CN111250074B - Method for synthesizing MOF derivative semiconductor heterojunction material by solvothermal method - Google Patents
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Abstract
The invention discloses a method for synthesizing MOF derivative semiconductor heterojunction material by a solvothermal method, belonging to the field of catalyst material. The method specifically comprises the steps of carrying out hydrothermal crystallization on a mixed reaction system of a soluble ligand organic matter dissolved in an organic solvent and tetra-n-butyl titanate, washing and drying an obtained product, then carrying out continuous 2-step calcination in air, dissolving the calcined product and a metal compound in an alkaline solution containing an alcohol solvent, carrying out hydrothermal crystallization for a period of time, washing for multiple times, and finally drying the solid matter to obtain a target product. The MOF derivative semiconductor heterojunction material product obtained by the method has high chemical stability and excellent photocatalytic performance, and the preparation method has the characteristics of simple process flow, low cost and high product yield.
Description
Technical Field
The invention belongs to the field of catalyst materials, relates to a preparation method of a novel catalytic material, and particularly relates to a preparation method of an MOF derivative semiconductor heterojunction material synthesized by a solvothermal method.
Background
Metal-organic frameworks (MOFs), also known as Porous Coordination Polymers (PCPs), are two-or three-dimensional porous crystalline materials with infinite lattices synthesized by coordinative connection of secondary building blocks (SBUs), metal cation salts or clusters, and multidentate organic ligands. MOFs are excellent catalyst templates due to their excellent properties of metal centers, highly ordered porous structures, uniform pore sizes and environments, extremely high specific surface area and functional organic linking groups, tailorability, and ultra-high specific surface area. In recent years, MOFs derivatives have potential application prospects in a plurality of research fields, and especially the deep research and development of catalytic applications thereof have become research hotspots at present.[1]
From the course of the photolytic water reaction, photocatalytic water splitting in the presence of a photocatalyst involves four main stages: (1) Light capture, (2) absorption of photons by a photocatalyst to generate electron-hole pairs, (3) separation and migration of photogenerated charges, and (4) surface chemical reactions. Aiming at the separation and migration processes of photo-generated charges, designing a heterostructure is a main way for enhancing the migration distance and the service life of the photo-generated charges so as to obtain the optimal photocatalytic efficiency.[2]Currently, many reports are reported on the synthesis of semiconductor heterojunction materials, such as Subha N[3]Titanium isopropoxide hydrolysis and strontium nitrate are respectively used as a titanium source and a strontium source to hydrothermally synthesize the SrTiO3/TiO2 heterojunction material, and the method heats and crystallizes the mixed solution to obtain a titanium oxide product with rutile crystal form, irregular appearance and fewer pores, so that the catalytic performance of the product is limited. Meanwhile, XW Lou et al[4]In the preparation process, Ti-Fe-O nano particles are converted into Fe2TiO5/TiO2 with a heterostructure through a post-annealing process, and the heterostructure obtained in the way cannot ensure the uniform distribution of active sites so as to influence the subsequent photocatalytic reaction. R Li and the like[5]The TiO2 nanotube is used as a template and a reactant, and the BaTiO3/TiO2 heterostructure nanotube array is prepared by an in-situ hydrothermal method, but the TiO2 nanotube is harsh in preparation conditions, harsh in requirements on experimental equipment, and difficult to realize under common laboratory conditions. So far, the preparation of semiconductor heterojunction materials by the solvothermal method with Ti-MOF has not been reported.
[1]Wang Q,Astruc D.State of the Art and Prospects in Metal–Organic Framework(MOF)-Based and MOF-Derived Nanocatalysis[J].Chemical Reviews,2019.
[2]Zhang L J,Li S,Liu B K,et al.Highly Efficient CdS/WO3Photocatalysts:Z-Scheme Photocatalytic Mechanism for Their Enhanced Photocatalytic H2Evolution under Visible Light[J].Acs Catalysis,2014,4(10):3724-3729.
