-27分钟;In step (1), the red phosphorus is first purified and dried, that is, the red phosphorus is taken, placed in deionized water for purification for 15-19 minutes, and then dried in an oven with a vacuum degree of 10 -2 -10 -3 Pa for 20-27 minutes. minute; 步骤(2)中,所述Sn和SnI4的质量比为1.14-2:1,所述红磷薄膜:Sn:SnI4质量比为1:(2.28-4):2;In step (2), the mass ratio of the Sn and SnI is 1.14-2 :1, and the red phosphorus film:Sn:SnI mass ratio is 1 :(2.28-4):2; 步骤(2)中,所述逐渐降至室温是指以每30-32分钟降温50-52.2℃逐渐降至室温;In step (2), the step of gradually lowering to room temperature refers to gradually lowering the temperature to room temperature by 50-52.2°C every 30-32 minutes; 步骤(3)中,所述Fe离子溶液为Fe(NO3)3溶液,浓度为0.04-0.1g/mL;所述覆有黑磷薄膜的Si衬底放入Fe离子溶液中反应15-30分钟。In step (3), the Fe ion solution is Fe(NO 3 ) 3 solution with a concentration of 0.04-0.1 g/mL; the Si substrate covered with the black phosphorus film is put into the Fe ion solution to react for 15-30 minute. 2.根据权利要求1所述的用于催化离解二氯甲烷的金属Fe修饰的黑磷烯,其特征在于,所述金属Fe修饰的黑磷烯是以红磷为原料制得的二维层状结构材料,层数为10-25层;其中,所述金属Fe的负载密度为7.9%-10%。2. The metal Fe-modified black phosphorene for catalytic dissociation of dichloromethane according to claim 1, wherein the metal Fe-modified black phosphorene is a two-dimensional layer obtained from red phosphorus as a raw material The number of layers is 10-25 layers; wherein, the loading density of the metal Fe is 7.9%-10%. 3.根据权利要求1所述的用于催化离解二氯甲烷的金属Fe修饰的黑磷烯,其特征在于,所述金属Fe修饰的黑磷烯对二氯甲烷的吸附能达到1.008-1.034eV,二氯甲烷的离解能为0.648-0.720eV。3. The metal Fe-modified black phosphorene for catalytic dissociation of dichloromethane according to claim 1, wherein the adsorption energy of the metal Fe-modified black phosphorene to dichloromethane reaches 1.008-1.034 eV , the dissociation energy of dichloromethane is 0.648-0.720eV. 4.一种二氯甲烷离解催化器,其特征在于,包括中轴(1),沿中轴(1)向外分布若干隔层(2),相邻隔层(2)之间为催化剂填充层(5),位于最外层的隔层(2)外包裹有外壳(3),所述中轴(1)、隔层(2)和外壳(3)之间通过支撑层(4)交叉连接;所述催化剂填充层(5)内填充权利要求1所述的金属Fe修饰的黑磷烯作为二氯甲烷离解催化剂;4. A methylene chloride dissociation catalyst, characterized in that it comprises a central axis (1), several partitions (2) are distributed outwardly along the central axis (1), and a catalyst is filled between adjacent partitions (2). layer (5), the outermost layer (2) is wrapped with an outer shell (3), and the central axis (1), the outer layer (2) and the outer shell (3) are intersected by a support layer (4) connection; the catalyst filling layer (5) is filled with the metal Fe-modified black phosphorene of claim 1 as a dichloromethane dissociation catalyst; 所述二氯甲烷离解催化器为圆柱形;The dichloromethane dissociation catalyst is cylindrical; 所述中轴、隔层、外壳和支撑层为不锈钢材质;其中中轴为圆柱形,所述外壳的厚度>支撑层的厚度>隔层的厚度;The central axis, the interlayer, the outer shell and the support layer are made of stainless steel; wherein the central axis is cylindrical, and the thickness of the outer shell>the thickness of the supporting layer>the thickness of the interlayer; 所述中轴为直径5mm,高150mm的不锈钢圆柱;隔层为0.1mm厚的不锈钢,高度为150mm,根据不同层次隔离层选择不同的长度,弯曲制成隔层;外壳为2mm厚的不锈钢,长为377mm,高度150mm,沿着长边弯曲制成直径60mm的圆环作为外壳;支撑层为高150mm,长25.5mm,厚1mm的矩形不锈钢金属板;The central axis is a stainless steel cylinder with a diameter of 5mm and a height of 150mm; the partition layer is made of stainless steel with a thickness of 0.1mm and a height of 150mm, and different lengths are selected according to different levels of isolation layers, and the partition layer is formed by bending; the outer shell is made of stainless steel with a thickness of 2mm. The length is 377mm, the height is 150mm, and it is bent along the long side to form a ring with a diameter of 60mm as the shell; the support layer is a rectangular stainless steel metal plate with a height of 150mm, a length of 25.5mm, and a thickness of 1mm; 其中,外壳和中轴高的比为1:1,半径的比为12:1;隔层厚度要小于隔层间距,每个隔层间距控制在1.8-2.5mm,以便于填充催化剂和含二氯甲烷气体的通过;隔层宽度等于外壳空心圆柱的半径减去中轴半径。Among them, the ratio of the height of the shell to the central axis is 1:1, and the ratio of the radius is 12:1; the thickness of the interlayer is smaller than the interlayer distance, and the distance of each interlayer is controlled at 1.8-2.5mm, so as to facilitate the filling of the catalyst and the containing two The passage of methyl chloride gas; the width of the partition is equal to the radius of the hollow cylinder of the shell minus the radius of the central axis.
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