CN112142110B - Preparation method of tungsten sulfide nanosheet with catalytic performance - Google Patents
Preparation method of tungsten sulfide nanosheet with catalytic performance Download PDFInfo
- Publication number
- CN112142110B CN112142110B CN201910576942.7A CN201910576942A CN112142110B CN 112142110 B CN112142110 B CN 112142110B CN 201910576942 A CN201910576942 A CN 201910576942A CN 112142110 B CN112142110 B CN 112142110B
- Authority
- CN
- China
- Prior art keywords
- benzylamine
- tungsten sulfide
- reaction
- preparation
- tungsten
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G41/00—Compounds of tungsten
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention discloses a preparation method of a tungsten sulfide nanosheet with catalytic performance, and particularly relates to a method for preparing tungsten sulfide by a colloid method, wherein the tungsten sulfide nanosheet has the property of catalyzing coupling reaction of benzylamine. Preparing loose nano sheets at a certain reaction temperature by taking oleylamine as a solvent and taking a sulfur source and a tungsten source in a certain ratio as reactants; the nanosheet has the function of efficiently catalyzing benzylamine to be coupled into N-benzyl methylene benzylamine; in acetonitrile solvent, the yield of N-benzyl methylene benzylamine obtained by coupling benzylamine is as high as 98%. The catalyst has high catalytic efficiency, does not use noble metal, has low cost, and still maintains higher catalytic performance after 5 times of cycle experiments. The preparation method is simple in preparation process, easy to operate, free of organic templates and surfactants and suitable for industrial production.
Description
Technical Field
The invention belongs to the technical field of material preparation and application, and particularly relates to a tungsten sulfide nanosheet prepared by a colloid method, wherein the tungsten sulfide nanosheet has the property of catalyzing the coupling of benzylamine to generate imine.
Background
The research of the two-dimensional transition metal chalcogenide with atomic thickness reveals some interesting physical phenomena, including quantum spin Hall effect, valley polarization and two-dimensional superconductor, and brings potential application prospects for the fields of nano-electronics, photonics, sensing, energy storage, photoelectrons and the like. Song, et al (Carbon, 2019, 142, 697-706) and the like adopt an improved one-step hydrothermal method to prepare graphene-doped honeycomb WS with controllable morphology and excellent electrochemical performance 2 As a composite anode material for lithium/sodium ion batteries; ruppert, et al (Nano letter, 2017, 17, 644-651) utilizesWS has been studied by femtosecond broadband pumping probe spectrum 2 Transient changes in the optical response of the monolayer film; li, et al (sensor. Actual. B-chem., 2017, 240, 273-277.) in WS 2 The nano-sheet is a sensing material, and a selective room-temperature ammonia sensor is developed; liu, et al (Nanoscale, 2017, 9, 5806-5811) applied Pulsed Laser Deposition (PLD) method to WS 2 Deposited on the side of the tapered fiber and applied to the preparation of Saturable Absorbers (SA). The related patents are: (1) application No.: 201510005822.3, name: preparation of WS having solid lubrication by atomic layer deposition 2 Thin film method for preparing WS having solid lubrication effect by atomic layer deposition 2 A film, the application being in an effective period; (2) application No.: 201510263421.8, name: solvothermal method for preparing three-dimensional nano-layered structure WS 2 And electrochemical application thereof, and preparation of three-dimensional nano-layered structure WS by adopting solvothermal method 2 And applying the catalyst to lithium ion batteries and electrocatalytic hydrogen evolution reaction, wherein the application is in the validity period; (3) application No.: 201610480368.1, name: a tungsten disulfide nanosheet tubular aggregate and a preparation method thereof are disclosed, wherein WS is obtained by directly evaporating sulfur powder as a sulfur source in a vacuum tube furnace by using a thermal evaporation technology 2 A nanosheet tubular aggregate, the application being in the useful life.
