FeOCl Catalytic Material Intercalated with Organic Molecules and Preparation Method Thereof

Abstract

The present invention discloses an organic molecule intercalated FeOCl catalytic material, which is specifically implemented according to the following steps: grinding and mixing a small amount of small molecule alcohol with FeCl<subgt;3< / subgt>·6H<subgt;2< / subgt>O; calcining the mixture, washing and drying it, and finally obtaining alcohol molecule intercalated FeOCl. The present invention discloses a preparation method of an organic molecule intercalated FeOCl catalytic material. Compared with the traditional preparation technology, the preparation method of the present invention is simple and efficient, requires less organic solvents, and is easy to achieve large-scale preparation; compared with the non-intercalated FeOCl, the prepared organic molecule intercalated FeOCl exhibits more excellent catalytic performance in the reaction of activating hydrogen peroxide to degrade organic matters in water.

Description

Technical Field

[0001] The present invention belongs to the technical field of preparation methods of catalytic materials, and particularly relates to an FeOCl catalytic material intercalated with organic molecules. The present invention also relates to a preparation method of the FeOCl catalytic material intercalated with organic molecules. Background Art

[0002] Iron oxychloride (FeOCl) is an inorganic material with a two-dimensional layered structure, and the layers are constrained by the van der Waals forces of Cl atoms. A large number of studies have proven that FeOCl is an excellent heterogeneous Fenton reaction catalytic material, which can effectively activate H2O2 to degrade organic pollutants in water and maintain good activity under neutral conditions. On the other hand, the layer spacing of the FeOCl material can be effectively enlarged by embedding guest molecules (or ions) between the FeOCl layers. Compared with the original FeOCl, some FeOCl intercalated with organic molecules exhibit more excellent catalytic performance. For example, under different pH conditions, FeOCl intercalated with polyaniline has a higher degradation efficiency than the original FeOCl in the Fenton reaction for the degradation of 2-methylphenol (pH-Dependent Structure-Activity Relationship of Polyaniline-IntercalatedFeOCl for Heterogeneous Fenton Reactions, ACS Omega, 2019, 4: 21945.).

[0003] Currently, the method for preparing the FeOCl material intercalated with organic guest molecules is mainly a two-step method, that is: first, the original FeOCl is prepared by heating FeCl3 (FeCl3·6H2O can also be used) or a mixture of FeCl3 and Fe2O3; then the original FeOCl is converted into an FeOCl intercalation compound under certain conditions. For example, Dai et al. dispersed FeOCl in an acetone solution of 8-hydroxyquinoline and reacted at 80°C for 15 days to prepare an FeOCl material intercalated with 8-hydroxyquinoline (Synthesis and Properties of the Intercalation Compound FeOCl(HQ)0.78, Journal of Nanjing University of Aeronautics and Astronautics, 2005, 37: 663.); again, under the condition of 110°C, FeOCl was soaked in methanol for 6 days to obtain an FeOCl material substituted by methoxy intercalation. However, these methods require the use of a large amount of organic solvents, have a long reaction time, and the product separation process is cumbersome, which limits their practical applications. Summary of the Invention

[0004] The first object of the present invention is to provide an FeOCl catalytic material intercalated with organic molecules.

[0005] The second object of the present invention is to provide a preparation method of an organic molecule intercalated FeOCl catalytic material, which solves the problems of the existing method for preparing an organic molecule intercalated FeOCl material, such as the need to use a large amount of organic solvents, long reaction time, and cumbersome product separation process.

[0006] The first technical solution adopted by the present invention is as follows: for the organic molecule intercalated FeOCl catalytic material, a small amount of small molecule alcohol is ground and mixed with FeCl3·6H2O; the mixture is calcined, washed, and dried, and finally an alcohol molecule intercalated FeOCl is obtained.

[0007] The second technical solution adopted by the present invention is as follows: a preparation method of an organic molecule intercalated FeOCl catalytic material, which is specifically implemented according to the following steps:

[0008] Step 1: Grind and mix FeCl3·6H2O and alcohol;

[0009] Step 2: Place the mixture in Step 1 in a covered crucible, react at 200°C to 300°C for 1h to 4h, and the reaction heating rate is 5 to 12°C / min;

[0010] Step 3: Wash the product in Step 2 with a cleaning agent and vacuum dry it at 40°C to 80°C for 6h to 24h to obtain an organic molecule intercalated FeOCl catalytic material.

