CN111151285B - Nitrogen-doped porous carbon loaded ZnS nano composite material and preparation method and application thereof - Google Patents

Nitrogen-doped porous carbon loaded ZnS nano composite material and preparation method and application thereof Download PDF

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CN111151285B
CN111151285B CN202010043102.7A CN202010043102A CN111151285B CN 111151285 B CN111151285 B CN 111151285B CN 202010043102 A CN202010043102 A CN 202010043102A CN 111151285 B CN111151285 B CN 111151285B
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zns
nitrogen
porous carbon
doped porous
zinc
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CN111151285A (en
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刘又年
方银
唐飞鹰
王立强
马凌
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Central South University
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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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • B01J35/39—
    • B01J35/50—
    • B01J35/618—
    • B01J35/635—
    • B01J35/647—
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/24—Preparation of compounds containing amino groups bound to a carbon skeleton by reductive alkylation of ammonia, amines or compounds having groups reducible to amino groups, with carbonyl compounds
    • C07C209/28—Preparation of compounds containing amino groups bound to a carbon skeleton by reductive alkylation of ammonia, amines or compounds having groups reducible to amino groups, with carbonyl compounds by reduction with other reducing agents
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/44—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D317/46—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems condensed with one six-membered ring
    • C07D317/48—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring
    • C07D317/62—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to atoms of the carbocyclic ring
    • C07D317/64—Oxygen atoms

Abstract

The invention discloses a nitrogen-doped porous carbon loaded ZnS nano composite material as well as a preparation method and application thereof. After dissolving and dispersing zinc salt and sulfur-containing protein into water, carrying out freeze drying and pyrolysis to obtain the nitrogen-doped porous carbon loaded ZnS nano composite material, wherein a template agent or acid-base is not required to be introduced for carrying out aftertreatment in the preparation process of the composite material, the obtained nano composite material has a large number of pore channel structures, abundant Lewis acid, alkaline sites and good photothermal conversion performance, and is applied to CO driven by light2The cycloaddition reaction and the methylation reaction show excellent selectivity and high catalytic activity, and have wide prospects in the field of photo-thermal catalytic materials.

Description

Nitrogen-doped porous carbon loaded ZnS nano composite material and preparation method and application thereof
Technical Field
The invention relates to a catalytic material, in particular to a nitrogen-doped porous carbon-loaded ZnS nano composite material, and also relates to a method for utilizing protein-zinc ion (Zn)2+) Method for constructing N-doped porous carbon supported ZnS catalyst by using complex network as precursor, and application of N-doped porous carbon supported ZnS nano composite material in CO2The application of photo-thermal catalytic conversion belongs to the technical field of photo-thermal catalytic materials.
Background
Currently, carbon dioxide (CO)2) Has caused serious environmental problems such as global warming, ocean acidification, etc. On the other hand, CO2Is also an important C1 resource and can be used for synthesizing various high value-added chemicals, such as carbonate, carboxylic acid derivatives, alcohol, N-methylamine derivatives and the like. However, carbon dioxide is extremely chemically stable. The bond energy of C ═ O bond in carbon dioxide molecule is up to 750kJ mol-1This enables activation and utilization of CO2Has certain challenges. In order to lower the energy barrier of carbon dioxide in the conversion process, a number of catalysts have been developed, including both homogeneous catalysts, such as ionic liquids, metal complexes, etc., and heterogeneous catalysts, such as Metal Organic Frameworks (MOFs), Porous Organic Polymers (POPs), metal oxides, zeolites, etc. Usually, to increase CO2In addition to introducing the catalyst, the reaction temperature needs to be increased to increase the CO2The conversion speed of the method meets the requirement of actual production. However, the conventional heat input is mainly achieved by electric-to-heat conversion, which consumes a large amount of electric energy, causing secondary emission of carbon dioxide. Therefore, the design and synthesis can catalyze CO2The conversion of the catalyst can replace the conventional heating method and reduce the multifunctional catalytic system of electric energy input, and becomes a focus of attention of people at present.