From the above description and examples, it can be seen that there are many methods for producing tungsten sulfide nanosheets, but most of the methods require high reaction conditions and have high technical difficulty, and few reports report that tungsten sulfide nanosheets are synthesized by a colloid method. Different from the reports in the above documents, the inventor adopts a colloid method, takes sulfur powder and tungsten hexachloride as raw materials, takes oleylamine as a solvent, and prepares a tungsten sulfide nano sheet; the material shows excellent catalytic performance on N-benzyl methylene benzylamine generated by coupling benzylamine.
Disclosure of Invention
The invention aims to provide a preparation method of a material with catalytic property and application of the material in catalyzing benzylamine to generate N-benzyl methylene benzylamine. The method has simple preparation process and good repeatability, can be synthesized in a large scale, and is suitable for industrial production. The prepared nano-flake has higher catalytic performance, and the conversion rate of catalytic benzylamine is up to 98%.
The preparation method of the nano-flake comprises the following steps:
A. adding a certain amount of sulfur source into oleylamine with a certain volume, and magnetically stirring at room temperature until sulfur powder is completely dissolved.
B. Adding a certain amount of tungsten source into a certain volume of oleylamine, heating to 60 ℃ after three cycles of vacuum nitrogen, degassing for 1 hour, and then heating the solution to 320 ℃.
C. Injecting the sulfur source precursor prepared in the step A into the step B, reacting for 60 minutes, placing reaction liquid into centrifuge tubes after the reaction is finished, adding 3 ml of trichloromethane dispersed reaction liquid into each centrifuge tube, adding 3 ml of ethanol for washing, using 6500 r/min for centrifugation for 5 minutes, repeatedly washing precipitates for 3 times, and drying the product in a vacuum drying oven at 60 ℃.
The reactant sulfur source is sulfur powder;
the reactant tungsten source is tungsten hexachloride.
The specific operation of catalyzing benzylamine coupling reaction by using the tungsten sulfide nanosheet prepared by the invention is as follows:
putting magnetons into a glass tube, adding a certain amount of tungsten sulfide product as a catalyst, adding a certain volume of benzylamine into the glass tube by using a liquid transfer gun, then adding a certain volume of solvent (acetonitrile, normal hexane, cyclohexane, ethanol and water respectively), magnetically stirring at 60 ℃ for reaction for 30 hours, centrifuging to separate the catalyst, and quantitatively analyzing the product by using gas chromatography to obtain the conversion rate.
The solvents of acetonitrile, normal hexane, cyclohexane and ethanol are in chromatographic purity grade;
the gas chromatography is Shimadzu GC-2010 plus, japan.
The tungsten sulfide nanosheet prepared by the invention has good catalytic performance on benzylamine coupling reaction, and the preparation and detection method of the material is simple, can be synthesized in a large amount, has small using amount and can be repeatedly used.
Description of the drawings:
fig. 1 is a Transmission Electron Micrograph (TEM) of tungsten sulfide nanosheets prepared in example 1;
figure 2 is an X-ray powder diffraction pattern (XRD) of tungsten sulfide nanosheets prepared in example 1;
fig. 3 is an X-ray photoelectron spectroscopy (XPS) spectrum of the tungsten sulfide nanosheet prepared in example 1;
FIG. 4 is a bar graph of the yield of catalytic benzylamine coupling in different solvents as in example 2;
FIG. 5 is a graph showing the effect of temperature on the catalytic reaction in example 2 (taking 6 hours as an example);
FIG. 6 is a graph of a cyclic experiment of the catalytic benzylamine coupling of example 2;
the specific implementation mode is as follows:
the invention is specifically illustrated by the following examples:
example 1: preparing tungsten sulfide nano sheets:
adding 1 mmol of sulfur powder (0.032 g) into 3 ml of oleylamine solution, and magnetically stirring at room temperature until the sulfur powder is completely dissolved to obtain a sulfur source precursor. 0.5 mmol of tungsten chloride (0.199 g) was added to 30 ml of oleylamine solution, vacuum nitrogen was circulated three times to remove air in the reaction system, and the reaction system was heated to 60 ℃ and degassed by vacuum for 1 hour to remove low boiling substances in the reaction system. And (3) heating to 320 ℃, injecting the sulfur source precursor, reacting for 60 minutes, placing the reaction solution into centrifuge tubes after the reaction is finished, adding 3 ml of trichloromethane dispersed reaction solution into each centrifuge tube, adding 3 ml of ethanol, washing, rotating at 6500 rpm, centrifuging for 5 minutes, repeatedly washing the precipitate for 3 times, and drying in a vacuum drying oven at 60 ℃ to obtain the final product.