[3]Subha N,Mahalakshmi M,Myilsamy M,et al.Influence of synthesis conditions on the photocatalytic activity of mesoporous Ni doped SrTiO3/TiO2 heterostructure for H2 production under solar light irradiation[J].Colloids and Surfaces A:Physicochemical and Engineering Aspects,2017,522:193-206.
[4]Lou X W.Fabrication of Heterostructured Fe2TiO5-TiO2 Nanocages with Enhanced Photoelectrochemical Performance for Solar Energy Conversion[J].Angewandte Chemie,2020.
[5]Li R,Li Q,Zong L,et al.BaTiO3/TiO2 heterostructure nanotube arrays for improved photoelectrochemical and photocatalytic activity[J].Electrochimica Acta,2013,91:30-35.
Disclosure of Invention
The invention aims to provide an MOF derivative semiconductor heterojunction material synthesized by a solvothermal method and a preparation method thereof, so that the MOF derivative semiconductor heterojunction material is widely applied to scientific research and industrial production.
Technical scheme
The invention provides a method for synthesizing MOF derivative semiconductor heterojunction material by a solvothermal method, wherein the method comprises the following steps:
(1) respectively dissolving appropriate metal salt solution and organic ligand in organic solvent solution containing strong acid, mixing and ultrasonically treating, uniformly dispersing, and performing hydrothermal crystallization;
(2) fully washing the obtained product, and centrifugally drying to obtain a precursor MOFs;
(3) calcining the obtained precursor MOFs in a muffle furnace in the atmosphere of air;
(4) mixing the obtained powder and a certain amount of metal compounds in an alkaline solution containing alcohol substances, ultrasonically stirring, uniformly dispersing, and carrying out hydrothermal crystallization;
(5) removing the solvent, fully washing, and centrifugally drying to obtain the product.
Wherein the metal salt solution is tetrabutyl titanate; the organic ligand is terephthalic acid; the organic solvent is a mixed solution of anhydrous methanol and N, N-Dimethylformamide (DMF), and the volume ratio of the mixed solution is controlled to be 1:5 to 1: 100; the strong acid is one or more of hydrochloric acid and acetic acid; the strong acid is preferably acetic acid, various strong acids can be directly used or used in the form of solution, the solution is preferably used, and the concentration of the acetic acid can be 0.1-1 mol/L; the metal compound can be strontium hydroxide, ferric hydroxide, barium hydroxide and the like; the alcohol substances are ethylene glycol, propylene glycol and the like; the basic source is tetrabutylammonium hydroxide solution.
Further, in the step (1), the adding amount of the tetrabutyl titanate and the terephthalic acid is 1:8 to 1:2 in a molar ratio, the mixing temperature is 19-30 ℃, the ultrasonic time is 5-30 minutes, the tetrabutyl titanate and the terephthalic acid are uniformly mixed, the pH of the stirring solution is 1-7, and the pH of the solution is preferably 1-3.
Further, in the step (1), the crystallization is performed in a crystallization kettle known in the art. The crystallization conditions may be various conditions commonly used in the art, but preferably, the crystallization conditions include a crystallization temperature of 160-.
Further, in the step (2), the centrifugal rotation speed is 6000-; the washing process is that N, N-dimethylformamide and absolute methanol are alternately washed for 2 to 5 times; the drying temperature is 60 ℃, and the drying time is 6-24 hours.
Further, in the step (3), the calcination is divided into 2 major steps. Firstly, the heating rate is 0.5-5 ℃/min, the temperature is raised to 250 ℃, and the temperature is kept for 0.5-1.5 h; then, the temperature rise rate is 0.5-10 ℃/min, the temperature is raised to 500 ℃ at 450 ℃, and the temperature is kept for 0.5-1.5 h.
Further, in the step (4), the metal compound may be used as it is, or may be used in the form of a solution. Preferably used directly. The amount of the metal compound added is very important, and in general, the molar ratio of the metal compound to the amount of the powder obtained is 2:1 to 1: 2; preferably, the molar ratio of the metal compound to the powder obtained is from 1.5:1 to 1: 1.
