Fe-cerium-zirconium trimetallic MOFs derived carbon material, preparation method and application thereof
By preparing Fe-Ce-Zr trimetallic MOFs-derived carbon materials, the adsorption competition and stability problems of existing VOCs adsorption materials have been solved, achieving efficient and selective VOCs adsorption, which is particularly suitable for the treatment of low-concentration VOCs.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- ZINGKE (CHONGQING) ADVANCED MATERIALS RES INST CO LTD
- Filing Date
- 2026-03-31
- Publication Date
- 2026-05-29
AI Technical Summary
Existing VOCs adsorption materials suffer from the problem of competitive adsorption between water and VOCs gases. The MOF framework structure is easily destroyed, and the metal oxides are unevenly dispersed, resulting in poor loading stability and making it difficult to achieve efficient and selective VOCs adsorption.
Fe-Ce-Zr trimetallic MOFs-derived carbon materials were prepared by a solvothermal method. Subsequently, the carbon framework was calcined in an inert atmosphere to form a porous carbon framework. Through plasma treatment and amino functionalization, a hierarchical porous structure and multimetallic active sites were constructed to enhance the adsorption performance of VOCs.
It achieves highly efficient adsorption of VOCs, with large adsorption capacity, good selectivity and excellent moisture resistance, strong cycle stability, and is suitable for long-term VOCs treatment.
Smart Images
Figure CN122098532A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of gas adsorption materials technology, and in particular to Fe-Ce-Zr trimetallic MOFs derived carbon materials, their preparation methods and applications. Background Technology
[0002] VOCs are volatile organic compounds. They are easily volatilized at room temperature and possess characteristics such as toxicity, irritation, teratogenicity, and carcinogenicity, seriously threatening human health. The most effective way to control VOCs is through source control at the production level. However, due to limitations in production technology, industrial production inevitably still releases VOCs into the atmosphere. Controlling VOC emissions mainly involves two methods: source control and end-of-pipe treatment. Eliminating VOC emissions at the source has limited effectiveness, and end-of-pipe treatment remains the most crucial aspect of current VOC emission control. Combining end-of-pipe treatment and source control is essential to effectively reduce VOC emissions. Therefore, developing a highly efficient VOCs adsorption material is particularly important for the economic regulation of industrial VOCs.
[0003] Currently, adsorption materials used for VOCs adsorption include activated carbon, MOFs, ion exchange resins, and zeolites. Among these, MOFs have attracted widespread attention due to their advantages of large specific surface area, customizable structure, and numerous active sites. Patent CN116272904A discloses a MOFs composite VOCs adsorbent and its preparation method, which attaches carboxyl groups to the activated carbon adsorption surface through an organometallic framework, thereby improving the selective adsorption capacity of VOCs. However, this material suffers from the problem of competitive adsorption between water and VOCs gases, as well as the problem of water occupying adsorption sites and destroying the MOFs framework structure, leading to MOFs failure. Patent CN10251445A discloses a porous carbon adsorbent, its preparation method, and its application. The active components of the adsorbent are amorphous carbon and metal oxides. The preparation method involves impregnating natural polymer materials in a nitrate aqueous solution, followed by drying and carbonization. The prepared porous carbon adsorbent exhibits excellent adsorption performance and also enhances the adsorption of anionic inorganic pollutants. However, the dispersion of these metal oxides is uneven, resulting in poor loading stability, and its primary application is in adsorbing ionic compounds in water. Therefore, there is a need to develop a VOCs adsorbent material that is highly efficient, environmentally friendly, and has a simple manufacturing process. Summary of the Invention
[0004] In view of this, the purpose of this invention is to provide Fe-Ce-Zr trimetallic MOFs-derived carbon materials, their preparation methods and applications. The prepared Fe-Ce-Zr trimetallic MOFs-derived carbon materials combine the high specific surface area and hierarchical porous structure of MOFs, the strong adsorption effect of trimetallic sites, and the excellent hydrophobic stability and structural integrity of the carbon skeleton. They have outstanding advantages such as large adsorption capacity, good selectivity, excellent moisture resistance and strong cycle stability for volatile organic compounds.
[0005] The following is a summary of this disclosure to provide a basic understanding of some aspects. This summary is not intended to identify key or important elements, nor is it intended to limit the implementation or any aspects of the claims. Furthermore, this summary provides a simplified overview of some aspects that can be described in more detail in other parts of this disclosure.
[0006] The present invention solves the above-mentioned technical problems through the following technical means:
[0007] In a first aspect, embodiments of the present invention provide a method for preparing Fe-Ce-Zr trimetallic MOFs-derived carbon materials, comprising the following steps:
[0008] Ferric nitrate, cerium nitrate, zirconium nitrate, and phthalic acid were added to dimethylformamide, stirred and dissolved, and then reacted at 120-150℃ for 30-48h. After cooling to room temperature, the reaction solution was centrifuged to obtain a solid product, which was washed, dried, and Fe-Ce-Zr-MOFs were prepared.
[0009] Fe-Ce-Zr-MOFs were placed in an argon atmosphere and calcined at 600-800℃ for 2-4 hours at a heating rate of 10-12℃ / min to obtain Fe-Ce-Zr-MOFs-C.