The obtained sample was subjected to morphology characterization by using Japanese Electron JEM-2100 Transmission (TEM), and the chemical composition of the sample was analyzed by using SmartLab 9 KW X-ray diffractometer (XRD) and Escalab 250Xi X-ray photoelectron Spectroscopy (XPS).
As can be seen from the transmission electron micrograph of the sample of fig. 1, the product is formed by the aggregation of a plurality of loose nano-flakes, without the sequential random stacking between the thin layers; FIG. 2 is an x-ray powder diffraction (XRD) pattern and hexagonal 2H-WS pattern of the product 2 The PDF card numbers of the phases are consistent, and no obvious impurities exist. FIG. 3 shows the W and S peaks in the productXPS analysis spectra. From the left image, two characteristic peaks are observed, located in the vicinity of 32.2 eV and 34.3 eV, respectively, which may correspond to 4f of W 7/2 And W4 f 5/2 . In addition, a couple of doublets in the spectrum at 33.1 eV and 34.3 eV is attributed to WO 2 W4 f in (1) 7/2 And W4 f 5/2 Or WO in non-stoichiometric proportions 3-x Due to surface oxidation of W under air exposure conditions. A broad peak corresponding to W5 p was also observed at 37.2 eV. From the XPS spectrum of the S on the right, two characteristic peaks appearing at 161.9 eV and 163.2 eV are observed, corresponding to S2 p 3/2 And 2p 1/2 。
Example 2: catalytic coupling of tungsten sulfide nanosheets to benzylamine:
the coupling method of benzylamine catalyzed by the tungsten sulfide nanosheet prepared by the invention comprises the following steps: 55 microliter benzylamine is measured and dissolved in 0.5 ml of different solvents, and the conversion rate of the reaction is tested after the reaction is carried out for a period of time at a certain temperature.
Selecting five solvents of acetonitrile, n-hexane, cyclohexane, ethanol and water for testing the catalytic performance.
The specific operation is as follows:
putting magnetons into a glass tube, adding 30 mg of tungsten sulfide product as a catalyst, adding 55 microliters (0.5 mmol) of benzylamine into the glass tube by using a pipette, then adding 0.5 ml of solvent, carrying out magnetic stirring reaction at 60 ℃ for 30 hours, adding the same solvent for dilution, centrifuging the catalyst, carrying out quantitative analysis on the product by using gas chromatography, and obtaining the yield.
As can be seen from the bar graph of FIG. 4, when the solvent is acetonitrile, the coupling of benzylamine gives N-benzylmethylenebenzylamine in yields of up to 98%, respectively. FIG. 5 is a graph showing the measured yields after the reactions were allowed to stand at 20 deg.C, 40 deg.C, 60 deg.C and 80 deg.C, respectively, for 6 hours. The yields of N-benzylmethylenebenzylamine were 11%, 25%, 51%, 84%, respectively, indicating that higher temperatures favor efficient reaction. Fig. 6 is a graph of the conversion and selectivity of each reaction after five times of catalyst recycling, and it can be seen from the graph that the catalyst still maintains excellent catalytic performance after repeated use for several times.