[0011] The characteristics of the second technical solution adopted by the present invention are further as follows:

[0012] The alcohol in Step 1 is any one of ethanol, propanol, or isopropanol.

[0013] The mass ratio of FeCl3·6H2O to alcohol in Step 1 is 1:0.1 to 0.3.

[0014] The mass ratio of FeCl3·6H2O to alcohol in Step 1 is 1:0.24.

[0015] The reaction temperature in Step 2 is preferably 230°C to 280°C.

[0016] The reaction heating rate in Step 2 is preferably 10°C / min, and the reaction time is preferably 2h.

[0017] The cleaning agent in Step 3 is one or several of acetone, ethanol, isopropanol, and water; the drying temperature is preferably 60°C, and the drying time is preferably 12h.

[0018] The beneficial effects of the present invention are as follows:

[0019] The present invention provides an organic molecule intercalated FeOCl catalytic material and a preparation method thereof. The organic molecule is directly mixed with an iron salt, and through a partial thermal decomposition method, the intercalation reaction is completed while forming FeOCl, avoiding the extensive use of organic solvents in the intercalation reaction. Compared with the existing two-step method, it saves more time and cost, is more simple and efficient in operation, and is conducive to large-scale preparation.

[0020] The preparation method of the present invention uses common small molecule alcohols, which have relatively low toxicity and danger.

[0021] The organic molecule intercalated FeOCl catalytic material prepared by the present invention has excellent catalytic performance for the Fenton reaction, showing a significant improvement compared with the non-intercalated FeOCl material. Brief Description of the Drawings

[0022] Figure 1 It is the XRD pattern of the products of Comparative Example 1, Example 1 and Example 2 of the present invention;

[0023] Figure 2 It is the XRD pattern of the products of Comparative Examples 2, 3 and 4 of the present invention;

[0024] Figure 3 It is the scanning electron microscope (SEM) image of the non-intercalated FeOCl prepared in Comparative Example 1 of the present invention;

[0025] Figure 4 It is the SEM image of the ethanol intercalated FeOCl prepared in Example 1 of the present invention;

[0026] Figure 5 It is the catalytic performance graph of the degradation of tetracycline hydrochloride (TC) by Comparative Example 1, Example 1 and Example 2 of the present invention. Detailed Description of the Embodiments

[0027] The present invention will be described in detail below with reference to the drawings and embodiments.

[0028] The present invention provides an organic molecule intercalated FeOCl catalytic material. A small amount of small molecule alcohol is ground and mixed with FeCl3·6H2O; the mixture is calcined, washed and dried, and finally an alcohol molecule intercalated FeOCl is obtained.

[0029] The preparation method of the organic molecule intercalated FeOCl catalytic material provided by the present invention is specifically implemented according to the following steps:

[0030] Step 1: Grind and mix FeCl3·6H2O and alcohol. The alcohol is any one of ethanol, propanol or isopropanol. The mass ratio of FeCl3·6H2O to alcohol is 1:0.1 - 1:0.3, preferably 1:0.24;

[0031] Step 2: Place the mixture obtained in Step 1 in a crucible with a lid, react at 200°C - 300°C for 1h - 4h, the heating rate of the reaction is 5 - 12°C / min, the reaction temperature is preferably 230°C - 280°C, more preferably 250°C, the heating rate of the reaction is preferably 10°C / min, and the reaction time is preferably 2h;

[0032] Step 3: Wash the product obtained in Step 2 with a cleaning agent and vacuum dry it at 40°C - 80°C for 6h - 24h to obtain an organic molecule intercalated FeOCl catalytic material. The cleaning agent is one or more of acetone, ethanol, isopropanol and water; the drying temperature is preferably 60°C and the drying time is preferably 12h.

[0033] Example 1

[0034] Ethanol is selected in Step 1, and the specific operation steps are as follows:

[0035] After grinding and mixing 1g of FeCl3·6H2O and 0.24g of ethanol evenly, place it in a crucible with a lid, and heat it to 250°C at a heating rate of 10°C / min in an air furnace and keep it warm for 2h. Wash the obtained product with acetone and ethanol, and place the washed product in a vacuum drying oven at 60°C for drying for 12h to obtain an ethanol intercalated FeOCl catalytic material.

[0036] Example 2

[0037] n - Propanol is selected in Step 1, and the specific operation steps are as follows:

[0038] After grinding and mixing 1g of FeCl3·6H2O and 0.24g of n - propanol evenly, place it in a crucible with a lid, and heat it to 250°C at a heating rate of 10°C / min in an air furnace and keep it warm for 2h. Wash the obtained product with acetone and ethanol, and place the washed product in a vacuum drying oven at 60°C for drying for 12h to obtain an n - propanol intercalated FeOCl catalytic material.

[0039] Example 3

[0040] Isopropanol is selected in Step 1, and the specific operation steps are as follows:

[0041] After grinding and mixing 1g of FeCl3·6H2O and 0.1g of n - propanol evenly, place it in a crucible with a lid, and heat it to 200°C at a heating rate of 5°C / min in an air furnace and keep it warm for 1h. Wash the obtained product with acetone and isopropanol, and place the washed product in a vacuum drying oven at 40°C for drying for 6h to obtain an n - propanol intercalated FeOCl catalytic material.

[0042] Example 4

[0043] Isopropanol is selected in Step 1, and the specific operation steps are as follows:

[0044] After grinding and mixing 1 g of FeCl3·6H2O and 0.3 g of n-propanol evenly, place them in a crucible with a lid, and heat them in an air furnace at a heating rate of 12 °C / min to 300 °C and hold for 4 h. Wash the obtained product with acetone and water, and place the washed product in a vacuum drying oven at 80 °C for 24 h to obtain the FeOCl catalytic material intercalated with n-propanol.

[0045] Example 5

[0046] Isopropanol is selected in Step 1, and the specific operation steps are as follows:

[0047] After grinding and mixing 1 g of FeCl3·6H2O and 0.3 g of n-propanol evenly, place them in a crucible with a lid, and heat them in an air furnace at a heating rate of 12 °C / min to 230 °C and hold for 4 h. Wash the obtained product with acetone, ethanol, isopropanol and water, and place the washed product in a vacuum drying oven at 80 °C for 24 h to obtain the FeOCl catalytic material intercalated with n-propanol.

[0048] Example 6

[0049] Isopropanol is selected in Step 1, and the specific operation steps are as follows:

[0050] After grinding and mixing 1 g of FeCl3·6H2O and 0.1 g of n-propanol evenly, place them in a crucible with a lid, and heat them in an air furnace at a heating rate of 5 °C / min to 280 °C and hold for 1 h. Wash the obtained product with ethanol, isopropanol and water, and place the washed product in a vacuum drying oven at 40 °C for 6 h to obtain the FeOCl catalytic material intercalated with n-propanol.

[0051] Comparative Example 1

[0052] No small molecule alcohol is added in Step 1, and the specific operation steps are as follows:

[0053] After grinding 1 g of FeCl3·6H2O evenly, place it in a crucible with a lid, and heat it in an air furnace at a heating rate of 10 °C / min to 250 °C and hold for 2 h. Wash the obtained product with acetone and ethanol, and place the washed product in a vacuum drying oven at 60 °C for 12 h to obtain the un-intercalated FeOCl catalytic material.

[0054] Comparative Example 2

[0055] Methanol is selected in Step 1, and the specific operation steps are as follows:

[0056] After grinding and mixing 1 g of FeCl3·6H2O and 0.24 g of methanol evenly, place them in a crucible with a lid, and heat them in an air furnace at a heating rate of 10 °C / min to 250 °C and keep warm for 2 h. Wash the obtained product with acetone and ethanol, and place the washed product in a vacuum drying oven at 60 °C for drying for 12 h. The obtained product is un-intercalated FeOCl, that is, using methanol cannot achieve the one-step preparation of an organic-intercalated FeOCl catalytic material.

[0057] Comparative Example 3

[0058] In Step 1, n-butanol is selected, and the specific operation steps are as follows:

[0059] After grinding and mixing 1 g of FeCl3·6H2O and 0.24 g of n-butanol evenly, place them in a crucible with a lid, and heat them in an air furnace at a heating rate of 10 °C / min to 250 °C and keep warm for 2 h. Wash the obtained product with acetone and ethanol, and place the washed product in a vacuum drying oven at 60 °C for drying for 12 h. The obtained product is a mixture of FeOCl and Fe2O3.

[0060] Comparative Example 3

[0061] In Step 1, ethylene glycol is selected, and the specific operation steps are as follows:

[0062] After grinding and mixing 1 g of FeCl3·6H2O and 0.24 g of ethylene glycol evenly, place them in a crucible with a lid, and heat them in an air furnace at a heating rate of 10 °C / min to 250 °C and keep warm for 2 h. Wash the obtained product with acetone and ethanol, and place the washed product in a vacuum drying oven at 60 °C for drying for 12 h. The final obtained product is Fe2O3.

