CN109908884B - Integrated honeycomb zinc-based composite material ((ZnO @ C)/C) and preparation method and application thereof - Google Patents
Integrated honeycomb zinc-based composite material ((ZnO @ C)/C) and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to the technical field of catalyst preparation, in particular to a complete honeycomb zinc-based composite material ((ZnO @ C)/C) and a preparation method and application thereof, wherein the preparation method comprises the following steps: 1) pretreatment of the carrier: taking massive biomass and acid solution for reflux reaction, washing with deionized water, drying at normal temperature, and sealing for later use; 2) respectively weighing zinc salt and 2-methylimidazole, dissolving in methanol, and uniformly stirring to obtain a solution A; 3) immersing pretreated biomass in the solution A at normal temperature for a period of time, or putting the pretreated biomass and the solution A into a hydrothermal reaction kettle together for constant-temperature hydrothermal reaction, and then cooling to room temperature; taking out the massive biomass, and cooling to room temperature; 4) putting the obtained biomass in a porcelain boat, and introducing N2Calcining under the condition of (1) to prepare the integral honeycomb zinc-based composite material ((ZnO @ C)/C). The product can be used for photocatalytic degradation of organic wastewater.
Description
Technical Field
The invention relates to the technical field of catalyst preparation, in particular to a honeycomb zinc-based composite material and a preparation method thereof.
Background
In recent years, organic wastewater pollution is more and more serious, and wastewater treatment is an urgent need. Wood-derived materials, particularly cellulose nanofibers and cellulose nanocrystals, have made great progress in recent years in emerging application fields, particularly have been widely applied in the field of catalyst carriers, and a metal organic framework material is used as a good catalyst for degrading organic wastewater materials, so that the effective combination of the two materials brings hopes for the research of clean and renewable energy sources.
Metal-Organic Frameworks (MOFs) are a new porous network structure material formed by coordination and connection of Metal ions and Organic ligands. The crystal material is a crystal material which is self-assembled by utilizing organic ligands and metal ions or metal clusters through coordination bonds or intermolecular interaction force and has a one-dimensional, two-dimensional or three-dimensional infinite network structure. Because of the advantages of large specific surface area, adjustable aperture size, chemical modification according to target requirements, abundant structure and the like, the MOFs show great application potential in the aspect of catalysis.
The porous carbon material has the advantages of high chemical stability, strong adsorption capacity, acid resistance, alkali resistance, strong heat resistance, regular gap structure and the like, so that the porous carbon material is widely applied to the fields of catalyst carriers, adsorbents, electrochemical energy storage and the like.
The porous carbon material derived from the MOFs material has large specific surface area, good acid resistance, alkali resistance, heat resistance and higher chemical stability, and sp of the porous carbon material2The hybridized carbon can generate strong pi-pi interaction and hydrophobic interaction with organic molecules, and porous carbon materials with different pore and pore diameter structures can generate size exclusion effect on analytes with different structures, so that selective extraction is facilitated, and therefore, the metal porous composite material derived from the MOFs material is expected to become a novel catalyst with excellent performance.
Disclosure of Invention
The invention aims to provide a complete honeycomb zinc-based composite material ((ZnO @ C)/C) and a preparation method and application thereof.
In order to achieve the purpose, the invention provides the following technical scheme:
a preparation method of a complete honeycomb zinc-based composite material ((ZnO @ C)/C) comprises the following steps:
(1) pretreatment of the carrier: taking 0.5-5 g of blocky biomass and 30-150 mL of acid solution to perform reflux reaction at the temperature of 50-120 ℃ for 1-36 hours, washing the biomass with deionized water, drying at normal temperature, and storing in a sealed manner for later use;
(2) weighing a mixture with a molar ratio of 1: dissolving 1-36 zinc salt solution and 2-methylimidazole in methanol, and uniformly stirring to obtain solution A;
(3) soaking the pretreated biomass in the step (1) in the solution A at normal temperature for 5-36 hours, or placing the pretreated biomass and the solution C into a polytetrafluoroethylene hydrothermal reaction kettle together for constant temperature reaction at 80-130 ℃ for 10-30 hours, and then cooling to room temperature; taking out the massive biomass, and cooling to room temperature;
(4) putting the biomass obtained in the step (3) into a porcelain boat, and introducing N2Calcining under the condition of (1) to prepare the integral honeycomb zinc-based composite material ((ZnO @ C)/C).
Wherein the acid solution in the step (1) is nitric acid, hydrogen peroxide or potassium permanganate solution.
Wherein, the biomass in the step (1) is a biomass material with natural macropores.