[0010] In conjunction with the first aspect, in some embodiments, the mass ratio of ferric nitrate, cerium nitrate, zirconium nitrate, and phthalic acid is 1:(0.8-1.2):(0.9-1.5):(0.5-0.8).
[0011] By adopting the above technical solution, on the one hand, the Zr in Fe-Ce-Zr-MOFs-C material... 4The Fe-Ce-Zr trimetallic alloy possesses strong Lewis acidic sites, exhibiting high affinity for oxygen-containing VOCs (aldehydes, ketones, esters). Its abundant oxygen vacancies allow for the adsorption of aromatic VOCs through acid-base interactions, electrostatic interactions, and π-interactions. Fe-based oxides provide magnetic / oxidation sites, enhancing interactions with unsaturated VOCs. The combined effect of these multiple active sites makes the Fe-Ce-Zr-MOFs-C material more robust and stable in its VOC adsorption. Furthermore, the carbon skeleton in the calcined Fe-Ce-Zr-MOFs-C material inhibits metal particle aggregation, maintaining high dispersion. The metal-carbon structure is less prone to collapse and does not lose active components, resulting in high adsorption capacity retention after multiple cycles, making it suitable for long-term, continuous VOC treatment. Additionally, the Ce and Fe elements in the Fe-Ce-Zr-MOFs-C material possess redox properties, and the carbon material is conductive, facilitating electron transfer and enabling integrated adsorption and degradation of VOCs, making it particularly suitable for the adsorption of low-concentration VOCs. In addition, during the inert atmosphere calcination process, the template agent is thermally removed, and a continuous and uniform mesoporous structure is constructed in the Fe-Ce-Zr-MOFs-C material, which significantly improves the diffusion and transport efficiency and adsorption capacity of VOCs molecules.
[0012] In conjunction with the first aspect, in some embodiments, the preparation method of the Fe-Ce-Zr-MOFs is as follows:
[0013] Ferric nitrate, cerium nitrate, zirconium nitrate, phthalic acid, and a pore-expanding agent were added to dimethylformamide and stirred to dissolve. The resulting precursor solution was placed at 120–150 °C for 30–48 h and cooled to room temperature. The resulting reaction solution was centrifuged to obtain a solid product, which was then washed, dried, and Fe-Ce-Zr-MOFs were prepared.
[0014] In conjunction with the first aspect, in some embodiments, the amount of the pore-expanding agent is 5% to 20% of the total mass of ferric nitrate, cerium nitrate, and zirconium nitrate, and the pore-expanding agent is selected from one of P123, F127, and CTBA.
[0015] In the precursor solution preparation stage, the pore expander is added to dimethylformamide along with ferric nitrate, cerium nitrate, zirconium nitrate, phthalic acid, and the pore expander to form a homogeneous mixture. After a solvothermal reaction, MOF crystals grow in situ around the template micelles. During the subsequent inert atmosphere calcination process, the template is thermally removed, constructing a continuous and uniform mesoporous structure in the material, which significantly improves the diffusion and transport efficiency and adsorption capacity of VOCs molecules.
[0016] In conjunction with the first aspect, in some embodiments, the washing involves washing the solid product 2 to 4 times each with dimethylformamide and methanol.
[0017] In conjunction with the first aspect, in some embodiments, the prepared Fe-Ce-Zr-MOFs-C is spread on a quartz substrate, placed in a low-temperature plasma device, evacuated to 50-100 Pa, and plasma-treated for 5-15 minutes under air atmosphere, power 40-60 W, and room temperature conditions.
[0018] Plasma treatment of Fe-Ce-Zr-MOFs-C materials can effectively break metal-oxygen bonds and induce the release of lattice oxygen, thereby constructing a large number of oxygen vacancies and Ce³⁺ active sites on the material surface and in the bulk phase. This enhances the chemical adsorption of VOCs molecules and improves the adsorption performance of the material.
[0019] In conjunction with the first aspect, in some embodiments, plasma-treated Fe-Ce-Zr-MOFs-C is weighed and dispersed in anhydrous ethanol, and ultrasonically treated to obtain a uniform suspension; then ethylenediamine is added as an amino donor, and the mixture is stirred in a constant temperature water bath at 50-65°C for 3-5 hours. The solid sample is then collected by centrifugation, washed with anhydrous ethanol, and then washed with deionized water until the filtrate is neutral. After drying, amino-functionalized Fe-Ce-ZrMOFs-C is obtained.
[0020] In conjunction with the first aspect, in some embodiments, Fe-Ce-Zr-MOFs-C is weighed and dispersed in anhydrous ethanol, and ultrasonically treated to obtain a uniform suspension; then ethylenediamine is added as an amino donor, and the mixture is stirred in a constant temperature water bath at 50-65°C for 3-5 hours. After centrifugation, the solid sample is collected, washed with anhydrous ethanol, and then washed with deionized water until the filtrate is neutral. After drying, amino-functionalized Fe-Ce-ZrMOFs-C is obtained.