The photo-thermal catalytic system can not only reduce the energy barrier in the reaction process, but also efficiently convert light energy into heat energy to accelerate the reaction process, and CO is used as the energy barrier2Provides a new idea for the catalytic conversion of (2). An efficient photothermal catalytic system comprises at least two components: (i) can adsorb and activate reactant (such as CO)2) The active site of (1). For CO2Although the mechanism of action is different, the conversion can be catalyzed by both Lewis acid and basic sites; (ii) the high-efficiency photo-thermal conversion module is used for converting light energy into heat energy. In various photothermal catalytic systems, e.g. noble metal materials (Pd, Au, Ru, etc.), semiconductors (MoO)3-x，Bi2S3CuS, black phosphorus, etc.) and nanocarbon materials (carbon quantum dots, graphene, hollow porous carbon, carbon nanotubes, etc.), heteroAtom-doped porous carbon-supported catalysts are of particular interest. They have the following characteristics: (1) the material has a porous structure, is beneficial to exposing active sites, improves the mass transfer process so as to increase the reaction kinetics, provides a limited-area environment for the reaction and improves the photo-thermal conversion capacity of the carbon substrate; (2) the catalyst has Lewis acid and basic sites, and the Lewis acid and the basic sites can play a synergistic effect to endow the catalyst with excellent performance; (3) has high photo-thermal conversion efficiency and high strength, and can resist photobleaching, acid and alkali corrosion, and the like. For example, researchers have utilized graphene-supported layered MnO2Realizes the light-driven catalytic oxidation of formaldehyde under mild conditions. Chen et al reported a nickel/reduced graphene oxide combined photothermal catalytic system. The light in the near infrared-II region can be used for promoting the catalytic reduction of the 4-nitrophenol. However, current photothermal catalytic systems are relatively inactive, and only a few are used for CO2The catalytic conversion process of (1), wherein the synthesis method is an important reason for limiting the performance thereof. Typically, carbon supported catalysts are prepared by cracking a mixture of metal ions and a carbon source. However, during pyrolysis, a dense carbon structure is often formed, and in addition, metal sites are often agglomerated during pyrolysis and even embedded in the dense carbon-based material. The above conditions are such that CO is included2The reaction substrates inside are difficult to access to the active site, limiting the adsorption and activation process. To address this problem, river and coworkers have proposed a solution to engineer the carbon matrix into a hollow porous structure while imparting sufficient lewis acidic and basic sites to the catalyst. Specifically, they developed a Zn, N-co-doped hollow porous carbon catalyst by pyrolyzing ZIF-8 prepared using polystyrene spheres as a template. Wherein Zn and N can synergistically catalyze CO2The transformation of (3). However, the introduction of a templating agent during the cleavage process may limit large scale preparation and application.
Disclosure of Invention
Aiming at CO in the prior art2The invention aims to provide a catalyst with wide light absorption range, a large number of pore structures, abundant Lewis acid and basic sitesThe nitrogen-doped porous carbon loaded ZnS nano composite photocatalytic material.
The second purpose of the invention is to provide a simple, environment-friendly and economical method for preparing the nitrogen-doped porous carbon-supported ZnS nanocomposite photothermal catalytic material.
The third purpose of the invention is to apply the nitrogen-doped porous carbon-supported ZnS nanocomposite material to CO driven by light2The cycloaddition reaction or methylation reaction shows high-efficiency catalytic activity and selectivity.
In order to achieve the technical purpose, one embodiment of the invention provides a preparation method of a nitrogen-doped porous carbon-supported ZnS nano composite material, which is obtained by dissolving and dispersing zinc salt and sulfur-containing protein into water, and then carrying out freeze drying and pyrolysis.
In the above scheme, the key point of the preparation method of the exemplified nitrogen-doped porous carbon-supported ZnS nanocomposite is that sulfur (S) in sulfur-containing protein is utilized to anchor zinc (Zn), part of Zn can be used as a pore-forming agent due to low boiling point, and plays a pore-forming role for a carbon material in a high-temperature cracking process, so that the pore structure of the carbon material is enriched, and part of Zn2+Can be anchored by sulfur (S) of proteins to form ZnS in situ. And the protein molecules are rich in nitrogen and can be used as a precursor for preparing heteroatom nitrogen-doped carbon. In addition, the sulfur-containing protein is complexed with zinc ion by coordination to form protein-zinc ion (Zn)2+) The complex network can be used as a precursor of the porous carbon material, and can generate the porous carbon supported ZnS composite catalytic material with rich Lewis acidic and basic sites without introducing an additional template. The porous structure, especially the mesoporous structure, of the generated nitrogen-doped porous carbon-loaded ZnS nano composite material is beneficial to enriching CO2The adsorption and activation processes are promoted, and the collection and reflection of light are enhanced, the photo-thermal performance of the catalyst is improved, and the activity of the catalyst is improved. The catalyst has excellent photothermal effect and rich CO2Adsorption and activation sites and porous structure, is good CO2A photothermal conversion catalytic material.
Preferably, the zinc salt is a common easily-soluble zinc salt, specifically at least one of zinc chloride, zinc acetate, zinc sulfate, and zinc nitrate.
Preferably, the sulfur-containing protein is at least one of common protein materials, such as BSA and egg white.
In a preferable scheme, the mass ratio of the zinc salt to the sulfur-containing protein is 1.15: 1-3: 1. Most preferably 2.25: 1.
In a preferred embodiment, the pyrolysis conditions are: and pyrolyzing for 2-4 h at 700-1000 ℃ in a protective atmosphere. Most preferred pyrolysis conditions are: and pyrolyzing for 2 hours at 800 ℃ under a protective atmosphere. The protective atmosphere may be nitrogen. If the pyrolysis temperature is too high, the zinc is excessively volatilized, the component content of the zinc sulfide is reduced, and the pore-forming effect is relatively poor if the pyrolysis temperature is too low.