Wherein, the biomass in the step (1) comprises wood blocks and bamboos.
Wherein the washing times in the step (1) are 3-6 times.
Wherein, the zinc salt in the step (2) is zinc chloride or zinc nitrate; the solvent is methanol.
Wherein the calcining temperature in the step (4) is 300-900 ℃.
Wherein, the calcination in the step (4) is carried out for 0.5-6 hours.
The complete honeycomb zinc-based composite material ((ZnO @ C)/C) prepared by the preparation method is provided.
The combination of metal catalyst derived from MOFs material and massive biomass catalyst carrier, wherein the massive biomass has a pore canal without bending, H2And CO is limited to pass through the pore canal, and is more favorable for H2And CO, so that the CO is forced to be fully contacted with the MOFs-derived metal catalyst and react. Therefore, the integrated honeycomb zinc-based composite material ((ZnO @ C)/C) synthesized by the invention can be excellent in performanceA novel catalyst. The complete honeycomb zinc-based composite material ((ZnO @ C)/C) can be used for photocatalytic degradation of organic wastewater.
Compared with the prior art, the invention has the beneficial effects that:
the invention takes a solvent thermal synthesis method as an auxiliary and then charrs, so that a porous material derived from ZIF-8 is generated in a pore channel by taking a carbon pore channel as a reaction container, and a honeycomb zinc-based composite material ((ZnO @ C)/C) with good activity and high thermal stability is effectively generated. The preparation method optimizes the process reaction conditions, greatly simplifies the synthesis process and reduces the experiment cost.
Drawings
FIG. 1 is an XRD pattern of a complete honeycomb zinc-based composite ((ZnO @ C)/C) made in example 1;
FIG. 2 is an SEM topography of a complete honeycomb zinc-based composite ((ZnO @ C)/C) made in example 1;
FIG. 3 shows the results of a methylene blue solution test of a complete honeycomb zinc-based composite ((ZnO @ C)/C) prepared in example 1 for photocatalyst degradation of 10mg/100 mL.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A preparation method of a complete honeycomb zinc-based composite material ((ZnO @ C)/C) comprises the following steps:
(1) taking 2g of cubic wood block, carrying out reflux reaction on the cubic wood block and 50mL of hydrogen peroxide at 100 ℃ for 24 hours, repeatedly washing the wood block for 5 times under the boiling condition by using deionized water, drying at normal temperature, and sealing for later use;
(2) weighing 0.341g of zinc chloride, dissolving the zinc chloride in 25ml of methanol, uniformly stirring to obtain a solution A, weighing 1.642g of 2-methylimidazole, dissolving the 2-methylimidazole in 25ml of methanol, uniformly stirring to obtain a solution B, pouring the solution A into the solution B, and stirring for 1 hour at room temperature to obtain a mixed solution C;
(3) putting the pretreated massive biomass in the step (1) and the mixed solution C into a hydrothermal reaction kettle with a polytetrafluoroethylene lining, carrying out hydrothermal reaction at 100 ℃ for 24 hours, cooling to room temperature, taking out the wood block, and drying at room temperature;
(4) putting the biomass obtained in the step (3) into a porcelain boat, and introducing N2And calcining for 3 hours at the temperature of 600 ℃ to prepare the sample honeycomb zinc-based composite material ((ZnO @ C)/C).
The XRD pattern of the honeycomb zinc-based composite material ((ZnO @ C)/C) is obtained in example 1, and it is obvious from figure 1 that after the wood block is carbonized, the frame material exists in a form of carbon-coated zinc oxide, which is beneficial to improving the catalytic activity.
The SEM image of the honeycomb zinc-based composite ((ZnO @ C)/C) obtained in example 1 is shown in FIG. 2, from which it can be seen that ZIF-8 derived porous materials are grown significantly in the voids of the carbon prepared according to the experimental method.
Example 2
A preparation method of a complete honeycomb zinc-based composite material ((ZnO @ C)/C) comprises the following steps:
(1) taking 2g of bamboo chips, carrying out reflux reaction on the bamboo chips and 100mL of potassium permanganate solution at 120 ℃ for 12 hours, repeatedly washing the bamboo chips for 5 times under the boiling condition by using deionized water, drying at normal temperature, and sealing for later use;
(2) weighing 0.182g of zinc nitrate, dissolving the zinc nitrate in 30ml of methanol, uniformly stirring to obtain a solution A, weighing 1.642g of 2-methylimidazole, dissolving the 2-methylimidazole in 30ml of methanol, uniformly stirring to obtain a solution B, pouring the solution A into the solution B, and stirring for 1h at room temperature to obtain a mixed solution C;
(3) soaking the pretreated massive biomass in the step (1) in the mixed solution C at normal temperature, aging for 24 hours, taking out the wood block, and drying at normal temperature;
(4) putting the biomass obtained in the step (3) into a porcelain boat, and introducing N2The honeycomb zinc-based composite material is prepared by calcining for 3h at 700 ℃ under the condition of (1) to obtain a sample honeycomb zinc-based composite material ((ZnO @ C)/C).