Claims (1)
1. A preparation method of tungsten sulfide nanosheets with catalytic performance comprises the following specific steps: adding 1 mmol of sulfur powder into 3 ml of oleylamine, and magnetically stirring at room temperature until the sulfur powder is completely dissolved to obtain a sulfur source precursor; adding 0.5 mmol of tungsten chloride into 30 ml of oleylamine, circulating vacuum nitrogen for three times to remove air in a reaction system, heating to 60 ℃, vacuumizing and degassing for 1 hour to remove low-boiling-point substances in the reaction system; heating to 320 ℃, injecting a sulfur source precursor, reacting for 60 minutes, placing reaction liquid into centrifuge tubes after the reaction is finished, adding 3 ml of trichloromethane dispersed reaction liquid into each centrifuge tube, adding 3 ml of ethanol for washing, using 6500 r/min for centrifugation for 5 minutes, repeatedly washing precipitates for 3 times, and drying in a vacuum drying oven at 60 ℃ to obtain a final product;
the obtained tungsten sulfide nanosheet is used for catalyzing benzylamine coupling to generate N-benzyl methylene benzylamine, and the specific experimental steps are as follows: putting magnetons into a glass tube, adding 30 mg of tungsten sulfide product as a catalyst, adding 55 microliters of benzylamine into the glass tube by using a liquid transfer gun, then adding 0.5 milliliter of solvent, carrying out magnetic stirring reaction at 60 ℃ for 30 hours, adding the same solvent for dilution, then carrying out centrifugal separation on the catalyst, and carrying out quantitative analysis on the product by using gas chromatography to obtain the yield; the results show that when the solvent is acetonitrile, the yield of N-benzylmethylenebenzylamine obtained by coupling benzylamine is as high as 98%.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201910576942.7A CN112142110B (en) | 2019-06-28 | 2019-06-28 | Preparation method of tungsten sulfide nanosheet with catalytic performance |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201910576942.7A CN112142110B (en) | 2019-06-28 | 2019-06-28 | Preparation method of tungsten sulfide nanosheet with catalytic performance |
Publications (2)
Publication Number | Publication Date |
---|---|
CN112142110A CN112142110A (en) | 2020-12-29 |
CN112142110B true CN112142110B (en) | 2023-04-07 |
Family
ID=73869544
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201910576942.7A Active CN112142110B (en) | 2019-06-28 | 2019-06-28 | Preparation method of tungsten sulfide nanosheet with catalytic performance |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN112142110B (en) |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2003286242A (en) * | 2002-01-24 | 2003-10-10 | Sumitomo Chem Co Ltd | Method for producing nitrone compound and catalyst therefor |
CN106946734A (en) * | 2017-02-20 | 2017-07-14 | 湖南大学 | A kind of method of high-selectivity oxidation benzylamine green syt N benzylidenebutyramides |
CN107416905A (en) * | 2017-06-22 | 2017-12-01 | 河南大学 | A kind of preparation method of oil-soluble tungsten disulfide nano slices |
CN107601443A (en) * | 2017-11-09 | 2018-01-19 | 安徽大学 | A kind of preparation method of ultra-thin tungsten selenide nanometer sheet |
-
2019
- 2019-06-28 CN CN201910576942.7A patent/CN112142110B/en active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2003286242A (en) * | 2002-01-24 | 2003-10-10 | Sumitomo Chem Co Ltd | Method for producing nitrone compound and catalyst therefor |
CN106946734A (en) * | 2017-02-20 | 2017-07-14 | 湖南大学 | A kind of method of high-selectivity oxidation benzylamine green syt N benzylidenebutyramides |
CN107416905A (en) * | 2017-06-22 | 2017-12-01 | 河南大学 | A kind of preparation method of oil-soluble tungsten disulfide nano slices |