In one illustrative aspect of the invention, a nitrogen-doped porous carbon-supported ZnS nanocomposite is provided. The nitrogen-doped porous carbon-loaded ZnS nanocomposite can be obtained by any one of the preparation methods.
In a preferred scheme, the nitrogen-doped porous carbon-loaded ZnS nano composite material has mesopores with the aperture of 2-10 nm and the aperture<2nm micropores with specific surface area of 1300-1800 m2g-1The specific surface area of the mesopores is 700-1200 m2g-1The total pore volume is 0.80-1.00 cm3g-1。
The nitrogen-doped porous carbon-supported ZnS nano composite material provided in one illustrative scheme of the invention is formed by in-situ supporting of ZnS in a nitrogen-doped carbon pore structure with a porous structure through Zn2+Is anchored by sulfur (S) of a protein precursor, forms ZnS in situ after pyrolysis and is uniformly distributed in the nitrogen-doped porous carbon nano structure.
The nitrogen-doped porous carbon loaded ZnS nanocomposite provided by the invention has the characteristic of large specific surface area of mesopores and micropores, can provide more active sites, and is favorable for improving the photo-thermal catalytic activity.
In an exemplary embodiment of the invention, an application of a nitrogen-doped porous carbon-supported ZnS nanocomposite as a photo-thermal catalyst for a cycloaddition reaction of carbon dioxide is provided.
In a preferable scheme, a nitrogen-doped porous carbon-supported ZnS nano composite material is used as a catalyst, and CO is introduced into a mixed system of tetra-n-butylammonium bromide, dimethylformamide and an epoxy compound2And carrying out catalytic cycloaddition reaction under the condition of illumination. The specific cycloaddition reaction process is as follows: a mixture of ZnS/NPCs composite photothermal catalyst, tetra-n-butylammonium bromide (TBAB), Dimethylformamide (DMF) and an epoxy compound was placed in a reactor tube, and CO was charged2Connected to the tube by a CO2Purging the reactor several times to fill the reactor and balloon with CO2. The catalytic cycloaddition reaction was performed under illumination from a Microlar 300Xe lamp and the light intensity was adjusted by varying the current. Epoxy compounds such as 3-chloropropylene, propylene oxide, styrene oxide and the like. Tetra-n-butylammonium bromide is a common phase transfer reagent. Dimethylformamide is a common organic solvent. More specific cycloaddition reaction conditions are: 0.10mmol of 3-chloropropylene, 10mg of ZnS/NPCs composite catalyst, 0.03mmol of TBAB, 1ml of DMF, 1bar of CO2Full spectrum radiation (300W), duration 12 h.
In one illustrative embodiment of the invention, the application of the nitrogen-doped porous carbon-supported ZnS nanocomposite as a photo-thermal catalyst in the methylation reaction of carbon dioxide is provided.
In a preferable scheme, nitrogen-doped porous carbon-supported ZnS nano composite material is used as a catalyst, and CO is introduced into a mixed system of phenylsilane and an amine substrate2And carrying out catalytic methylation reaction under the illumination condition. The specific methylation reaction process comprises the following steps: ZnS/NPCs composite photo-thermal catalyst, phenyl silane (PhSiH)3) A mixture of Dimethylformamide (DMF) and amine substrate is placed in a reactor tube and will be charged with CO2Connected to the tube by a CO2Purging the reactor several times to fill the reactor and balloon with CO2. The catalytic methylation reaction was performed under illumination from a Microlar 300Xe lamp and the light intensity was adjusted by varying the current. Phenylsilane primarily provides a source of hydrogen. Amine substrates such as N-methylAniline, N-methyl p-methylaniline and the like. The specific methylation reaction conditions are as follows: 0.10mmol amine substrate, 10mg ZnS/NPCs composite catalyst, 0.3mmol PhSiH3、1mLDMF，1bar CO2Full spectrum irradiation (300W), duration 13 h.
In an exemplary scheme of the invention, a preparation method of a nitrogen-doped porous carbon-loaded ZnS nanocomposite photothermal catalytic material (ZnS/NPCs) is provided, which specifically comprises the following steps: reacting ZnCl2And BSA in water (ZnCl)2The mass ratio of BSA to BSA is 0-3: 1, the obtained solid is transferred into a tubular furnace after being dried by a freeze dryer, and is pyrolyzed under nitrogen flow, and the temperature is firstly 10 ℃ for min-1Heating the sample to 500 ℃ at a heating rate of (1), and then at 5 ℃ for min-1Is heated to 800 ℃ and kept at 800 ℃ for 2h and then cooled to room temperature. The samples obtained were individually named NPC (ZnCl)2Mass ratio to BSA 0:1), ZnS/NPC.
The invention adopts ZnS/NPCs composite photo-thermal catalyst for catalyzing CO under the drive of light2The cycloaddition reaction is carried out as follows: a mixture of 10mg of catalyst, 0.03mmol of tetra-n-butylammonium bromide (TBAB), 1mL of Dimethylformamide (DMF) and 0.1mmol of epoxide was placed in a reactor tube and charged with CO2Connected to the tube by a CO2Purging the reactor several times to fill the reactor and balloon with CO2. The catalytic cycloaddition reaction was performed under illumination from a Microlar 300Xe lamp and the light intensity was adjusted by varying the current. The yield of the product was checked by 1H NMR using 1,1,2, 2-tetrachloroethane as an internal standard. For in low CO2Reaction under pressure with 0.15bar CO2And 0.85bar N2Instead of pure CO2The rest steps are as above.
The invention adopts ZnS/NPCs composite photo-thermal catalyst for catalyzing CO under the drive of light2The methylation reaction is specifically carried out as follows: 10mg of catalyst, 0.3mmol of phenylsilane (PhSiH)3) 1mL of Dimethylformamide (DMF), and 0.1mmol of amine substrate were placed in a reactor tube and charged with CO2Connected to the tube by a CO2Purging the reactor several times to fill the reactor and balloon with CO2. The catalytic methylation reaction was performed under the illumination of a Microlar 300Xe lamp and the light intensity was adjusted by varying the current. Substrate conversion and product selectivity were determined by HPLC.
Compared with the prior art, the invention has the advantages that the specific embodiment exemplified by the invention brings about:
(1) in one embodiment provided by the invention, BSA-Zn is used2+The network is used as a precursor, and the N-doped porous carbon loaded ZnS photothermal catalyst (ZnS/NPCs) is prepared through freeze drying and high-temperature carbonization, and the method does not need to introduce a template agent or carry out post-treatment by acid or alkali, is suitable for large-scale preparation, and overcomes the defects that the template agent needs to be introduced and the acid or alkali post-treatment is needed in the prior art.
(2) The ZnS/NPCs prepared in one scheme provided by the invention have a large number of pore channel structures, abundant Lewis acids and basic sites and a wide absorption range. The characteristics not only endow ZnS/NPCs with good photo-thermal conversion performance, but also give CO2Lays a foundation for adsorption, activation and rapid material transfer.
(3) In one scheme provided by the invention, ZnS/NPCs are used as a photo-thermal catalyst, and CO is used under the condition of illumination2As a C1 resource, can catalyze CO-based2Cycloaddition reaction of (2) and CO2The methylation reaction has good catalytic activity, selectivity and stability.
(4) The method for preparing the ZnS/NPCs composite photocatalyst in one scheme provided by the invention is simple, easy to operate, environment-friendly and applicable to industrialization, and adopts nontoxic and cheap raw materials without large-scale complex devices.
Drawings
FIG. 1 shows X-ray diffraction (XRD) pattern, XPS spectrum, Zn 2p spectrum, Raman spectrum, N spectrum of ZnS/NPC-X sample prepared in examples 1,2, 3, 4 and 5 of the present invention2Adsorption/desorption isotherms and pore size distribution profile of ZnS/NPC-X: (a) x-ray diffraction (XRD) patterns of ZnS/NPC-X and ZnS samples prepared in examples 1,2, 3, 4, 5; (b) examples 1,2, 3 and 4X-ray photoelectron spectroscopy (XPS) plots of ZnS/NPC-X samples; (c) zn 2p spectra of ZnS/NPC-X and ZnS samples prepared in examples 1,2, 3, 4, 5; (d) raman spectra of ZnS/NPC-X samples prepared in examples 1,2, 3, 4; (e) n of ZnS/NPC-X samples prepared in examples 1,2, 3, 42Adsorption/desorption isotherm plot; (f) pore size distribution of ZnS/NPC-X samples prepared in examples 1,2, 3, 4.
FIG. 2 is a Transmission Electron Microscope (TEM) image, a HADDF-TEM image and a spectrum scan of ZnS/NPC-X prepared in examples 1,2, 3, 4 of the present invention and ZnS/NPC-2 prepared in example 3: (a) NPC of sample prepared in example 1, (b) ZnS/NPC-1 of sample prepared in example 2, (d) ZnS/NPC-2 of sample prepared in example 3, (f) TEM image of ZnS/NPC-3 of sample prepared in example 4; (c) ZnS/NPC-1 sample prepared in example 2 and (e) HADDF-TEM image of ZnS/NPC-2 sample prepared in example 3; (g) example 3 the spectral scan of sample ZnS/NPC-2 prepared.
FIG. 3 is a diagram showing the photothermal effect, UV-visible absorption spectrum, temperature change of DMF solution and photothermal stability test of ZnS/NPC-X prepared in examples 1,2, 3 and 4 of the present invention for the sample ZnS/NPC-2 prepared in example 3: (a) a schematic diagram of photothermal effect of ZnS/NPC-X; (b) UV-VIS absorption spectrum of ZnS/NPC-X samples prepared in examples 1,2, 3 and 4; (c) temperature profiles of DMF solutions under light irradiation with or without ZnS/NPC-X samples prepared in examples 1,2, 3, 4; (d) photothermal stability test pattern of sample ZnS/NPC-2 prepared in EXAMPLE 3.