[0021] Amino modification of Fe-Ce-Zr-MOFs-C or plasma-treated Fe-Ce-Zr-MOFs-C with ethylenediamine has several advantages. First, the amino groups (-NH2) grafted onto the material surface provide abundant basic sites and lone pairs of electrons, forming strong π-π conjugation with the π electron clouds of the aromatic rings in benzene and toluene molecules. Simultaneously, weak hydrogen bonding exists between the amino groups and the aromatic rings, significantly enhancing the adsorption affinity for these nonpolar aromatic hydrocarbons and effectively solving the problem of insufficient adsorption selectivity of pure carbon materials for aromatic VOCs. Second, the carbonyl group (C=O) in the acetone molecule acts as a hydrogen bond acceptor, forming stable NH…O=C hydrogen bonds with the hydrogen atoms in the amino groups. This strong polar interaction significantly enhances the material's selective adsorption capacity for acetone, resulting in a more significant increase in acetone adsorption capacity compared to the unmodified sample. Furthermore, amino functionalization does not destroy the original hierarchical porous structure and trimetallic synergistic active sites of Fe-Ce-Zr-MOFs-C. The material still maintains a high specific surface area and good mass transfer efficiency, ultimately achieving efficient simultaneous removal of three types of VOCs: benzene, toluene, and acetone. This provides an adsorption material with both universality and selectivity for the treatment of complex VOC systems.
[0022] Secondly, embodiments of the present invention disclose a Fe-Ce-Zr trimetallic MOFs-derived carbon material, which is prepared using the preparation method described in the first aspect above.
[0023] Thirdly, embodiments of the present invention disclose the application of the Fe-Ce-Zr trimetallic MOFs-derived carbon materials described in the second aspect in the preparation of volatile organic compound adsorbent materials.
[0024] One or more technical solutions provided in the embodiments of the present invention have at least the following technical effects or advantages:
[0025] The preparation method of this invention uses ferric nitrate, cerium nitrate, and zirconium nitrate as metal sources and phthalic acid as an organic ligand. A solvothermal method is used to achieve coordination assembly of metal ions and ligands to prepare Fe–Ce–Zr trimetallic MOFs. Following high-temperature calcination under an inert atmosphere, the organic ligands are carbonized in situ into a porous carbon framework, and the metal nodes are transformed into highly dispersed metal oxides, ultimately yielding a Fe–Ce–Zr trimetallic MOFs-C composite material possessing a porous structure, multiple metal active sites, and a carbon matrix. This preparation method uses readily available raw materials, has mild reaction conditions, and is simple to operate.
[0026] The Fe-Ce-Zr trimetallic MOFs-derived carbon material of the present invention combines the high specific surface area and hierarchical porous structure of MOF derivatives, the strong adsorption effect of trimetallic sites, and the excellent hydrophobic stability and structural integrity of the carbon skeleton. It has outstanding advantages such as large adsorption capacity, good selectivity, excellent moisture resistance and strong cycle stability for volatile organic compounds. Attached Figure Description
[0027] Figure 1 These are nitrogen adsorption and desorption curves of Fe-Ce-ZrMOFs-C prepared in Example 1 and Fe-Ce-ZrMOFs prepared in Comparative Example 1.
[0028] Figure 2 These are TGA images of Fe-Ce-ZrMOFs-C prepared in Example 1 and Fe-Ce-ZrMOFs prepared in Comparative Example 1. Detailed Implementation
[0029] The following embodiments are provided to better understand the present invention and are not limited to the preferred embodiments described. They do not constitute a limitation on the content and scope of protection of the present invention. Any product that is the same as or similar to the present invention, derived by any person under the guidance of the present invention or by combining the features of the present invention with other prior art, falls within the protection scope of the present invention.
[0030] For experiments not specifically described in the examples, the procedures or conditions should be followed according to the conventional experimental procedures described in the literature in this field. Reagents or instruments whose manufacturers are not specified are all commercially available products.
[0031] The method for preparing Fe-Ce-Zr trimetallic MOFs-derived carbon materials in this application includes the following steps:
[0032] Ferric nitrate, cerium nitrate, zirconium nitrate, and phthalic acid were added to dimethylformamide and stirred to dissolve. The mixture was then reacted at 120–150 °C for 30–48 h. After cooling to room temperature, the resulting reaction solution was centrifuged to obtain a solid product, which was washed, dried, and Fe-Ce-Zr-MOFs were prepared. The Fe-Ce-Zr-MOFs were then placed under an argon atmosphere and calcined at 600–800 °C for 2–4 h at a heating rate of 10–12 °C / min to obtain Fe-Ce-Zr-MOFs-C. The mass ratio of ferric nitrate, cerium nitrate, zirconium nitrate, and phthalic acid was 1:(0.8–1.2):(0.9–1.5):(0.5–0.8).
[0033] In some embodiments, ferric nitrate, cerium nitrate, zirconium nitrate, phthalic acid, and a pore-expanding agent are added to dimethylformamide, stirred and dissolved, and then reacted at 120–150°C for 30–48 h. After cooling to room temperature, the resulting reaction solution is centrifuged to obtain a solid product, which is then washed, dried, and Fe-Ce-Zr-MOFs are prepared. The amount of the pore-expanding agent used is 5%–20% of the total mass of ferric nitrate, cerium nitrate, and zirconium nitrate, and the pore-expanding agent is selected from P123, F127, and CTBA.
[0034] In some embodiments, the prepared Fe-Ce-Zr-MOFs-C is spread on a quartz substrate, placed in a low-temperature plasma device, evacuated to 50-100 Pa, and plasma-treated for 5-15 min under air atmosphere, power 40-60 W, and room temperature conditions.
[0035] In some embodiments, plasma-treated Fe-Ce-Zr-MOFs-C is weighed and dispersed in anhydrous ethanol, and ultrasonically treated to obtain a uniform suspension. Then, ethylenediamine is added as an amino donor, and the mixture is stirred in a constant temperature water bath at 50-65°C for 3-5 hours to allow the amino group to be loaded onto the surface of the Fe-Ce-Zr-MOFs-C material through covalent grafting and physical adsorption. The solid sample is collected by centrifugation, washed with anhydrous ethanol to remove unreacted ethylenediamine, and then washed with deionized water until the filtrate is neutral. After drying, amino-functionalized Fe-Ce-ZrMOFs-C is obtained.
[0036] In another embodiment, Fe-Ce-Zr-MOFs-C without plasma treatment was weighed and dispersed in anhydrous ethanol, and ultrasonically treated to obtain a homogeneous suspension. Then, ethylenediamine was added as an amino donor, and the mixture was stirred in a constant temperature water bath at 50–65°C for 3–5 hours. The solid sample was collected by centrifugation, washed with anhydrous ethanol, and then washed with deionized water until the filtrate was neutral. After drying, amino-functionalized Fe-Ce-ZrMOFs-C was obtained. Specifically, 1 mL of ethylenediamine was used as the amino donor for every 0.1 g of Fe-Ce-Zr-MOFs-C.
[0037] In the specific implementation:
[0038] Example 1
[0039] The preparation method of the Fe-Ce-Zr trimetallic MOFs-derived carbon material in this embodiment is as follows:
[0040] 1g of ferric nitrate, 1g of cerium nitrate, 1.2g of zirconium nitrate, and 0.5g of phthalic acid were weighed and added to 30ml of dimethylformamide. The mixture was stirred continuously until a clear solution was observed, yielding the precursor solution. The precursor solution was transferred to a Teflon-lined autoclave reactor and reacted at 145℃ for 40h. After the reaction was complete, the autoclave was cooled to room temperature, and the solid product was obtained by centrifugation at 10000rpm. The collected solid product was washed three times each with dimethylformamide and methanol to remove unreacted precursors, and then dried overnight in a hot air oven to obtain Fe-Ce-ZrMOFs. The Fe-Ce-ZrMOFs were calcined at 650℃ for 3h under an argon atmosphere at a heating rate of 10℃ / min to obtain Fe-Ce-ZrMOFs-C, i.e., Fe-Ce-Zr trimetallic MOFs-derived carbon material.
[0041] Example 2
[0042] The preparation method of the Fe-Ce-Zr trimetallic MOFs-derived carbon material in this embodiment is as follows:
[0043] 1g of ferric nitrate, 1g of cerium nitrate, 1.2g of zirconium nitrate, and 0.8g of phthalic acid were weighed and added to 30ml of dimethylformamide. The mixture was stirred continuously until a clear solution was observed, yielding the precursor solution. The precursor solution was transferred to a Teflon-lined autoclave reactor and reacted at 145℃ for 40h. After the reaction was complete, the autoclave was cooled to room temperature, and the solid product was obtained by centrifugation at 10000rpm. The collected solid product was washed three times each with dimethylformamide and methanol to remove unreacted precursors, and then dried overnight in a hot air oven to obtain Fe-Ce-ZrMOFs. The Fe-Ce-ZrMOFs were calcined at 650℃ for 3h under an argon atmosphere at a heating rate of 10℃ / min to obtain Fe-Ce-ZrMOFs-C, i.e., Fe-Ce-Zr trimetallic MOFs-derived carbon material.
[0044] Example 3
[0045] The preparation method of the Fe-Ce-Zr trimetallic MOFs-derived carbon material in this embodiment is as follows:
[0046] 1g of ferric nitrate, 1g of cerium nitrate, 1.2g of zirconium nitrate, and 0.5g of phthalic acid were weighed and added to 30ml of dimethylformamide. The mixture was stirred continuously until a clear solution was observed, yielding the precursor solution. The precursor solution was transferred to a Teflon-lined autoclave reactor and reacted at 145℃ for 40h. After the reaction was complete, the autoclave was cooled to room temperature, and the solid product was obtained by centrifugation at 10000rpm. The collected solid product was washed three times each with dimethylformamide and methanol to remove unreacted precursors, and then dried overnight in a hot air oven to obtain Fe-Ce-ZrMOFs. The Fe-Ce-ZrMOFs were calcined at 750℃ for 3h under an argon atmosphere at a heating rate of 10℃ / min to obtain Fe-Ce-ZrMOFs-C, i.e., Fe-Ce-Zr trimetallic MOFs-derived carbon material.