CN107601443A (en) * | 2017-11-09 | 2018-01-19 | 安徽大学 | A kind of preparation method of ultra-thin tungsten selenide nanometer sheet |
Non-Patent Citations (3)
Title |
---|
Visible-Light-Driven Oxidative Coupling Reactions of Amines by Photoactive WS2 Nanosheets;Faizan Raza et al.;《ACS Catal.》;20160317;第6卷;2754-2759 * |
油溶性二硫化钨纳米微粒的制备及其摩擦学性能研究;蒋正权;《中国优秀博硕士学位论文全文数据库(硕士)工程科技Ⅰ辑》;20170315(第3期);B019-574 * |
蒋正权.油溶性二硫化钨纳米微粒的制备及其摩擦学性能研究.《中国优秀博硕士学位论文全文数据库(硕士)工程科技Ⅰ辑》.2017,(第3期),B019-574. * |
Also Published As
Publication number | Publication date |
---|---|
CN112142110A (en) | 2020-12-29 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Shuck et al. | Taking MXenes from the lab to commercial products | |
Liu et al. | Graphitic carbon nitride “reloaded”: emerging applications beyond (photo) catalysis | |
Wang et al. | A mesoporous rod-like g-C3N5 synthesized by salt-guided strategy: as a superior photocatalyst for degradation of organic pollutant | |
Jia et al. | Graphitic carbon nitride films: emerging paradigm for versatile applications | |
Tan et al. | High-yield exfoliation of ultrathin two-dimensional ternary chalcogenide nanosheets for highly sensitive and selective fluorescence DNA sensors | |
Islam et al. | Ultrathin assembles of porous array for enhanced H2 evolution | |
Li et al. | Selective preparation of 1T-and 2H-phase MoS2 nanosheets with abundant monolayer structure and their applications in energy storage devices | |
Jian et al. | Construction of carbon quantum dots/proton-functionalized graphitic carbon nitride nanocomposite via electrostatic self-assembly strategy and its application | |
Li et al. | Synergistic effects between doped nitrogen and phosphorus in metal-free cathode for zinc-air battery from covalent organic frameworks coated CNT | |
Moolayadukkam et al. | Role of transition metals in layered double hydroxides for differentiating the oxygen evolution and nonenzymatic glucose sensing | |
CN101658786B (en) | Method for preparing graphene-based titanium dioxide composite photocatalyst by radiation of electron beams | |
CN102145887B (en) | Method for preparing and purifying graphene oxide | |
CN108301017B (en) | A kind of water electrolysis hydrogen production catalyst Co9S8@CNT and preparation method thereof | |
Liu et al. | Study on ultrasound-assisted liquid-phase exfoliation for preparing graphene-like molybdenum disulfide nanosheets | |
CN108698849A (en) | Pass through the production of the graphene-based composite nanostructure of non-loading type graphene nano on piece growing zinc oxide nanorod or the micron bar acquisition in suspension | |
CN107601443A (en) | A kind of preparation method of ultra-thin tungsten selenide nanometer sheet | |
Li et al. | Eosin Y covalently anchored on reduced graphene oxide as an efficient and recyclable photocatalyst for the aerobic oxidation of α-aryl halogen derivatives | |
CN105271411A (en) | Preparation method for molybdenum disulfide quantum dot | |
Chen et al. | Supercritical etching method for the large-scale manufacturing of MXenes | |
CN105833887B (en) | A kind of BiOCl/ β FeOOH composite nano materials and preparation method thereof | |
CN104528684B (en) | A kind of method that under the conditions of alkalescence, carbon quantum dot is prepared in ketone carbonization | |
Du et al. | Quasi-metal microwave route to MoN and Mo2C ultrafine nanocrystalline hollow spheres as surface-enhanced Raman scattering substrates | |
CN103693693A (en) | Preparation method for synthesizing molybdenum sulfide nanospheres by microwave-assisted liquid phase deposition | |
Wang et al. | Recycling valuable elements from the chemical synthesis process of nanomaterials: a sustainable view | |
CN104787806A (en) | Rosette nano cobaltosic oxide and preparation method thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |