Ni-coated NiS2-coated MoSx / NF composite catalyst and preparation method and application thereof

Abstract

The invention belongs to the technical field of environmental catalytic materials and pollutant control, and particularly relates to a Ni-coated NiS < 2 >-coated MoS < x > / NF composite catalyst and a preparation method and application thereof. According to the preparation method of the Ni-coated NiS2-coated MoSx / NF composite catalyst provided by the invention, the Ni-coated NiS2-coated MoSx / NF composite catalyst with a self-supported metal / crystalline / amorphous heterojunction is constructed by virtue of a collaborative strategy of directional self-assembly and internal Ni source and water dispersion, and meanwhile, the activation efficiency of peroxymonosulfate (PMS) can be remarkably improved by combining an Ni-Mo bimetal active center, so that the activation efficiency of the Ni-coated NiS2-coated MoSx / NF composite catalyst is improved. The problems that an existing catalyst is limited in active site and poor in structural stability are solved, the excellent capacity of activating PMS to remove antibiotics is shown, therefore, efficient degradation of antibiotic pollutants is achieved, and the catalyst has wide application prospects in antibiotic wastewater treatment.

Description

Technical Field

[0001] The present invention belongs to the technical field of environmental catalytic materials and pollutant control, and specifically relates to a Ni@NiS2@MoS x / NF composite catalyst and its preparation method and application. Background Art

[0002] As a class of highly biotoxic pollutants, antibiotics pose a serious threat to the aquatic environment and human health due to their difficulty in degradation and ecological accumulation. In recent years, advanced oxidation technologies (AOPs) have been widely used to remove antibiotics and other refractory organic pollutants due to their strong oxidative capacity. Among them, the activation technology based on peroxymonosulfate (PMS) has the ability to efficiently generate reactive oxygen species (such as •OH and SO4 •⁻ ) characteristics, has attracted widespread attention. The key to PMS-based activation technology lies in the selection of catalysts. However, the performance of existing PMS-activated catalysts is still limited by the following key issues: (1) Limited active sites: The active sites of traditional metal sulfide catalysts (such as MoS2) only exist on the edge sulfur atoms; (2) Existing technologies mostly rely on high-temperature calcination or toxic solvents, which can easily cause catalyst structure collapse, excessive generation of sulfur vacancies, and pollute the environment; (3) Insufficient synergistic effect: Monometallic catalysts lack electronic synergy between bimetallics, which limits the efficiency of PMS activation.

[0003] Currently, heterojunctions between amorphous and crystalline phases have attracted widespread attention in the catalysis field due to their unique properties arising from the interactions between their different components, particularly in terms of enhancing the exposure of active sites, promoting interfacial charge transfer, and generating synergistic catalytic effects. Theoretically, amorphous catalyst materials (short-range order and lack of periodicity) are believed to have higher intrinsic catalytic activity than most studied crystalline materials due to their chemical disorder, atomic-scale structural flexibility, and rich local configurations. The crystalline phase can compensate for the deficiencies of the amorphous phase in terms of electronic conduction efficiency and structural and chemical stability. Therefore, constructing a heterogeneous structure of amorphous and crystalline phases can integrate the advantages of each phase and achieve a balance between the stability of the catalyst in long-term operation and the activity of efficient activation of PMS.

[0004] Based on the above problems, the patent application with application number CN202210687773.6 discloses a catalyst composed of MoS2 nanosheets and copper oxide nanoflower arrays, but its structural design fails to fully expose the edge active sites of MoS2 and lacks a bimetallic synergistic enhancement mechanism. The patent application with application number 202510057305.4 discloses a MoS2 nanosheet with a nano-network structure. m (Mo3S 11)n / Ni Foam catalysts utilize bimetallic synergy to enhance catalytic activity. However, they are loaded onto a nickel foam substrate via drop casting (0.2–0.8 mL / min). Imprecise flow rate control can lead to uneven catalyst layer thickness, impacting mass transfer efficiency. Furthermore, an external nickel source is required to achieve bimetallic synergistic catalysis, increasing preparation costs.

[0005] Therefore, how to provide a simple and green method for preparing a composite catalyst to prepare a new bimetallic crystalline / amorphous structure catalyst with excellent ability to activate PMS to degrade antibiotic pollutants has become a technical problem to be solved by the present invention. Summary of the Invention

[0006] In order to overcome the deficiencies in the prior art, the present invention aims to provide a Ni@NiS2@MoS x / NF composite catalyst and its preparation method and application. The Ni@NiS2@MoS x The preparation method of the Ni@NiS2@MoS / NF composite catalyst is to construct a Ni@NiS2@MoS / NF composite catalyst with a metal / crystalline / amorphous heterojunction through a coordinated strategy of directed self-assembly, internal Ni source, and water dispersion. x / NF composite catalyst. The present invention uses the "self-supplied nickel source" characteristic of the acidified nickel foam substrate to achieve the acidification of nickel foam and MoS x In-situ chemical reaction of the solution to form self-supporting Ni@NiS2@MoS x The unique bimetallic crystalline / amorphous structure and strong Ni-S-Mo hybridization of the Ni / NF composite catalyst enable it to exhibit excellent PMS activation and degradation capabilities for antibiotic pollutants. This method also avoids the introduction of an external Ni source, achieving a Ni-Mo bimetallic active center and a metal / crystalline / amorphous heterojunction, significantly improving PMS activation efficiency and pollutant degradation performance. This provides a new approach to the design of efficient and stable catalytic materials for antibiotic wastewater treatment.

[0007] One of the purposes of the present invention is achieved by adopting the following technical solution:

[0008] A Ni@NiS2@MoS x The preparation method of the NF composite catalyst comprises the following steps:

[0009] (NH4)2Mo3S 13 nH2O was ultrasonically dispersed in methanol to obtain [Mo3S 13 ] 2- Cluster solution; the [Mo3S 13 ] 2-The cluster solution is heated to evaporate methanol to achieve cluster self-assembly, obtaining MoS x powder; MoS x The powder was dissolved in water and ultrasonically mixed to obtain MoS x dispersion;

[0010] Another nickel foam substrate is acidified to obtain an acidified nickel foam;

[0011] The acidified nickel foam is immersed in the MoSx dispersion for impregnation treatment, and then dried to obtain the Ni@NiS2@MoS x / NF composite catalyst.

[0012] As a preferred solution, (NH4)2Mo3S 13 The ratio of nH2O, methanol, and water is (1-2) mg: (1-2) mL: (1-2) mL. In this step, a small amount of methanol solvent results in a high cluster concentration and prevents the Tyndall effect. However, a large amount of methanol solvent prolongs the subsequent evaporation time, affecting the catalyst's self-assembly process.

[0013] As a preferred solution, the frequency of the ultrasonic dispersion is 40k~70kHz, and the ultrasonic dispersion time is 1~3h. In this step, the system will produce Tyndall effect through ultrasonic dispersion, and the obtained colloidal solution is dark red, indicating that (NH4)2Mo3S 13 nH2O forms [Mo3S 13 ] 2- Clusters. Ultrasonic waves can also create a cavitation effect through high-frequency vibration, allowing the solution to mix quickly and evenly. If stirring is used to disperse the solution, the dissolution time will be too long (approximately 12-24 hours), causing the clusters to oxidize and turn black.

[0014] As a preferred solution, the heating temperature is 60-70°C. In this step, the [Mo3S 13 ] 2- Clusters self-assemble to form disordered linked black powder MoS x If the heating temperature is lower than 60°C, the evaporation rate of the induced solvent is too slow, and the catalyst cannot be effectively self-assembled; if the heating temperature is higher than 70°C, the structure of the catalyst will be destroyed. Therefore, the heating temperature is selected to be 60~70°C.

[0015] As a preferred solution, the frequency of the ultrasonic mixing is 40k~70kHz, and the ultrasonic mixing time is 3~10min. The ultrasonic mixing in this step can promote the penetration of water molecules into the gaps between clusters, generate hydrogen bonds with sulfur atoms, weaken the van der Waals force between clusters and induce the rearrangement of Mo-S bonds, forming MoS with interconnected pores. x network.

[0016] As a preferred embodiment, the nickel foam substrate is pre-degreased before acidification; the dimensions of the nickel foam substrate range from 1 cm x 1 cm to 10 cm x 10 cm; the acidification treatment comprises ultrasonically treating the nickel foam substrate in a hydrochloric acid solution; the pH of the hydrochloric acid solution is 1 to 3. Further preferably, the ultrasonic frequency of the hydrochloric acid treatment is 60 to 80 kHz, and the ultrasonication time is 1 to 3 hours. This acidification step yields an activated nickel foam support containing active nickel species; this activated nickel foam support not only serves as a support for subsequent reactions but also serves as a nickel source for the in-situ reaction that generates the Ni@NiS2 component in the product.

[0017] As a preferred embodiment, the immersion treatment time is 1.5 to 3 hours. By setting the long immersion treatment time range, the acidified nickel foam and MoS x The solution undergoes in-situ chemical reaction to prepare self-supporting Ni@NiS2@MoS x / NF composite catalyst. At the same time, the catalyst prepared by the impregnation and drying method is more evenly dispersed and more firmly bonded than the catalyst prepared by the drop casting and drying method.

[0018] As a preferred embodiment, the drying temperature is 60-80° C. and the drying time is 1-3 hours.

[0019] The three-dimensional porous network structure of the acidified nickel foam of the present invention provides abundant loading sites, which is beneficial to the MoS x The uniform dispersion and stable combination of nanomaterials and in-situ generated Ni@NiS2 components effectively increase the exposure of active sites, thereby improving the efficiency of the catalytic reaction; on the other hand, the nickel element contained in it also serves as a nickel source for participating in the reaction to generate the Ni@NiS2 component in the final product. Based on this, the present invention successfully prepared an integrated self-supporting Ni@NiS2 / MoS with high catalytic performance through a coordinated strategy of directed self-assembly, internal Ni source, and water dispersion. x / NF composite catalyst, the Ni@NiS2@MoS x The / NF composite catalyst is a metal / crystalline / amorphous heterojunction catalyst.

[0020] The second object of the present invention is achieved by adopting the following technical solution:

[0021] A Ni@NiS2@MoS prepared by the above preparation method x / NF composite catalyst, the Ni@NiS2@MoS x The / NF composite catalyst is a metal / crystalline / amorphous heterojunction catalyst.

[0022] The third object of the present invention is achieved by adopting the following technical solution:

[0023] A Ni@NiS2@MoS x Application of Ni@NiS2@MoS / NF composite catalyst x Application of a / NF composite catalyst in the degradation of organic pollutants based on peroxymonosulfate; the organic pollutants are one or two of tetracycline hydrochloride and ranitidine.

[0024] The advantages and beneficial effects of the above technical solution provided by the present invention are:

[0025] 1. Ni@NiS2@MoS provided by the present invention x The preparation method of the Ni@NiS2@MoS / NF composite catalyst is to construct a Ni@NiS2@MoS / NF composite catalyst with a metal / crystalline / amorphous heterojunction through a coordinated strategy of directed self-assembly, internal Ni source, and water dispersion. x The Ni / NF composite catalyst, incorporating Ni-Mo bimetallic active centers, significantly improves the activation efficiency of peroxymonosulfate (PMS), addressing the limited active sites and poor structural stability of existing catalysts and achieving efficient degradation of antibiotic contaminants. Furthermore, the process is simple and environmentally friendly, using only methanol and water as solvents throughout the preparation process, avoiding the use of complex and potentially hazardous chemical reagents and solvents, thereby reducing the use of hazardous substances at the source.

[0026] 2. The core of the present invention is that the acidified nickel foam carrier can provide internal nickel ions (such as Ni²⁺), whose specific d orbital electronic characteristics (such as unpaired electrons or suitable electronic energy level structure) can react with amorphous MoS x In-situ chemical reaction occurs to form Ni@NiS2@MoS heterojunction of metal / crystalline / amorphous x This method avoids the introduction of an external nickel source, reducing costs, and in-situ chemical reactions reduce the number of steps typically required to prepare a metal / crystalline / amorphous heterojunction.

[0027] 3. The present invention adopts methanol volatilization to induce [Mo3S 13 ] 2- Directed aggregation of clusters and lattice reorganization to form amorphous MoS with highly exposed edges x The catalyst avoids the structural collapse caused by traditional high-temperature calcination, the excessive generation of sulfur vacancies caused by thermal stress, or the deactivation of active sites due to the breakage of Mo-S bonds. 13 ] 2- The clusters are randomly connected, and almost all sulfur atoms serve as edge active sites.

[0028] 4. In terms of organic pollutant degradation performance, the metal / crystalline / amorphous heterojunction Ni@NiS2@MoS prepared by the present invention x / NF composite catalyst is used to activate PMS to degrade antibiotic pollutants. This metal / crystalline / amorphous heterojunction has few application cases in the field of antibiotic degradation. The present invention confirms that the Ni@NiS2@MoS x / NF composite catalyst exhibits excellent ability to activate PMS to remove antibiotics (tetracycline hydrochloride, ranitidine, etc.), and therefore has broad application prospects in antibiotic wastewater treatment. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 (NH4)2Mo3S in the present invention 13 SEM image of nH2O;

[0030] Figure 2 (NH4)2Mo3S in the present invention 13 nH2O, nickel foam matrix raw materials and Ni@NiS2@MoS prepared in Example 1 x XRD pattern of / NF composite catalyst;

[0031] Figure 3 Ni@NiS2@MoS of Example 1 of the present invention x XPS pattern of / NF composite catalyst;

[0032] Figure 4 Ni@NiS2@MoS of Example 1 of the present invention x HRTEM image of / NF composite catalyst;

[0033] Figure 5 Ni@NiS2@MoS based on Example 1 of the present invention x A partial enlarged view of the HRTEM image analysis of the Ni / NF composite catalyst, and the results of further detailed analysis of the Ni lattice;

[0034] Figure 6 Ni@NiS2@MoS based on Example 1 of the present invention x A partial enlarged view of the HRTEM image analysis of the NiS2 / NF composite catalyst, and the results of further detailed analysis of the NiS2 lattice;

[0035] Figure 7 Ni@NiS2@MoS of Example 1 of the present invention x / NF composite catalyst (Ni@NiS2@MoS x / NF+PMS), nickel foam (Ni Foam+PMS), and blank experiment (TC+PMS) in the degradation of tetracycline hydrochloride in the activated PMS system;

[0036] Figure 8 Ni@NiS2@MoS prepared in Example 1 of the present invention x / NF composite materials were respectively mixed with MoS prepared in Comparative Examples 1 to 4. x Comparative effect of / Ni Foam composite catalyst material in activating PMS to degrade tetracycline hydrochloride;

[0037] Figure 9 Ni@NiS2@MoS prepared in Example 1 of the present invention x Comparative effect diagram of the degradation of tetracycline hydrochloride and ranitidine by / NF composite materials in activated PMS. DETAILED DESCRIPTION

[0038] The technical solutions and technical effects of the present invention will be clearly and completely described below with reference to specific embodiments and experimental examples. However, those skilled in the art should understand that the embodiments are only used to illustrate the technical solutions of the present invention and should not be regarded as limiting the scope of protection of the present invention. The experimental methods used in the following examples are all conventional methods unless otherwise specified; the raw materials used are all materials commonly used in the art and available to the public through commercial channels unless otherwise specified. In the present invention, room temperature has the conventional understanding in the field, that is, 25±5°C.

[0039] In the following embodiments of the present invention, the raw material of the nickel foam matrix comes from Kunshan Shengzhaoduan New Materials Co., Ltd.

[0040] (NH4)2Mo3S used in the present invention 13 nH2O, which can be prepared by referring to the existing technology (patent application CN119771449A), and the present invention does not impose any special restrictions on it. For example, (NH4)2Mo3S 13 The preparation method of nH2O comprises the following steps: adding 30-40g of sulfur powder to 100-120mL of ammonium sulfide to obtain a polysulfide ammonium solution with a concentration of 20%-25%; then adding 2-4g of ammonium molybdate to the polysulfide ammonium solution, and reacting in an oil bath at 90-95°C for 4-5 days; after the reaction, cooling the product to room temperature and centrifuging it at a speed of 5000-8000 rpm to obtain a crude product. The crude product is washed with 300-1000mL of carbon disulfide and deionized water, followed by drying at a temperature of 40-60°C for 10-24 hours to obtain a dark red powder, namely (NH4)2Mo3S 13 ·nH2O.

[0041] Specifically, (NH4)2Mo3S used in the following examples and comparative examples of the present invention 13 nH2O was prepared as follows: 40g of sulfur powder was added to 120mL of ammonium sulfide to obtain a 25% polysulfide ammonium solution. 4g of ammonium molybdate was then added to the polysulfide ammonium solution and reacted in a 95°C oil bath for 5 days. After the reaction, the product was cooled to room temperature and centrifuged (at 8000 rpm) to obtain a crude product. The crude product was washed with 1000mL of carbon disulfide and deionized water, followed by drying (at 60°C for 10 hours) to obtain a dark red powder, namely (NH4)2Mo3S 13 ·nH2O.

[0042] Example 1

[0043] This embodiment provides a Ni@NiS2@MoS x The preparation method of the / NF composite catalyst comprises the following steps:

[0044] (1) Add 15 mg of (NH4)2Mo3S 13 nH2O was added to 10 mL of methanol for ultrasonic dispersion at a frequency of 70 kHz and a dispersion time of 2 h to obtain [Mo3S 13 ] 2- Cluster solution, the solution has Tyndall effect; [Mo3S 13 ] 2- The cluster solution was heated at 70°C to volatilize methanol. The clusters were self-assembled by heating to induce methanol volatilization, thereby obtaining a black powder, which was recorded as MoS x ; then in MoS x 10 mL of distilled water was added to the mixture and the powder was mixed uniformly by ultrasound (ultrasonic frequency was 70 kHz and ultrasound time was 5 min) to obtain MoS x dispersion;

[0045] (2) The nickel foam substrate raw material was pretreated with degreasing using an organic solvent (anhydrous ethanol), and then cut into a size of 3 cm × 3 cm. The obtained nickel foam substrate was then placed in a hydrochloric acid (HCl) aqueous solution with a pH of 2 and ultrasonically treated at room temperature (ultrasonic frequency of 70 kHz, ultrasonic time of 2 h) for acidification activation. The obtained nickel foam material was then repeatedly rinsed with deionized water until neutral and dried to obtain an acidified nickel foam carrier.

[0046] (3) The acidified nickel foam carrier obtained in step (2) is placed in parallel and then completely immersed in the MoS obtained in step (1). xThe dispersion was immersed in the solution at room temperature for 2 h. After the immersion was completed, the solution was moved into an oven and dried at a constant temperature of 70 ° C for 1 h to obtain the target product of this embodiment, namely Ni@NiS2@MoS x / NF composite catalyst.

[0047] Example 2

[0048] This embodiment provides a Ni@NiS2@MoS x The preparation method of the / NF composite catalyst comprises the following steps:

[0049] (1) Add 15 mg of (NH4)2Mo3S 13 nH2O was added to 10 mL of methanol for ultrasonic dispersion at a frequency of 70 kHz and a dispersion time of 2 h to obtain [Mo3S 13 ] 2- Cluster solution, the solution has Tyndall effect; [Mo3S 13 ] 2- The cluster solution was heated at 60°C to volatilize methanol. The clusters were self-assembled by heating to induce methanol volatilization, thereby obtaining a black powder, which was recorded as MoS x ; then in MoS x 10 mL of distilled water was added to the mixture and the powder was mixed uniformly by ultrasound (ultrasonic frequency was 70 kHz and ultrasound time was 5 min) to obtain MoS x dispersion;

[0050] (2) The nickel foam substrate raw material was pretreated with degreasing using an organic solvent (anhydrous ethanol), and then cut into a size of 3 cm × 3 cm. The obtained nickel foam substrate was then placed in a hydrochloric acid (HCl) aqueous solution with a pH of 2 and ultrasonically treated at room temperature (ultrasonic frequency of 70 kHz, ultrasonic time of 2 h) for acidification activation. The obtained nickel foam material was then repeatedly rinsed with deionized water until neutral and dried to obtain an acidified nickel foam carrier.

[0051] (3) The acidified nickel foam carrier obtained in step (2) is placed in parallel and then completely immersed in the MoS obtained in step (1). x The dispersion was immersed in the solution at room temperature for 3 h. After the immersion was completed, the solution was moved into an oven and dried at a constant temperature of 60 ° C for 2 h to obtain the target product of this embodiment, namely Ni@NiS2@MoS x / NF composite catalyst.