[0047] Example 4
[0048] The preparation method of the Fe-Ce-Zr trimetallic MOFs-derived carbon material in this embodiment is as follows:
[0049] 1g of ferric nitrate, 1g of cerium nitrate, 1.2g of zirconium nitrate, and 0.8g of phthalic acid were weighed and added to 30ml of dimethylformamide. The mixture was stirred continuously until a clear solution was observed, yielding the precursor solution. The precursor solution was transferred to a Teflon-lined autoclave reactor and reacted at 145℃ for 40h. After the reaction was complete, the autoclave was cooled to room temperature, and the solid product was obtained by centrifugation at 10000rpm. The collected solid product was washed three times each with dimethylformamide and methanol to remove unreacted precursors, and then dried overnight in a hot air oven to obtain Fe-Ce-ZrMOFs. The Fe-Ce-ZrMOFs were calcined at 750℃ for 3h under an argon atmosphere at a heating rate of 10℃ / min to obtain Fe-Ce-ZrMOFs-C, i.e., Fe-Ce-Zr trimetallic MOFs-derived carbon material.
[0050] Example 5
[0051] The preparation method of the Fe-Ce-Zr trimetallic MOFs-derived carbon material in this embodiment is as follows:
[0052] 1g of ferric nitrate, 0.8g of cerium nitrate, 0.9g of zirconium nitrate, 0.5g of phthalic acid, and 0.54g of CTBA were weighed and added to 30ml of dimethylformamide. The mixture was stirred continuously until a clear solution was observed, yielding the precursor solution. The precursor solution was transferred to a Teflon-lined autoclave reactor and reacted at 120℃ for 48h. After the reaction was complete, the autoclave was cooled to room temperature, and the solid product was obtained by centrifugation at 9000rpm. The collected solid product was washed twice each with dimethylformamide and methanol to remove unreacted precursors, and then dried overnight in a hot air oven to obtain Fe-Ce-ZrMOFs. The Fe-Ce-ZrMOFs were calcined at 600℃ for 4h under an argon atmosphere at a heating rate of 11℃ / min to obtain Fe-Ce-ZrMOFs-C, i.e., Fe-Ce-Zr trimetallic MOFs-derived carbon material.
[0053] Example 6
[0054] The preparation method of the Fe-Ce-Zr trimetallic MOFs-derived carbon material in this embodiment is as follows:
[0055] 1g of ferric nitrate, 1.2g of cerium nitrate, 1.5g of zirconium nitrate, 0.8g of phthalic acid, and 0.185g of F127 were weighed and added to 30ml of dimethylformamide. The mixture was stirred continuously until a clear solution was observed, yielding the precursor solution. The precursor solution was transferred to a Teflon-lined autoclave reactor and reacted at 150℃ for 30h. After the reaction was complete, the autoclave was cooled to room temperature, and the solid product was obtained by centrifugation at 9500rpm. The collected solid product was washed four times each with dimethylformamide and methanol to remove unreacted precursors, and then dried overnight in a hot air oven to obtain Fe-Ce-ZrMOFs. The Fe-Ce-ZrMOFs were calcined at 800℃ for 2h under an argon atmosphere at a heating rate of 12℃ / min to obtain Fe-Ce-ZrMOFs-C, i.e., Fe-Ce-Zr trimetallic MOFs-derived carbon material.
[0056] The prepared Fe-Ce-ZrMOFs-C was spread on a quartz substrate and placed in a low-temperature plasma device. The vacuum was evacuated to 50 Pa, and plasma was treated for 15 min under air atmosphere, power of 40 W, and room temperature conditions. This is the Fe-Ce-Zr trimetallic MOFs-derived carbon material of this embodiment.
[0057] Example 7
[0058] The preparation method of the Fe-Ce-Zr trimetallic MOFs-derived carbon material in this embodiment is as follows:
[0059] 1g of ferric nitrate, 1g of cerium nitrate, 1.2g of zirconium nitrate, 0.8g of phthalic acid, and 0.32g of P123 were weighed and added to 30ml of dimethylformamide. The mixture was stirred continuously until a clear solution was observed, yielding the precursor solution. The precursor solution was transferred to a Teflon-lined autoclave reactor and reacted at 145℃ for 40h. After the reaction was complete, the autoclave was cooled to room temperature, and the solid product was obtained by centrifugation at 10000rpm. The collected solid product was washed three times each with dimethylformamide and methanol to remove unreacted precursors, and then dried overnight in a hot air oven to obtain Fe-Ce-ZrMOFs. The Fe-Ce-ZrMOFs were calcined at 750℃ for 3h under an argon atmosphere at a heating rate of 10℃ / min to obtain Fe-Ce-ZrMOFs-C, i.e., Fe-Ce-Zr trimetallic MOFs-derived carbon material.
[0060] The prepared Fe-Ce-ZrMOFs-C was spread evenly on a quartz substrate and placed in a low-temperature plasma device. The vacuum was evacuated to 80 Pa, and plasma treatment was performed for 10 min under air atmosphere, 50 W power, and room temperature. 0.1 g of the plasma-treated Fe-Ce-ZrMOFs-C was weighed and dispersed in 10 mL of anhydrous ethanol. The suspension was ultrasonically treated to obtain a uniform suspension. Then, 1 mL of ethylenediamine was added as an amino donor, and the mixture was stirred in a 60 °C constant temperature water bath for 4 h. The solid sample was collected by centrifugation, washed with anhydrous ethanol, and then washed with deionized water until the filtrate was neutral. After drying, amino-functionalized Fe-Ce-ZrMOFs-C was obtained, which is the Fe-Ce-Zr trimetallic MOFs-derived carbon material of this embodiment.