Further, in the step (4), the stirring conditions are not particularly limited as long as the obtained mixed solution is a uniform, clear and transparent solution, but preferably, the stirring conditions include that the ultrasonic stirring temperature is 15-30 ℃ and the stirring time is 5-40 minutes; more preferably, the stirring temperature is 23 to 25 ℃ and the stirring time is 10 to 30 minutes.
Further, in the step (4), the crystallization is performed in a crystallization kettle known in the art. The crystallization conditions may be various conditions commonly used in the art, but preferably, the crystallization conditions include a crystallization temperature of 120-.
Further, in the step (5), the centrifugal rotation speed is 6000-; the washing process is that 0.1M hydrochloric acid solution and deionized water are alternately washed for 2 to 5 times; the drying temperature is 60 ℃, and the drying time is 6-24 hours.
The invention adopts a very simple solvothermal synthesis mode, and has simple and efficient process. Firstly, according to the application characteristics of the material, a precursor MOF is hydrothermally synthesized by corresponding transition metal elements and organic ligands in a proper solution, then the obtained precursor MOFs is placed into a high-temperature treatment container (such as a muffle furnace), the obtained precursor MOFs is calcined in the air through a continuous 2-step method, the calcined product and metal compounds are dissolved in an alkaline solution containing an alcohol solvent, the hydrothermal crystallization is carried out for a period of time, the obtained solution is washed for multiple times, finally the solid matter is dried, and finally the semiconductor heterojunction material can be obtained.
In the material synthesis process, the used process is safe and efficient (only normal-temperature stirring and hydrothermal crystallization are used, and complex environments such as vacuum and the like are not involved), the instruments are simple (the main instruments of solvothermal synthesis are a beaker and a centrifuge; and the main instrument in the calcination process is a muffle furnace), and the process continuity is high.
The MOF derivative semiconductor heterojunction material synthesized by adopting the solvothermal synthesis method has the advantages of stable structure, regular appearance and good thermal stability. Therefore, the synthesis method is expected to be widely applied to the research and production of novel catalyst materials. The invention has low preparation cost and simple synthesis process, and is suitable for large-scale mass production. Therefore, the method has wider scientific research and practical value.
Drawings
FIG. 1 is a transmission electron microscope image of SrTiO3/TiO2 heterojunction material.
Detailed Description
Embodiments of the present invention will be described in detail with reference to examples. It will be appreciated by those skilled in the art that the following examples are only preferred embodiments of the invention to facilitate a better understanding of the invention and therefore should not be taken as limiting the scope of the invention. Various modifications and changes may be made by those skilled in the art, and any modification, equivalent replacement or improvement made without departing from the spirit and principle of the present invention should be covered within the protection scope of the present invention. The experimental methods in the following examples are all conventional methods unless otherwise specified; the experimental materials used, unless otherwise specified, were purchased from conventional biochemical manufacturers.
The centrifugation in the following examples was performed using a bench-top high speed centrifuge (XiangYi H-1650); transmission electron micrographs were obtained using a lanthanum hexaboride transmission electron microscope (Tecnai G220S-TWIN).
The first embodiment is as follows:
weighing 2.49g of terephthalic acid (PTA) (15mmol) and 2.56mL of tetrabutyl titanate (7.5mmol) at 25 ℃, dissolving the PTA (15mmol) and the tetrabutyl titanate in 45mL of N, N-Dimethylformamide (DMF) containing 0.87mL of acetic acid (15mmol) and 5mL of anhydrous methanol, putting the solutions into an ultrasonic machine for ultrasonic treatment, mixing and stirring the solutions until the solutions are completely dissolved, transferring the solutions into a crystallization kettle, crystallizing the solutions at 180 ℃ for 16 hours, and after crystallization is finished, centrifugally drying the solutions for 24 hours to obtain an MIL-125 material; then calcined in a muffle furnace: firstly, the heating rate is 0.5-1 ℃/min, the temperature is increased to 300 ℃ at 250-; then, the temperature rise rate is 0.5-2 ℃/min, the temperature rises to 450-28H2O (1mmol) in 10mL of deionized water, 10mL of ethylene glycol, 2mL of 1, 2-propylene glycol and 2g of tetrabutylammonium hydroxide solution (TBAH, 25wt), transferring into a crystallization kettle, crystallizing at 160 ℃ for 4H, after crystallization, washing with 0.1M HCl solution and deionized water, and drying at 70 ℃ for 6H to finally obtain the SrTiO3/TiO2 heterojunction material.