The honeycomb zinc-based composite ((ZnO @ C)/C) obtained in example 1 was subjected to a photocatalyst degradation test using a methylene blue solution of 10mg/100mL, and the test results are shown in FIG. 3. The honeycomb zinc-based composite material ((ZnO @ C)/C) prepared by the implementation method has high catalytic activity, the degradation rate can reach 97.9%, and the effect is obvious.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (6)
1. A preparation method of a complete honeycomb zinc-based composite material ((ZnO @ C)/C) is characterized by comprising the following steps:
(1) pretreatment of the carrier: taking 0.5-5 g of blocky biomass and 30-150 mL of acid solution to perform reflux reaction at the temperature of 50-120 ℃ for 1-36 hours, washing the biomass with deionized water, drying at normal temperature, and storing in a sealed manner for later use; the massive biomass is wood blocks or bamboos; the acid solution is nitric acid, hydrogen peroxide or potassium permanganate solution;
(2) weighing a mixture with a molar ratio of 1: dissolving 1-36 zinc salt solution and 2-methylimidazole in methanol, and uniformly stirring to obtain solution A;
(3) soaking the pretreated biomass in the step (1) in the solution A at normal temperature for 5-36 hours, or placing the pretreated biomass and the solution A into a polytetrafluoroethylene hydrothermal reaction kettle together for constant temperature reaction at 80-130 ℃ for 10-30 hours, and then cooling to room temperature; taking out the massive biomass, and cooling to room temperature;
(4) putting the biomass obtained in the step (3) into a porcelain boat, and introducing N2Calcining at the temperature of 300-900 ℃; calcining for 0.5-6 hours to prepare the complete honeycomb zinc-based composite material ((ZnO @ C)/C).
2. The method of preparing a monolithic honeycomb zinc-based composite ((ZnO @ C)/C) according to claim 1, wherein: and (2) washing in the step (1) for 3-6 times.
3. The method of preparing a monolithic honeycomb zinc-based composite ((ZnO @ C)/C) according to claim 1, wherein: the zinc salt in the step (2) is zinc chloride or zinc nitrate; the solvent is methanol.
4. A complete honeycomb zinc-based composite ((ZnO @ C)/C) prepared by the method of any one of claims 1 to 3.
5. Use of the complete honeycomb zinc-based composite ((ZnO @ C)/C) according to claim 4 for photocatalytic degradation of organic waste water.
6. Use of a complete honeycomb zinc-based composite ((ZnO @ C)/C) according to claim 5, for photocatalytic degradation of organic waste water, characterized in that: the organic wastewater is methyl orange or methylene blue.
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| CN106179314A (en) * | 2016-07-06 | 2016-12-07 | 南京工业大学 | A kind of multicomponent composite photo-catalyst and its preparation method and application |
| CN108557918A (en) * | 2018-04-13 | 2018-09-21 | 兰州大学 | A kind of filtration membrane and its preparation method and application |
| CN109174092A (en) * | 2018-09-21 | 2019-01-11 | 东华大学 | A kind of zinc oxide/platinum composite material microballoon and its preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106179314A (en) * | 2016-07-06 | 2016-12-07 | 南京工业大学 | A kind of multicomponent composite photo-catalyst and its preparation method and application |
| CN108557918A (en) * | 2018-04-13 | 2018-09-21 | 兰州大学 | A kind of filtration membrane and its preparation method and application |
| CN109174092A (en) * | 2018-09-21 | 2019-01-11 | 东华大学 | A kind of zinc oxide/platinum composite material microballoon and its preparation method and application |
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Effective date of registration: 20211229 Address after: 212300 Liangxi Road, Lucheng Town Industrial Park, Danyang City, Zhenjiang City, Jiangsu Province Patentee after: DANYANG HUAFA ENVIRONMENTAL PROTECTION MACHINERY Co.,Ltd. Address before: 213001 No. 1801 Wu Cheng Road, Changzhou, Jiangsu Patentee before: JIANGSU University OF TECHNOLOGY |
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