[0061] Example 8
[0062] The preparation method of the Fe-Ce-Zr trimetallic MOFs-derived carbon material in this embodiment is as follows:
[0063] 1g of ferric nitrate, 1g of cerium nitrate, 1.2g of zirconium nitrate, 0.8g of phthalic acid, and 0.32g of P123 were weighed and added to 30ml of dimethylformamide. The mixture was stirred continuously until a clear solution was observed, yielding the precursor solution. The precursor solution was transferred to a Teflon-lined autoclave reactor and reacted at 145℃ for 40h. After the reaction was complete, the autoclave was cooled to room temperature, and the solid product was obtained by centrifugation at 10000rpm. The collected solid product was washed three times each with dimethylformamide and methanol to remove unreacted precursors, and then dried overnight in a hot air oven to obtain Fe-Ce-ZrMOFs. The Fe-Ce-ZrMOFs were calcined at 750℃ for 3h under an argon atmosphere at a heating rate of 10℃ / min to obtain Fe-Ce-ZrMOFs-C, i.e., Fe-Ce-Zr trimetallic MOFs-derived carbon material.
[0064] The prepared Fe-Ce-ZrMOFs-C was spread evenly on a quartz substrate and placed in a low-temperature plasma device. The vacuum was evacuated to 100 Pa, and plasma treatment was performed for 15 min under air atmosphere, 60 W power, and room temperature. 0.1 g of the plasma-treated Fe-Ce-ZrMOFs-C was weighed and dispersed in 10 mL of anhydrous ethanol. The suspension was ultrasonically treated to obtain a uniform suspension. Then, 1 mL of ethylenediamine was added as an amino donor, and the mixture was stirred in a 50 °C constant temperature water bath for 5 h. The solid sample was collected by centrifugation, washed with anhydrous ethanol, and then washed with deionized water until the filtrate was neutral. After drying, amino-functionalized Fe-Ce-ZrMOFs-C was obtained, which is the Fe-Ce-Zr trimetallic MOFs-derived carbon material of this embodiment.
[0065] Example 9
[0066] The preparation method of the Fe-Ce-Zr trimetallic MOFs-derived carbon material in this embodiment is as follows:
[0067] 1g of ferric nitrate, 1g of cerium nitrate, 1.2g of zirconium nitrate, and 0.8g of phthalic acid were weighed and added to 30ml of dimethylformamide. The mixture was stirred continuously until a clear solution was observed, yielding the precursor solution. The precursor solution was transferred to a Teflon-lined autoclave reactor and reacted at 145℃ for 40h. After the reaction was complete, the autoclave was cooled to room temperature, and the solid product was obtained by centrifugation at 10000rpm. The collected solid product was washed three times each with dimethylformamide and methanol to remove unreacted precursors, and then dried overnight in a hot air oven to obtain Fe-Ce-ZrMOFs. The Fe-Ce-ZrMOFs were calcined at 750℃ for 3h under an argon atmosphere at a heating rate of 10℃ / min to obtain Fe-Ce-ZrMOFs-C, i.e., Fe-Ce-Zr trimetallic MOFs-derived carbon material.
[0068] The prepared Fe-Ce-ZrMOFs-C was spread on a quartz substrate and placed in a low-temperature plasma device. The vacuum was evacuated to 80 Pa, and plasma was treated for 10 min under air atmosphere, power of 50 W, and room temperature conditions. This is the Fe-Ce-Zr trimetallic MOFs-derived carbon material of this embodiment.
[0069] Example 10
[0070] The preparation method of the Fe-Ce-Zr trimetallic MOFs-derived carbon material in this embodiment is as follows:
[0071] 1g of ferric nitrate, 1g of cerium nitrate, 1.2g of zirconium nitrate, and 0.8g of phthalic acid were weighed and added to 30ml of dimethylformamide. The mixture was stirred continuously until a clear solution was observed, yielding the precursor solution. The precursor solution was transferred to a Teflon-lined autoclave reactor and reacted at 145℃ for 40h. After the reaction was complete, the autoclave was cooled to room temperature, and the solid product was obtained by centrifugation at 10000rpm. The collected solid product was washed three times each with dimethylformamide and methanol to remove unreacted precursors, and then dried overnight in a hot air oven to obtain Fe-Ce-ZrMOFs. The Fe-Ce-ZrMOFs were calcined at 750℃ for 3h under an argon atmosphere at a heating rate of 10℃ / min to obtain Fe-Ce-ZrMOFs-C, i.e., Fe-Ce-Zr trimetallic MOFs-derived carbon material.
[0072] 0.1 g of Fe-Ce-ZrMOFs-C was weighed and dispersed in 10 mL of anhydrous ethanol. The mixture was ultrasonically treated to obtain a uniform suspension. Then, 1 mL of ethylenediamine was added as an amino donor. The mixture was stirred in a 60 °C constant temperature water bath for 4 h. The solid sample was collected by centrifugation, washed with anhydrous ethanol, and then washed with deionized water until the filtrate was neutral. After drying, amino-functionalized Fe-Ce-ZrMOFs-C was obtained, which is the Fe-Ce-Zr trimetallic MOFs-derived carbon material of this embodiment.