Example two
2.49g of terephthalic acid (PTA) (15mmol) and 2.56mL of tetra-N-butyl titanate (7.5mmol) were weighed at 25 ℃ and dissolved in 45mL of N, N-Dimethylformamide (DMF) containing 0.87mL of acetic acid (15mmol) and 5mL of anhydrous methanol, the mixture was sonicated by a sonicator, mixed and stirred until all dissolved, and transferred to crystallizationCrystallizing at 180 deg.C for 16h in a kettle, and centrifugally drying for 24h to obtain MIL-125 material; then calcined in a muffle furnace: firstly, the heating rate is 0.5-1 ℃/min, the temperature is increased to 300 ℃ at 250-; then, the temperature rise rate is 0.5-2 ℃/min, the temperature rises to 450-2(1mmol) of 10mL of deionized water, 10mL of ethylene glycol, 2mL of 1, 2-propylene glycol and 2g of tetrabutylammonium hydroxide solution (TBAH, 25wt), transferring to a crystallization kettle, crystallizing at 160 ℃ for 4h, washing with 0.1M HCl solution and deionized water after crystallization is finished, and drying at 70 ℃ for 6h to finally obtain the Fe2TiO5/TiO2 heterojunction material.
EXAMPLE III
Weighing 2.49g of terephthalic acid (PTA) (15mmol) and 2.56mL of tetrabutyl titanate (7.5mmol) at 25 ℃, dissolving the PTA (15mmol) and the tetrabutyl titanate in 45mL of N, N-Dimethylformamide (DMF) containing 0.87mL of acetic acid (15mmol) and 5mL of anhydrous methanol, putting the solutions into an ultrasonic machine for ultrasonic treatment, mixing and stirring the solutions until the solutions are completely dissolved, transferring the solutions into a crystallization kettle, crystallizing the solutions at 180 ℃ for 16 hours, and after crystallization is finished, centrifugally drying the solutions for 24 hours to obtain an MIL-125 material; then calcined in a muffle furnace: firstly, the heating rate is 0.5-1 ℃/min, the temperature is increased to 300 ℃ at 250-; then, the temperature rise rate is 0.5-2 ℃/min, the temperature rises to 450-2(1mmol) of 10mL of deionized water, 10mL of ethylene glycol, 2mL of 1, 2-propylene glycol and 2g of tetrabutylammonium hydroxide solution (TBAH, 25wt), transferring the mixture into a crystallization kettle, crystallizing the mixture at 160 ℃ for 4 hours, washing the crystallized mixture with 0.1M HCl solution and deionized water, and drying the crystallized mixture at 70 ℃ for 6 hours to finally obtain the BaTiO3/TiO2 heterojunction material.
The present invention is described in detail by the embodiments, but the present invention is not limited to the details and the methods, and it is not intended that the present invention be implemented by relying on the details and the methods. It will be apparent to those skilled in the art that any modification of the invention, equivalent substitutions of selected components and additions of auxiliary components, selection of specific modes, etc., and other variations within the knowledge of one skilled in the art without departing from the spirit of the invention, fall within the scope and disclosure of the invention.