[0052] Example 3

[0053] This embodiment provides a Ni@NiS2@MoS x The preparation method of the / NF composite catalyst comprises the following steps:

[0054] (1) Add 20 mg of (NH4)2Mo3S 13 nH2O was added to 20 mL of methanol for ultrasonic dispersion at a frequency of 60 kHz and a dispersion time of 2 h to obtain [Mo3S 13 ] 2- Cluster solution, the solution has Tyndall effect; [Mo3S 13 ] 2- The cluster solution was heated at 70°C to volatilize methanol. The clusters were self-assembled by heating to induce methanol volatilization, thereby obtaining a black powder, which was recorded as MoS x ; then in MoS x 20 mL of distilled water was added to the mixture and the powder was mixed uniformly by ultrasound (ultrasonic frequency was 60 kHz and ultrasound time was 5 min) to obtain MoS x dispersion;

[0055] (2) The nickel foam substrate raw material was pretreated with degreasing using an organic solvent (anhydrous ethanol), and then cut into a size of 5 cm × 5 cm. The obtained nickel foam substrate was then placed in a hydrochloric acid (HCl) aqueous solution with a pH of 2 and ultrasonically treated at room temperature (ultrasonic frequency of 70 kHz, ultrasonic time of 2 h) for acidification activation. The obtained nickel foam material was then repeatedly rinsed with deionized water until neutral and dried to obtain an acidified nickel foam carrier.

[0056] (3) The acidified nickel foam carrier obtained in step (2) is placed in parallel and then completely immersed in the MoS obtained in step (1). x The dispersion was immersed in the solution at room temperature for 2.5 h. After the immersion was completed, the solution was moved into an oven and dried at a constant temperature of 60 ° C for 2 h to obtain the target product of this embodiment, namely Ni@NiS2@MoS x / NF composite catalyst.

[0057] Example 4

[0058] This embodiment provides a Ni@NiS2@MoS x The preparation method of the / NF composite catalyst comprises the following steps:

[0059] (1) 10 mg of (NH4)2Mo3S 13 nH2O was added to 20 mL of methanol for ultrasonic dispersion at a frequency of 60 kHz and a dispersion time of 2 h to obtain [Mo3S 13 ] 2- Cluster solution, the solution has Tyndall effect; [Mo3S 13 ] 2-The cluster solution was heated at 70°C to volatilize methanol. The clusters were self-assembled by heating to induce methanol volatilization, thereby obtaining a black powder, which was recorded as MoS x ; then in MoS x 20 mL of distilled water was added to the mixture and the powder was mixed uniformly by ultrasound (ultrasonic frequency was 60 kHz and ultrasound time was 5 min) to obtain MoS x dispersion;

[0060] (2) The nickel foam substrate raw material was pretreated with degreasing using an organic solvent (anhydrous ethanol), and then cut into a size of 5 cm × 5 cm. The obtained nickel foam substrate was then placed in a hydrochloric acid (HCl) aqueous solution with a pH of 2 and ultrasonically treated at room temperature (ultrasonic frequency of 70 kHz, ultrasonic time of 2 h) for acidification activation. The obtained nickel foam material was then repeatedly rinsed with deionized water until neutral and dried to obtain an acidified nickel foam carrier.

[0061] (3) The acidified nickel foam carrier obtained in step (2) is placed in parallel and then completely immersed in the MoS obtained in step (1). x The mixture was immersed in the dispersion at room temperature for 2 h. After the immersion was completed, the mixture was moved into an oven and dried at a constant temperature of 60 ° C for 2 h to obtain the target product of this embodiment, namely Ni@NiS2@MoS x / NF composite catalyst.

[0062] Comparative Example 1

[0063] This comparative example provides a 1-MoS x / Ni Foam composite catalyst, the preparation method thereof comprises the following steps:

[0064] (1) Add 15 mg of (NH4)2Mo3S 13 nH2O was added to 10 mL of methanol for ultrasonic dispersion at a frequency of 70 kHz and a dispersion time of 2 h to obtain [Mo3S 13 ] 2- Cluster solution, the solution has Tyndall effect; [Mo3S 13 ] 2- The cluster solution was heated at 70°C to volatilize methanol. The clusters were self-assembled by heating to induce methanol volatilization, thereby obtaining a black powder, which was recorded as MoS x ; then in MoS x 10 mL of distilled water was added to the mixture and the powder was mixed uniformly by ultrasound (ultrasonic frequency was 70 kHz and ultrasound time was 5 min) to obtain MoS x dispersion;

[0065] (2) The nickel foam substrate raw material was pretreated by degreasing with an organic solvent (anhydrous ethanol), and then cut into a size of 3 cm × 3 cm, and then dried to obtain a nickel foam support (not acidified);

[0066] (3) The nickel foam carrier obtained in step (2) is placed in parallel and then completely immersed in the MoS x The dispersion was immersed in water at room temperature for 2 h. After the immersion was completed, the mixture was moved into an oven and dried at a constant temperature of 70 ° C for 1 h to obtain the target product of this comparative example, which was recorded as 1-MoS x / Ni Foam composite catalyst.

[0067] Comparative Example 2

[0068] This comparative example provides a 2-MoS x / Ni Foam composite catalyst, the preparation method thereof comprises the following steps:

[0069] (1) Add 15 mg of (NH4)2Mo3S 13 nH2O was added to 10 mL of methanol and stirred for 12 h to obtain [Mo3S 13 ] 2- Cluster solution, the solution does not have Tyndall effect; [Mo3S 13 ] 2- The cluster solution was heated at 70°C to evaporate methanol to allow clusters to self-assemble, resulting in a black powder, designated as MoS x ; then in MoS x 10 mL of distilled water was added to the mixture and the powder was mixed uniformly by ultrasound (ultrasonic frequency was 70 kHz and ultrasound time was 5 min) to obtain MoS x dispersion;

[0070] (2) The nickel foam substrate raw material was pretreated with degreasing using an organic solvent (anhydrous ethanol), and then cut into a size of 3 cm × 3 cm. The obtained nickel foam substrate was then placed in a hydrochloric acid (HCl) aqueous solution with a pH of 2 and ultrasonically treated at room temperature (ultrasonic frequency of 70 kHz, ultrasonic time of 2 h) for acidification activation. The obtained nickel foam material was then repeatedly rinsed with deionized water until neutral and dried to obtain an acidified nickel foam carrier.

[0071] (3) The nickel foam carrier obtained in step (2) is placed in parallel and then completely immersed in the MoS x The dispersion was immersed in water at room temperature for 2 h. After the immersion was completed, the mixture was moved into an oven and dried at a constant temperature of 70 ° C for 1 h to obtain the target product of this comparative example, which was recorded as 2-MoS x / Ni Foam composite catalyst.

[0072] Comparative Example 3

[0073] This comparative example provides a 3-MoS x / Ni Foam composite catalyst, the preparation method thereof is as follows:

[0074] (1) Add 15 mg of (NH4)2Mo3S 13 nH2O was dissolved in 10 mL of N,N-dimethylformamide (DMF) to obtain (NH4)2Mo3S 13 After standing for 20 hours, MoS self-assembled based on electrostatic attraction was obtained. x solution;

[0075] (2) The nickel foam substrate raw material was pretreated by degreasing with an organic solvent (anhydrous ethanol), and then cut into a size of 3 cm × 3 cm, and then dried to obtain a nickel foam support (not acidified);

[0076] (3) 10 mL of MoS x The solution was added dropwise onto the nickel foam support at a drop casting rate of 0.2 mL / min to obtain the target product of this comparative example, which was recorded as 3-MoS x / Ni Foam composite catalyst.

[0077] Comparative Example 4

[0078] This comparative example provides a 4-MoS x / Ni Foam composite catalyst, the preparation method thereof comprises the following steps:

[0079] (1) Add 15 mg of (NH4)2Mo3S 13 nH2O was added to 10 mL of methanol for ultrasonic dispersion at a frequency of 70 kHz and a dispersion time of 2 h to obtain [Mo3S 13 ] 2- Cluster solution, which exhibits Tyndall effect;

[0080] (2) The nickel foam substrate raw material was pretreated with degreasing using an organic solvent (anhydrous ethanol), and then cut into a size of 3 cm × 3 cm. The obtained nickel foam substrate was then placed in a hydrochloric acid (HCl) aqueous solution with a pH of 2 and ultrasonically treated at room temperature (ultrasonic frequency of 70 kHz, ultrasonic time of 2 h) for acidification activation. The obtained nickel foam material was then repeatedly rinsed with deionized water until neutral and dried to obtain an acidified nickel foam carrier.

[0081] (3) The acidified nickel foam carrier obtained in step (2) is placed in parallel and then completely immersed in the [Mo3S 13 ] 2- The cluster solution was immersed in the solution at room temperature for 2 h. After the immersion was completed, the solution was moved into an oven and dried at a constant temperature of 70 ° C for 1 h to obtain the target product of this comparative example, which was recorded as 4-MoS x / Ni Foam composite catalyst.

[0082] Experimental Example 1: Structural Characterization

[0083] Scanning electron microscopy (SEM) was used to investigate the molybdenum-based precursor compound (NH4)2Mo3S 13 The morphology of nH2O raw materials was analyzed and characterized, and the SEM images obtained were as follows: Figure 1 As shown. Figure 1 It can be seen that (NH4)2Mo3S 13 The nH2O raw material samples are mainly rod-shaped and micron-sized.

[0084] Furthermore, X-ray diffraction was used to characterize (NH4)2Mo3S 13 nH2O raw material, nickel foam matrix raw material, and Ni@NiS2@MoS prepared in Example 1 x / NF composite catalyst was analyzed. Figure 2 (NH4)2Mo3S 13 nH2O (Figure a), nickel foam, and Ni@NiS2@MoS prepared in Example 1 x / NF composite material (Figure b).

[0085] Depend on Figure 2 It can be seen that (NH4)2Mo3S 13 nH2O peak is consistent with the standard card peak (Figure a). Ni@NiS2@MoS x In the / NF composite material, MoS x The nickel foam peak then weakened, indicating that MoS x It was successfully grown on nickel foam and formed an amorphous state (Figure b).

[0086] X-ray photoelectron spectroscopy (XPS) was further used to investigate the Ni@NiS2@MoS x / NF structural composition. Figure 3 Ni@NiS2@MoS prepared in Example 1 x XPS graph of / NF composite material. Figure 3By analyzing the total spectrum (Figure a), Ni 2p (Figure b), S 2p (Figure c), and Mo 3d (Figure d) spectra, the elemental composition, chemical valence state, and possible oxidation / defect sites are determined. Figure 3 It can be seen that a clear Cl 2p characteristic peak can be found at 200 eV, confirming the influence of hydrochloric acid acidification on the material synthesis during the synthesis process (Figure a). Further observation revealed the presence of Ni 2+ (NiS2), Ni 0 (base) coexistence peak (Fig. b), and S 2- (NiS2, MoS x )、S2 2- (polysulfide), S=O (surface oxidation) (Figure c), and Mo 5+ / Mo 6+ (MoS x ) (Figure d).

[0087] The Ni@NiS2@MoS of Example 1 was further analyzed using high-resolution transmission electron microscopy (HRTEM). x / NF structure. Figure 4 Ni@NiS2@MoS prepared in Example 1 x HRTEM image of / NF composite material. Figure 4 As can be seen in Figure a, the assembled catalyst is a thin layer structure, nanoscale, and Figure 1 The raw material structures are obviously different, and the smaller size is more conducive to providing catalytic active sites. Figure 4 Figure b is a partial enlargement of the red frame in Figure a, where the crystalline / amorphous heterojunction can be seen.

[0088] Furthermore, based on the above HRTEM image, the metallic Ni phase was further analyzed. Figure 5 Figures a to e in the figure are Ni@NiS2@MoS in Example 1. x A partial enlarged view of the HRTEM image analysis of the Ni / NF composite catalyst, and the results of further detailed analysis of the Ni lattice. Figure 5 The results show that the lattice fringe is 0.217 nm, corresponding to the (002) plane of metallic Ni, confirming the existence of metallic Ni.

[0089] Furthermore, based on the above HRTEM image, the metallic NiS2 phase was further analyzed. Figure 6 Figures a to e in the figure are Ni@NiS2@MoS in Example 1. x A partial enlarged view of the HRTEM image analysis of the NiS / NF composite catalyst, and the results of further detailed analysis of the NiS2 lattice. Figure 6The results show that the lattice fringe is 0.252nm, corresponding to the (210) plane of metallic Ni, confirming the existence of metallic NiS2.

[0090] Based on the above structural characterization results, it can be seen that the present invention realizes Ni@NiS2@MoS x Successful preparation of / NF composite catalyst materials.

[0091] Experimental Example 2: Pollutant Degradation Performance Test

[0092] This experimental example examines the effects of different catalytic materials in activating PMS to degrade tetracycline hydrochloride, in order to evaluate its pollutant degradation performance and the superiority of the preparation method of the present invention.

[0093] The specific test method is as follows: Ni@NiS2@MoS x / NF composite catalyst material, 1-MoS of Comparative Example 1 x / Ni Foam composite catalyst material, 2-MoS of Comparative Example 2 x / Ni Foam composite catalyst material, 3-MoS of Comparative Example 3 x / Ni Foam composite catalyst material, 4-MoS of Comparative Example 4 x The Ni / Ni Foam composite catalyst materials were added to a 10 mg / L tetracycline hydrochloride solution in the dark and allowed to adsorb for 30 minutes to allow adsorption-desorption equilibrium to be reached between the catalyst and the solution. Then, 0.05 g of peroxymonosulfate (PMS) was added to initiate the PMS activation reaction. Samples were taken periodically, and the absorbance of the tetracycline hydrochloride was measured using a UV-Vis spectrophotometer to observe changes in tetracycline hydrochloride concentration. A control experiment was conducted on unmodified nickel foam using the same procedures as above (denoted as Ni Foam + PMS). A blank experiment consisted of the PMS activation reaction in the dark without the addition of any materials, using the same procedures as above (denoted as TC + PMS).

[0094] Figure 7 Ni@NiS2@MoS of Example 1 x / NF composite catalyst (Ni@NiS2@MoS x / NF+PMS), nickel foam (NiFoam+PMS), and blank experiment (TC+PMS) in the activated PMS system to degrade tetracycline hydrochloride. Figure 7 As shown, Ni@NiS2@MoS xThe degradation rate of the NiFoam+PMS system for 100 mL of 10 mg / L tetracycline hydrochloride within 60 minutes was 97.4%. The degradation rates of the TC+PMS system and the NiFoam+PMS system for 100 mL of 10 mg / L tetracycline hydrochloride within 60 minutes were 34.8% and 45.9%, respectively.

[0095] Figure 8 Ni@NiS2@MoS of Example 1 x / NF composite catalyst and MoS of Comparative Examples 1 to 4 x / Ni Foam composite catalyst material in the activated PMS system to degrade tetracycline hydrochloride. Figure 8 It can be seen that the Ni@NiS2@MoS prepared in Example 1 of the present invention x / NF composite material, the degradation rate of 100mL of 10mg / L tetracycline hydrochloride was 90.1% within 20min. x / NF activated PMS, the degradation rate of 100mL of 10mg / L tetracycline hydrochloride was 61.7% within 20min. x / NF activated PMS, the degradation rate of 100mL of 10mg / L tetracycline hydrochloride was only 39.6% within 20min. x / NF activated PMS, the degradation rate of 100mL of 10mg / L tetracycline hydrochloride was 76.3% within 20min. x / NF activated PMS, and the degradation rate of 100mL of 10mg / L tetracycline hydrochloride was 61.5% within 20min.

[0096] By comparing with Comparative Example 1, it is shown that the acidification of the present invention has a great influence on the Ni@NiS2@MoS x / NF composite materials showed significantly enhanced degradation activity. By comparing with Comparative Example 2, it is shown that the self-assembled Ni@NiS2@MoS x / NF composite materials have stronger ability to remove antibiotic pollutants. By comparing with comparative example 3, it is shown that the Ni@NiS2@MoS x / NF composite materials showed a stronger ability to remove antibiotic pollutants, which also shows that the present invention has better advantages than the drop casting method. By comparing with Comparative Example 4, it is shown that the Ni@NiS2@MoS xThe / NF composite material showed a stronger ability to remove antibiotic pollutants, which also showed that the present invention had better excellence than the single methanol dissolution assembly method.

[0097] Furthermore, under the same test conditions as above, degradation application experiments of tetracycline hydrochloride (TC) and ranitidine (RAN) were carried out. Figure 9 Ni@NiS2@MoS prepared in Example 1 of the present invention x Comparative effect diagram of the degradation of tetracycline hydrochloride and ranitidine by / NF composite materials in activated PMS.

[0098] Depend on Figure 9 It can be seen that the Ni@NiS2@MoS prepared in Example 1 of the present invention x / NF composite materials, the degradation rate of 100mL of 10mg / L tetracycline hydrochloride (TC) and ranitidine (RAN) reached more than 97% within 60min. The experimental data show that Ni@NiS2@MoS x Under the same reaction conditions, the / NF composite material showed efficient and consistent degradation performance for quinolone (tetracycline) and receptor antagonist (ranitidine) antibiotics with significant structural differences.

[0099] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principles of the present invention. These improvements and modifications should also be regarded as within the scope of protection of the present invention.

Claims

1. A Ni@NiS2@MoS x The preparation method of the / NF composite catalyst is characterized in that: The following steps are involved: (NH4)2Mo3S 13 nH2O was ultrasonically dispersed in methanol to obtain [Mo3S 13 ] 2- Cluster solution; the [Mo3S 13 ] 2- The cluster solution is heated to evaporate methanol to achieve cluster self-assembly, obtaining MoS x powder; MoS x The powder was dissolved in water and ultrasonically mixed to obtain MoS x dispersion; Another nickel foam substrate is acidified to obtain an acidified nickel foam; Immerse the acidified nickel foam in MoS x The Ni@NiS2@MoS dispersion was immersed in the solution and then dried to obtain the Ni@NiS2@MoS x / NF composite catalyst.

2. Ni@NiS2@MoS according to claim 1 x The preparation method of the / NF composite catalyst is characterized in that: (NH4)2Mo3S 13 The dosage ratio of nH2O, methanol, and water is (1~2) mg: (1~2) mL: (1~2) mL.

3. Ni@NiS2@MoS according to claim 1 x The preparation method of the / NF composite catalyst is characterized in that: The frequency of the ultrasonic dispersion is 40k~70kHz, and the time of the ultrasonic dispersion is 1~3h.

4. Ni@NiS2@MoS according to claim 1 x The preparation method of the / NF composite catalyst is characterized in that: The heating temperature is 60-70°C.

5. Ni@NiS2@MoS according to claim 1 x The preparation method of the / NF composite catalyst is characterized in that: The frequency of the ultrasonic mixing is 40k~70kHz, and the time of the ultrasonic mixing is 3~10min.

6. Ni@NiS2@MoS according to any one of claims 1 to 5 x The preparation method of the / NF composite catalyst is characterized in that: The nickel foam substrate is degreased before acidification treatment; the size of the nickel foam substrate is 1cm×1cm~10cm×10cm; the acidification treatment is to ultrasonically treat the nickel foam substrate in a hydrochloric acid solution; the pH of the hydrochloric acid solution is 1~3.

7. Ni@NiS2@MoS according to any one of claims 1 to 5 x The preparation method of the / NF composite catalyst is characterized in that: The immersion time is 1.5 to 3 hours.

8. Ni@NiS2@MoS according to any one of claims 1 to 5 x The preparation method of the / NF composite catalyst is characterized in that: The drying temperature is 60-80° C. and the drying time is 1-3 hours.

9. Ni@NiS2@MoS prepared by the preparation method according to any one of claims 1 to 8 x / NF composite catalyst, characterized in that The Ni@NiS2@MoS x The / NF composite catalyst is a metal / crystalline / amorphous heterojunction catalyst.

10. A Ni@NiS2@MoS as claimed in claim 9 x The application of the / NF composite catalyst is characterized in that: The application is Ni@NiS2@MoS x Application of a / NF composite catalyst in the degradation of organic pollutants based on peroxymonosulfate; the organic pollutants are one or two of tetracycline hydrochloride and ranitidine.

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