[0073] Example 11
[0074] The preparation method of the Fe-Ce-Zr trimetallic MOFs-derived carbon material in this embodiment is as follows:
[0075] 1g of ferric nitrate, 1g of cerium nitrate, 1.2g of zirconium nitrate, 0.8g of phthalic acid, and 0.32g of P123 were weighed and added to 30ml of dimethylformamide. The mixture was stirred continuously until a clear solution was observed, yielding the precursor solution. The precursor solution was transferred to a Teflon-lined autoclave reactor and reacted at 145℃ for 40h. After the reaction was complete, the autoclave was cooled to room temperature, and the solid product was obtained by centrifugation at 10000rpm. The collected solid product was washed three times each with dimethylformamide and methanol to remove unreacted precursors, and then dried overnight in a hot air oven to obtain Fe-Ce-ZrMOFs. The Fe-Ce-ZrMOFs were calcined at 750℃ for 3h under an argon atmosphere at a heating rate of 10℃ / min to obtain Fe-Ce-ZrMOFs-C, i.e., Fe-Ce-Zr trimetallic MOFs-derived carbon material.
[0076] 0.1 g of Fe-Ce-ZrMOFs-C was weighed and dispersed in 10 mL of anhydrous ethanol. The mixture was ultrasonically treated to obtain a uniform suspension. Then, 1 mL of ethylenediamine was added as an amino donor. The mixture was stirred in a 65°C constant temperature water bath for 3 h. The solid sample was collected by centrifugation, washed with anhydrous ethanol, and then washed with deionized water until the filtrate was neutral. After drying, amino-functionalized Fe-Ce-ZrMOFs-C was obtained, which is the Fe-Ce-Zr trimetallic MOFs-derived carbon material of this embodiment.
[0077] Comparative Example 1
[0078] The preparation method of the Fe-Ce-Zr trimetallic MOF material in this comparative example is as follows:
[0079] 1g of ferric nitrate, 1g of cerium nitrate, 1.2g of zirconium nitrate, and 0.5g of phthalic acid were weighed and added to 30ml of dimethylformamide. The mixture was stirred continuously until a clear solution was observed, yielding the precursor solution. The precursor solution was transferred to a Teflon-lined autoclave reactor and reacted at 145℃ for 40h. After the reaction was completed, the autoclave was allowed to cool to room temperature, and then the solid product was obtained by centrifugation at 10000rpm. The collected solid product was washed three times each with dimethylformamide and methanol to remove unreacted precursors, and then dried overnight in a hot air oven to obtain Fe-Ce-ZrMOFs material.
[0080] Using the materials prepared in Examples 1-11 and Comparative Example 1 as samples, the adsorption performance of benzene, toluene and acetone was tested. Specifically, the adsorption of benzene, toluene and acetone gases was tested on the materials using a UTEST static adsorption device. The test flow rate (10 L / min), test resistance (<80 Pa), and test concentration (5 ppm) were controlled. The test results are shown in Table 1.
[0081] Table 1. Adsorption test results of benzene, toluene, and acetone gases
[0082]
[0083] The data in Table 1 show that the polymetallic MOF-derived carbon materials prepared by increasing the ratio of metal ions to ligands in Examples 1-2 showed a slight improvement in the initial efficiency and mass adsorption ratio of VOCs, but the effect was not significant. The polymetallic MOF-derived carbon materials obtained by increasing the calcination temperature in Examples 1-4 showed an approximately 20% increase in the initial efficiency for VOCs and a significant increase in the mass adsorption ratio of approximately 3.4%. The addition of pore-expanding agents, plasma treatment, and amination can all improve the initial efficiency or mass adsorption ratio of benzene, toluene, and acetone gases to some extent.
[0084] Using Fe-Ce-ZrMOFs-C prepared in Example 1 and Fe-Ce-ZrMOFs prepared in Comparative Example 1 as samples, nitrogen adsorption-desorption tests were performed, and the resulting nitrogen adsorption-desorption curves are shown in the figure. Figure 1 As shown. Figure 1 Data show that both Fe-Ce-ZrMOFs and Fe-Ce-ZrMOFs-C materials are filled with micropores, mesopores, and macropores. However, the specific surface area of the calcined Fe-Ce-ZrMOFs material is significantly increased, reaching as high as 4000 m². 2 The / g indicates that the Fe-Ce-Zr MOFs-C material has more active sites, which significantly improves the mass adsorption ratio of VOCs.
[0085] TGA images of Fe-Ce-ZrMOFs-C prepared in Example 1 and Fe-Ce-ZrMOFs prepared in Comparative Example 1 are shown below. Figure 2 As shown. From Figure 2 It can be seen that the thermal stability of Fe-Ce-Zr MOFs material is at 650℃, while the thermal stability of carbonized Fe-Ce-ZrMOFs-C material is at 750℃. This indicates that Fe-Ce-ZrMOFs-C material has better thermal stability and is less susceptible to the effects of high-temperature environments that could lead to pore collapse and thus reduce adsorption performance.