FIG. 4 is a graph showing the catalytic performance of ZnS/NPC-2 prepared in example 3 of the present invention on various substrates: (a) catalytic Performance of ZnS/NPC-2 catalyst prepared in example 3 on various substrates (reaction conditions: 0.10mmol of propylene-oxychloride, 10mg of catalyst, 0.03mmol of TBAB, 1mL of DMF, 1bar of CO)2Full spectrum radiation), the catalytic reaction product was analyzed and identified by 1H NMR using 1,1,2, 2-tetrachloroethane as an internal standard; (b) catalytic Performance of the catalyst ZnS/NPC-2 prepared in example 3 for various amine substrates (reaction conditions: 0.10mmol of amine substrate, 10mg of catalyst, 0.3 mmol) PhSiH3、1mLDMF，1bar CO2Full spectrum irradiation (300W) for 13h), analyzed and the conversion and selectivity of the catalytic reaction identified by HPLC.
FIG. 5 thermolysin protein-zinc ion (Zn)2+) Network preparation for catalytic conversion of CO2Schematic representation of the catalyst ZnS/NPCs of (1).
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples, but the scope of the present invention is not limited to the following examples.
Example 1
Preparation of sample NPC: BSA was dissolved in water, dried by a freeze dryer, and the obtained solid was transferred to a tube furnace and pyrolyzed under a nitrogen stream. First at 10 ℃ for min-1Heating the sample to 500 ℃ at a heating rate of (1), and then at 5 ℃ for min-1The sample obtained was named NPC by heating to 800 ℃ and holding at 800 ℃ for 2h and then cooling to room temperature.
Example 2
Preparation of catalyst sample ZnS/NPC-1: reacting ZnCl2And BSA in water (ZnCl)2The mass ratio of BSA to BSA was 1.5: 1) after drying by a freeze dryer, the obtained solid was transferred into a tube furnace and pyrolyzed under a nitrogen stream. First at 10 ℃ for min-1Heating the sample to 500 ℃ at a heating rate of (1), and then at 5 ℃ for min-1Is heated to 800 c and held at 800 c for 2h and then cooled to room temperature, and the obtained sample is named ZnS/NPC-1.
Example 3
Preparation of catalyst sample ZnS/NPC-2: reacting ZnCl2And BSA in water (ZnCl)2Mass ratio to BSA 2.25: 1) after drying by a freeze dryer, the obtained solid was transferred into a tube furnace and pyrolyzed under a nitrogen stream. First at 10 ℃ for min-1Heating the sample to 500 ℃ at a heating rate of (1), and then at 5 ℃ for min-1Is heated to 800 c and held at 800 c for 2h and then cooled to room temperature, and the obtained sample is named ZnS/NPC-2.
Example 4
Preparation of catalyst sample ZnS/NPC-3: reacting ZnCl2And BSA in water (ZnCl)2The mass ratio of BSA to BSA was 3: 1) after drying by a freeze dryer, the obtained solid was transferred into a tube furnace and pyrolyzed under a nitrogen stream. First at 10 ℃ for min-1Heating the sample to 500 ℃ at a heating rate of (1), and then at 5 ℃ for min-1Is heated to 800 c and held at 800 c for 2h and then cooled to room temperature, and the obtained sample is named ZnS/NPC-3.
Example 5
Preparation of sample ZnS: ZnS was prepared by a simple single pot wet chemical method. Adding ethylene glycol containing polyvinylpyrrolidone (PVP) at room temperature, and adding zinc sulfate (ZnSO)4 7H2O), trisodium citrate and NaOH solution. The product was separated from the reaction mixture by centrifugation, washed several times with ethanol and washed with 0.1M HNO3And (4) processing and collecting to obtain ZnS nano particles.
Example 6
Preparation of ZnS/AC catalyst: a mixture of Activated Carbon (AC), ZnS and ethanol (5mL) was stirred at room temperature for 1 hour, wherein the Zn content in ZnS/AC was the same as that in ZnS/NPC-3. The solid was collected by centrifugation and the obtained solid was dried in vacuo at 60 ℃ for 12 hours.