Claims (9)
1. A method for solvothermally synthesizing a MOF derivative semiconductor heterojunction material, characterized by comprising the steps of:
(1) respectively dissolving appropriate metal salt solution and organic ligand in organic solvent solution containing strong acid, mixing and ultrasonically treating, uniformly dispersing, and performing hydrothermal crystallization; the metal salt solution is tetrabutyl titanate; the organic ligand is terephthalic acid; the molar ratio of the addition amount of the tetrabutyl titanate to the addition amount of the terephthalic acid is 1:8 to 1:2, the mixing temperature is 19-30 ℃, the ultrasonic time is 5-30 minutes, the tetrabutyl titanate and the terephthalic acid are uniformly mixed, and the pH value of the stirring solution is 1-7;
(2) fully washing the obtained product, and centrifugally drying to obtain a precursor MOFs;
(3) calcining the obtained precursor MOFs in a muffle furnace in the atmosphere of air;
(4) mixing the obtained powder and a certain amount of metal compounds in an alkaline solution containing alcohol substances, ultrasonically stirring, uniformly dispersing, and carrying out hydrothermal crystallization;
(5) removing the solvent, fully washing, and centrifugally drying to obtain a product;
wherein the organic solvent is a mixed solution of anhydrous methanol and N, N-Dimethylformamide (DMF), and the volume ratio of the anhydrous methanol to the N, N-Dimethylformamide (DMF) in the mixed solution is controlled to be 1:5 to 1: 100; the strong acid is one or more of hydrochloric acid and acetic acid; the various strong acids may be used directly or in solution; the metal compound is strontium hydroxide, ferric hydroxide and barium hydroxide; the alcohol substances are ethylene glycol and propylene glycol; the alkaline solution is tetrabutylammonium hydroxide solution.
2. A method for solvothermally synthesizing a MOF derivative semiconductor heterojunction material according to claim 1, wherein said strong acid is acetic acid, and the concentration of said acetic acid is 0.1-1 mol/L.
3. The method for synthesizing the MOF derivative semiconductor heterojunction material by the solvothermal method as claimed in claim 1, wherein in the step (1), the crystallization conditions comprise a crystallization temperature of 160-190 ℃ and a crystallization time of 5-20 hours.
4. The method for synthesizing the MOF derivative semiconductor heterojunction material by the solvothermal method as claimed in claim 1, wherein in the step (2), the centrifugation rotation speed is 6000-10000 rpm, and the centrifugation time is 10-60 minutes; the washing process is that N, N-dimethylformamide and absolute methanol are alternately washed for 2 to 5 times; the drying temperature is 60 ℃, and the drying time is 6-24 hours.
5. The method for synthesizing the MOF derivative semiconductor heterojunction material by the solvothermal method as claimed in claim 1, wherein in the step (3), the calcination is divided into 2 major steps, firstly, the temperature rise rate is 0.5-5 ℃/min, the temperature is raised to 150-250 ℃, and the temperature is maintained for 0.5-1.5 h; then, the temperature rise rate is 0.5-10 ℃/min, the temperature is raised to 500 ℃ at 450 ℃, and the temperature is kept for 0.5-1.5 h.
6. A method of solvothermally synthesized MOF derivative semiconductor heterojunction material according to claim 1, wherein in step (4) the molar ratio of the metal compound to the amount of powder added is from 2:1 to 1: 2.
7. A method of solvothermally synthesized MOF derivative semiconductor heterojunction material according to claim 1, wherein in step (4), the ultrasonic agitation temperature is 15-30 ℃ and the agitation time is 5-40 minutes.
8. The method for synthesizing the MOF derivative semiconductor heterojunction material by the solvothermal method as claimed in claim 1, wherein in the step (4), the crystallization is performed in a crystallization kettle at the crystallization temperature of 120-180 ℃ for 0.2-48 hours.
9. The method for synthesizing a MOF derivative semiconductor heterojunction material according to the solvothermal method as claimed in claim 1, wherein in the step (5), the centrifugation rotation speed is 6000-10000 rpm, and the centrifugation time is 1-10 minutes; the washing process is that 0.1M hydrochloric acid solution and deionized water are alternately washed for 2 to 5 times; the drying temperature is 60 ℃, and the drying time is 6-24 hours.
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