[0063] Figure 1 XRD patterns of the products of Comparative Example 1, Example 1 and Example 2.

[0064] In the XRD of the product of Comparative Example 1, the diffraction peak of FeOCl can be observed, and the interlayer spacing of the (010) crystal plane (2θ = 11.2°) is 0.79 nm. In Examples 1 and 2, the diffraction peaks of the (010) characteristic crystal plane shift to a small angle, and the interlayer spacings are expanded to 1.27 nm and 1.17 nm respectively, indicating that ethanol-intercalated FeOCl and n-propanol-intercalated FeOCl are successfully prepared.

[0065] Figure 2 XRD patterns of the products of Comparative Example 2, 3 and 4.

[0066] From Figure 2It can be observed that when the added alcohols are methanol, n-butanol, and ethylene glycol, the XRD of the products corresponds to the mixture of un-intercalated FeOCl, Fe2O3, and FeOCl and Fe2O3 respectively, indicating that none of the above three alcohols can produce the corresponding intercalated FeOCl materials.

[0067] Figure 3 It is the scanning electron microscope (SEM) image of the un-intercalated FeOCl prepared in Comparative Example 1.

[0068] Figure 4 It is the SEM image of the ethanol-intercalated FeOCl prepared in Example 1. Compared with the un-intercalated FeOCl ( Figure 3 ), the ethanol-intercalated FeOCl has a smaller size.

[0069] Figure 5 It is the catalytic performance graph of degrading tetracycline hydrochloride (TC) in Comparative Example 1, Example 1, and Example 2.

[0070] The conditions for the degradation experiment were: [TC]=60mg / L, [H2O2]=1mM, [catalyst]=0.1g / L, [pH]=4.2. The specific experimental steps were as follows: Add 100 mL of TC solution with a concentration of 60 mg / L into a quartz tube. At room temperature, add 10 mg of the catalyst into the quartz tube containing TC. After a 20-min dark reaction, add H2O2 to initiate the experiment. At a predetermined time interval, draw 2 mL of the reaction solution from the quartz tube, filter it with a 0.22-μm filter head, and then analyze it using an ultraviolet-visible spectrophotometer.

[0071] From Figure 5 it can be seen that the un-intercalated FeOCl prepared in Comparative Example 1 and the organic-intercalated FeOCl catalytic materials prepared in Examples 1 and 2 have more excellent reaction performance.

[0072] For the organic molecule-intercalated FeOCl catalytic material, compared with the traditional preparation technology, this method is simple and efficient, requires less organic solvent, and is easy to achieve large-scale preparation; compared with the un-intercalated FeOCl, the prepared organic molecule-intercalated FeOCl exhibits more excellent catalytic performance in the reaction of activating hydrogen peroxide to degrade organic substances in water.

Claims

1. A method for preparing FeOCl catalytic materials with organic molecule intercalation, characterized in that: Please follow the steps below to implement: Step 1, grinding and mixing FeCl3·6H2O and alcohol; The alcohol is any one of ethanol, n-propanol or isopropanol; The mass ratio of FeCl3·6H2O to alcohol is 1:0.1~0.3; Step 2: Place the mixture in step 1 in a covered crucible and react at 200°C to 300°C for 1 h to 4 h at a heating rate of 5 to 12°C / min; Step 3: The product of step 2 is cleaned with a cleaning agent and vacuum-dried at 40° C. to 80° C. for 6 h to 24 h to obtain an organic molecule intercalated FeOCl catalytic material.

2. The method for preparing the organic molecule intercalated FeOCl catalytic material according to claim 1, characterized in that: In step 1, the mass ratio of FeCl3·6H2O to alcohol is 1:0.

24.

3. The method for preparing the organic molecule intercalated FeOCl catalytic material according to claim 1, characterized in that: The reaction temperature in step 2 is 230°C to 280°C.

4. The method for preparing the organic molecule intercalated FeOCl catalytic material according to claim 1, characterized in that: The reaction temperature rise rate of step 2 is 10°C / min and the reaction time is 2 h.

5. The method for preparing the organic molecule intercalated FeOCl catalytic material according to claim 1, characterized in that: The cleaning agent in step 3 is one or more of acetone, ethanol, isopropanol and water; the drying temperature is 60° C. and the drying time is 12 hours.

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