The catalysts prepared in examples 1-6 above were characterized as follows:
the XRD pattern of ZnS/NPC-X is shown in FIG. 1 (a). All samples had a bulge peak at 25 ° belonging to the (002) plane of the graphitic carbon. In addition to the above peaks, with respect to ZnS/NPC-1, ZnS/NPC-2 and ZnS/NPC-3 prepared in examples 2, 3 and 4, there were 4 peaks located at 28.3 °, 32.8 °, 47.1 ° and 55.9 °, belonging to the (111), (200), (220) and (400) crystal planes of ZnS. As shown in FIG. 1(b), X-ray photoelectron spectroscopy (XPS) of ZnS/NPC-X is shown. XPS measurement spectra of ZnS/NPC-1, ZnS/NPC-2 and ZnS/NPC-3 prepared in examples 2, 3, 4 showed peaks of Zn 2p, S2 p, N1S and C1S, while NPC prepared in example 1 showed peaks of S2 p, N1S and C1S. As shown in FIG. 1(c), a Zn 2p spectrum of ZnS/NPC-X is shown. In ZnS/NPC-1, ZnS/NPC-2 and ZnS/NPC-3The high resolution XPS spectrum of Zn 2p of (A) shows two peaks at 1021.5 and 1044.5eV, corresponding to Zn 2p respectively3/2And Zn 2p1/2. As shown in FIG. 1(D), a Raman spectrum of ZnS/NPC-X shows two different peaks, namely, a D band (about 1340 cm)-1) And G belt (about 1587 cm)-1) This is due to the defects and graphitization properties of the carbon structure, respectively. The ID/IG values of NPC, ZnS/NPC-1, ZnS/NPC-2 and ZnS/NPC-3 were 0.92, 1.02, 1.04 and 1.04, respectively. It is clear that with increasing Zn content in the precursor, the ID/IG increases slightly. This is mainly because the boiling point of Zn is low (about 900 ℃), which can etch the carbon-based material and cause a defective structure. N of ZnS/NPC-X as shown in FIG. 1(e)2The adsorption/desorption isotherm shows that the NPC prepared in example 1 itself has an extremely low adsorption amount. In contrast, Zn is introduced into the precursor2+Then, the N of the obtained catalysts ZnS/NPC-1, ZnS/NPC-2 and ZnS/NPC-32The adsorption amount is much higher than that of NPC, and the adsorption balance is rapidly raised in a low-pressure area and is achieved, and the typical microporous structure characteristic is realized. In addition, in P/P0At 0.4 to 0.8, there is also a significant hysteresis loop, indicating that there is a certain amount of mesoporous structure. FIG. 1(f) shows a pore size distribution diagram of ZnS/NPC-X, where 2 to 10nm of mesopores and<2nm pores. The porous structure, especially the mesoporous structure, is not only beneficial to the mass transfer in the reaction process, but also beneficial to enhancing the photo-thermal performance of the catalyst and improving the activity of the catalyst.
FIG. 2 shows a Transmission Electron Microscope (TEM) image of ZnS/NPC-X, a HADDF-TEM image, and a scanning spectrum of ZnS/NPC-2. NPC are dense and have no apparent pore structure, while ZnS/NPC-X have a loose porous structure, which is comparable to their N2The results of the adsorption/desorption isotherms were consistent. As shown in FIGS. 2(c), (e) are HADDF-TEM images of ZnS/NPC-1, ZnS/NPC-2 and ZnS/NPC-3, the ZnS/NPC-X catalyst sample has ultra-small ZnS nanoparticles (red cycle highlighting). FIG. 2(g) is a scanning spectrum of ZnS/NPC-2 catalyst prepared in example 3, showing that the ZnS/NPC-2 catalyst contains Zn, S, N and C elements.
FIG. 3(b) is a graph showing the UV-visible absorption spectrum of ZnS/NPC-X, showing ZnS/NPThe C-X has strong light absorption in the wavelength range of 200-1100 nm, so that the C-X can fully utilize light of each wavelength band and convert the light into heat. The ZnS/NPC-rich porous structure can enhance the light collection and reflection, thereby further improving the photothermal effect. As shown in FIG. 3(c), the temperature rise of the DMF solution caused by ZnS/NPC-1, ZnS/NPC-2 and ZnS/NPC-3 is more significant than that caused by NPC, which is probably caused by the combined action of ZnS and porous carbon. ZnS/NPC-2 showed the best photothermal effect in all samples. After 15 minutes of irradiation, the temperature of the solvent was raised to 65 ℃. As shown in FIG. 3(d), the photothermal stability test chart of ZnS/NPC-2 shows that almost no change occurs in photothermal properties after light cycle, indicating that ZnS/NPC-2 has very good photothermal stability. ZnS/NPC-X has excellent photothermal effect and rich CO2Adsorption and activation sites and porous structures, are potential CO2A photo-thermal catalyst.
Example 7
ZnS/NPCs composite photothermal catalyst for catalyzing CO under light drive2The cycloaddition reaction is carried out as follows: a mixture of 10mg of catalyst, 0.03mmol of tetra-n-butylammonium bromide (TBAB), 1mL of Dimethylformamide (DMF) and 0.1mmol of epoxide was placed in a reactor tube and charged with CO2Connected to the tube by a CO2Purging the reactor several times to fill the reactor and balloon with CO2. The catalytic cycloaddition reaction was performed under illumination from a Microlar 300Xe lamp and the light intensity was adjusted by varying the current. The yield of the product was checked by 1H NMR using 1,1,2, 2-tetrachloroethane as an internal standard. For in low CO2Reaction under pressure with 0.15bar CO2And 0.85bar N2Instead of pure CO2The rest steps are as above.