[0086] In summary, the Fe-Ce-Zr trimetallic MOFs-derived carbon material prepared by this invention combines the high specific surface area and hierarchical porous structure of MOFs, the strong adsorption effect of trimetallic sites, and the excellent hydrophobic stability and structural integrity of the carbon framework. It exhibits significant advantages for volatile organic compounds (VOCs), including large adsorption capacity, good selectivity, excellent moisture resistance, and strong cycling stability. Therefore, the Fe-Ce-Zr trimetallic MOFs-derived carbon material of this invention can be used in the preparation of adsorbents for VOCs, especially for benzene, toluene, and acetone.
[0087] The foregoing description includes examples from this specification. Of course, for the purposes of describing this specification, it is impossible to describe every conceivable combination of components or methods; however, those skilled in the art will understand that many other combinations and arrangements are possible. Therefore, this specification is intended to cover all such changes, modifications, and variations that fall within the spirit and scope of the appended claims. Furthermore, with regard to the use of the term "comprising" in the detailed description or claims, the term is intended to be inclusive in a manner similar to the term "including," as interpreted when "comprising" is used as a transitional word in the claims.
[0088] The above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit it. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all such modifications or substitutions should be covered within the scope of the claims of the present invention.
Claims
1. A method for preparing Fe-Ce-Zr trimetallic MOFs-derived carbon materials, characterized in that, Includes the following steps: Ferric nitrate, cerium nitrate, zirconium nitrate, and phthalic acid were added to dimethylformamide, stirred and dissolved, and then reacted at 120-150℃ for 30-48h. After cooling to room temperature, the reaction solution was centrifuged to obtain a solid product, which was washed, dried, and Fe-Ce-Zr-MOFs were prepared. Fe-Ce-Zr-MOFs were placed in an argon atmosphere and calcined at 600-800℃ for 2-4 hours at a heating rate of 10-12℃ / min to obtain Fe-Ce-Zr-MOFs-C.
2. The method for preparing Fe-Ce-Zr trimetallic MOFs-derived carbon materials according to claim 1, wherein, The mass ratio of ferric nitrate, cerium nitrate, zirconium nitrate, and phthalic acid is 1:(0.8-1.2):(0.9-1.5):(0.5-0.8).
3. The method for preparing Fe-Ce-Zr trimetallic MOFs-derived carbon materials according to claim 2, wherein, The preparation method of the Fe-Ce-Zr-MOFs is as follows: Ferric nitrate, cerium nitrate, zirconium nitrate, phthalic acid, and a pore-expanding agent were added to dimethylformamide and stirred to dissolve. The mixture was then placed at 120–150 °C for 30–48 h and cooled to room temperature. The resulting reaction solution was centrifuged to obtain a solid product, which was then washed, dried, and Fe-Ce-Zr-MOFs were prepared.
4. The method for preparing Fe-Ce-Zr trimetallic MOFs-derived carbon materials according to claim 3, wherein, The amount of the pore-expanding agent is 5% to 20% of the total mass of ferric nitrate, cerium nitrate, and zirconium nitrate, and the pore-expanding agent is selected from one of P123, F127, and CTBA.
5. The method for preparing Fe-Ce-Zr trimetallic MOFs-derived carbon materials according to claim 1, wherein, The washing process involves washing the solid product 2 to 4 times each with dimethylformamide and methanol.
6. The method for preparing Fe-Ce-Zr trimetallic MOFs-derived carbon materials according to claim 1 or 4, wherein, The prepared Fe-Ce-Zr-MOFs-C was spread on a quartz substrate and placed in a low-temperature plasma device. The vacuum was evacuated to 50–100 Pa, and plasma was treated for 5–15 min in an air atmosphere at a power of 40–60 W and at room temperature.
7. The method for preparing Fe-Ce-Zr trimetallic MOFs-derived carbon materials according to claim 6, wherein, The plasma-treated Fe-Ce-Zr-MOFs-C was dispersed in anhydrous ethanol and ultrasonically treated to obtain a uniform suspension. Then, ethylenediamine was added as an amino donor, and the mixture was stirred in a constant temperature water bath at 50-65℃ for 3-5 hours. The solid sample was collected by centrifugation, washed with anhydrous ethanol, and then washed with deionized water until the filtrate was neutral. After drying, amino-functionalized Fe-Ce-ZrMOFs-C was obtained.
8. The method for preparing Fe-Ce-Zr trimetallic MOFs-derived carbon materials according to claim 1 or 4, wherein, Fe-Ce-Zr-MOFs-C was weighed and dispersed in anhydrous ethanol, and ultrasonically treated to obtain a uniform suspension. Then, ethylenediamine was added as an amino donor, and the mixture was stirred in a constant temperature water bath at 50-65℃ for 3-5 hours. The solid sample was collected by centrifugation, washed with anhydrous ethanol, and then washed with deionized water until the filtrate was neutral. After drying, amino-functionalized Fe-Ce-ZrMOFs-C was obtained.
9. Fe-Ce-Zr trimetallic MOFs-derived carbon materials, characterized in that, It is prepared by the preparation method described in any one of claims 1-8.
10. The application of the Fe-Ce-Zr trimetallic MOFs-derived carbon material according to claim 9 in the preparation of volatile organic compound adsorbent materials.