TABLE 1
Figure BDA0002368434750000101
Figure BDA0002368434750000102
Figure BDA0002368434750000111
Table 1 shows 3-chloroepoxypropane and CO under various conditions2The catalytic cycloaddition reaction of (1). [ a ] A]Reaction conditions are as follows: 0.10mmol of 3-chloropropene, 10mg of the catalyst prepared in example 1,2, 3, 4, 5, 6, 0.03mmol of TBAB, 1ml of DMF, 1bar CO2Full spectrum radiation (300W), lasting 12 h; [ b ] a]No catalyst; [ c ] is]Heating at 65 deg.C for 12h instead of full spectrum irradiation for 12 h; [ d]By mixing ZnS/NPC-2 prepared in example 3 at 2M H2SO4Boiling for 8 hours to prepare ZnS/NPC-2-W; [ e ] a]No TBAB; [ f ] of]Replacing carbon dioxide with nitrogen; [ g ]]No light irradiation; [ h ] of]Mixing CO with 1bar2/N2(0.15/0.85, v/v) instead of 1bar CO2The reaction time is prolonged to 24 hours; [ i ]]The products of the cycloaddition reaction were analyzed and identified by 1H NMR using 1,1,2, 2-tetrachloroethane as an internal standard.
As shown in Table 1, 3-chloroepoxypropane and CO2Evaluation of the performance of the catalytic cycloaddition reaction under various conditions. As shown in table 1, entry 1, the yield of the product (4- (chloromethyl) -1, 3-dioxolan-2-one) was very low (8%) when light was applied without the participation of a catalyst. As shown in entries 2-5 of Table 1, the product yield was significantly improved by adding ZnS/NPC-X. Of all the catalysts, ZnS/NPC-2 performed best with a product yield of 98%, thanks to its extremely high photothermal conversion efficiency and good CO2A capture capability. Meanwhile, the performance of ZnS/NPC-X is also superior to that of ZnS or activated carbon loaded with ZnS (ZnS/AC). As shown in table 1, item 13, light also had a significant effect on the reaction, and when the light source was removed, the product yield dropped to 55%. Therefore, the good catalytic effect of ZnS/NPC-2 is the result of the cooperation of the catalyst and the light. As shown in table 1, entry 10, when catalyst is mixed with 2M H2SO4After the azeotropic treatment for 8 hours to remove ZnS from ZnS/NPC-2, the activity of the resulting ZnS/NPC-2-W was drastically decreased and the yield of the product was decreased to 57%. This confirms that ZnS is a key component of ZnS/NPC-X, possibly with NDoped porous carbon CO-use to promote CO2And (4) activating. However, 0.7% of Zn atoms remained after the acid treatment, which is likely to be anchored by N atoms. It is reported that Zn atom anchored by N atom is to CO2The cycloaddition reaction of (a) is catalytically active. Thus, after removal of ZnS, a yield of 57% was maintained on ZnS/NPC-2-W. As shown in table 1, entry 9, in studying the effect of light irradiation on the reaction, the yield remained at 95% by replacing the irradiation with heat at 65 ℃, so we speculated that the nature of the temperature-sensitive light-driven cycloaddition reaction is photothermal.
The flue gas being CO2Of significant origin, CO thereof2The content of (A) is about 10 to 20%. As shown in item 14 of table 1, under an atmosphere simulating smoke (CO)2/N20.15/0.85, v/v) the catalytic performance of ZnS/NPC-2 was evaluated. Under these conditions, the product yield was as high as 82%, indicating that ZnS/NPC-2 can be used for photo-driven CO in practical situations2Trapping and converting.
As shown in a) in FIG. 4, the catalytic performance of ZnS/NPC-2 on various substrates is shown, and the substrates which can be catalyzed have a very wide range and good yield (75-99%). These substrates include small size substrates (propylene oxide, 99%) and large size substrates (2- (phenoxymethyl) -ethylene oxide, 88%, 2- ((allyloxy) -methyl) -ethylene oxide, 82%). In view of the fact that ZnS/NPC-2 can adsorb and activate CO under the action of light drive2。
Example 8
ZnS/NPCs composite photothermal catalyst for catalyzing CO under light drive2The methylation reaction is specifically carried out as follows: 10mg of catalyst, 0.3mmol of phenylsilane (PhSiH)3) 1mL of Dimethylformamide (DMF), and 0.1mmol of amine substrate were placed in a reactor tube and charged with CO2Connected to the tube by a CO2Purging the reactor several times to fill the reactor and balloon with CO2. The catalytic methylation reaction was performed under the illumination of a Microlar 300Xe lamp and the light intensity was adjusted by varying the current. Substrate conversion and product selectivity were determined by HPLC.
As shown in b) of FIG. 4The evaluation of ZnS/NPC-2 on the basis of CO2Activity in aminomethylation reactions. In the case where ZnS/NPC-2 was not introduced, the conversion of N-methylamine and the selectivity of N, N-dimethylamine upon irradiation with light were 22% and 82%, respectively, which were much lower than those in the case where ZnS/NPC-2 was introduced (99%, 95%). When only the light irradiation was removed, the conversion and selectivity were 41% and 92%, respectively, indicating that light irradiation is critical for the catalytic reaction process. Similarly, ZnS/NPC-2 is suitable for different substrates and is very high in both yield and conversion (both)>99%). The above results show that ZnS/NPC-2 is a very useful photo-thermal catalyst for CO2The catalytic conversion of (2).
By way of example, the preparation method of ZnS/NPC-X composite photothermal catalyst and CO driven by light thereof are demonstrated2Effect of cycloaddition reaction and methylation reaction performance.
The above description is only a few specific embodiments of the present invention, and the protection scope of the present invention is not limited to the above embodiments, and all equivalent changes and modifications made in the claims of the present invention should be covered by the present invention, and the protection scope of the present invention is as shown in the claims of the present application.

Claims (12)

1. The application of the nitrogen-doped porous carbon loaded ZnS nano composite material is characterized in that: as a photo-thermal catalyst applied to the cycloaddition reaction of carbon dioxide; the nitrogen-doped porous carbon loaded ZnS nano composite material is prepared by the following preparation method: dissolving and dispersing zinc salt and sulfur-containing protein into water, and freeze-drying and pyrolyzing to obtain the zinc-containing zinc-sulfur-containing protein.
2. The use of the nitrogen-doped porous carbon-supported ZnS nanocomposite as claimed in claim 1, wherein: the method comprises the steps of taking a nitrogen-doped porous carbon loaded ZnS nano composite material as a catalyst, and introducing CO into a mixed system of tetra-n-butylammonium bromide, dimethylformamide and an epoxy compound2And carrying out catalytic cycloaddition reaction under the condition of illumination.
3. The use of the nitrogen-doped porous carbon-supported ZnS nanocomposite as claimed in claim 1, wherein:
the zinc salt is at least one of zinc chloride, zinc acetate, zinc sulfate and zinc nitrate;
the sulfur-containing protein is at least one of BSA and egg white.
4. Use of a nitrogen-doped porous carbon-supported ZnS nanocomposite according to claim 1 or 3, characterized in that: the mass ratio of the zinc salt to the sulfur-containing protein is 1.15: 1-3: 1.
5. The use of the nitrogen-doped porous carbon-supported ZnS nanocomposite as claimed in claim 1, wherein: the pyrolysis conditions are as follows: and pyrolyzing for 2-4 h at 700-1000 ℃ in a protective atmosphere.
6. The use of the nitrogen-doped porous carbon-supported ZnS nanocomposite as claimed in claim 5, wherein: the nitrogen-doped porous carbon-loaded ZnS nano composite material has mesopores with the aperture of 2-10 nm and the aperture<2nm micropores with specific surface area of 1300-1800 m2· g-1The specific surface area of the mesopores is 700-1200 m2· g-1The total pore volume is 0.80-1.00 cm3· g-1。
7. The application of the nitrogen-doped porous carbon loaded ZnS nano composite material is characterized in that: the catalyst is used as a photo-thermal catalyst for methylation of carbon dioxide; the nitrogen-doped porous carbon loaded ZnS nano composite material is prepared by the following preparation method: dissolving and dispersing zinc salt and sulfur-containing protein into water, and freeze-drying and pyrolyzing to obtain the zinc-containing zinc-sulfur-containing protein.
8. The use of the nitrogen-doped porous carbon-supported ZnS nanocomposite as claimed in claim 7, wherein: prepared by using nitrogen-doped porous carbon loaded ZnS nano composite materialIntroducing CO into a system for mixing phenylsilane and amine substrates as a catalyst2And carrying out catalytic methylation reaction under the illumination condition.
9. The use of the nitrogen-doped porous carbon-supported ZnS nanocomposite as claimed in claim 7, wherein:
the zinc salt is at least one of zinc chloride, zinc acetate, zinc sulfate and zinc nitrate;
the sulfur-containing protein is at least one of BSA and egg white.
10. Use of a nitrogen-doped porous carbon-supported ZnS nanocomposite according to claim 7 or 9, characterized in that: the mass ratio of the zinc salt to the sulfur-containing protein is 1.15: 1-3: 1.
11. The use of the nitrogen-doped porous carbon-supported ZnS nanocomposite as claimed in claim 7, wherein: the pyrolysis conditions are as follows: and pyrolyzing for 2-4 h at 700-1000 ℃ in a protective atmosphere.
12. The use of the nitrogen-doped porous carbon-supported ZnS nanocomposite as claimed in claim 7, wherein: the nitrogen-doped porous carbon-loaded ZnS nano composite material has mesopores with the aperture of 2-10 nm and the aperture<2nm micropores with specific surface area of 1300-1800 m2· g-1The specific surface area of the mesopores is 700-1200 m2· g-1The total pore volume is 0.80-1.00 cm3· g-1。
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