Zirconium-based MOF adsorbent material, preparation method and application thereof
The synthesis of zirconium-based MOF adsorbent materials has solved the complexity and pollution problems of Pt, Rh, and Pd separation and recovery in existing technologies, achieving efficient and simple separation and recovery of precious metals, suitable for industrial applications under acidic conditions.
Patent Information
- Application Number
- CN202610999856.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2026-07-07
- Publication Date
- 2026-11-03
AI Technical Summary
Existing technologies for separating and recovering ternary precious metals such as Pt, Rh, and Pd suffer from problems such as lengthy and complex processes, high energy consumption, poor selectivity, high environmental pollution risks, and low metal recovery rates, making it difficult to meet the needs of high-end applications.
Using zirconium-based MOF adsorbent materials, zirconium tetrachloride as the metal node and meso-2,3-dimercaptosuccinic acid as the organic ligand, a structurally stable Zr-MOF framework was synthesized to achieve selective adsorption and separation of ternary noble metals Pt, Rh, and Pd.
It achieves efficient separation and recovery of Pt, Rh, and Pd, simplifies the process, reduces energy consumption, reduces environmental pollution, improves metal recovery rate, and is suitable for acidic liquid treatment.
Smart Images
Figure CN123024527A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of separation and purification technology, specifically relating to a zirconium-based MOF adsorbent material, its preparation method, and its application. Background Technology
[0002] The ternary noble metals Pt, Pd, and Rh achieve functional complementarity and structural stability through synergistic electronic interactions, resulting in catalytic performance far exceeding that of single-component catalysts in fields such as three-way catalysis, industrial waste gas treatment, fuel cells, and fine chemicals. Currently, they have two main applications: one is as a catalyst for purifying gasoline vehicle exhaust, which contains HC, CO, and NO. x Pollutants such as particulate matter pose a serious threat to human health. Among the ternary noble metals Pt, Pd, and Rh, Pt and Pd primarily catalyze oxidation reactions, oxidizing CO and HC into CO2 and H2O, while Rh uniquely catalyzes reduction reactions, converting NO into CO2 and H2O. x The first is to reduce it to N2, thereby purifying the exhaust gas. The second is an alloy mesh with a mesh structure made of Pt, Pd and Rh ternary precious metal alloy wires. With the high activity of Pt, the high selectivity and stability of Rh and the economy of Pd, it plays a catalytic role in processes such as nitric acid industry and hydrogen cyanide production.
[0003] Currently, the mainstream technical route for separating and recovering ternary precious metals Pt, Rh, and Pd is pyrometallurgical enrichment coupled with hydrochemical extraction. First, platinum group metals are initially enriched through high-temperature smelting. Then, the enriched material is transferred to the liquid phase using methods such as aqua regia dissolution and sodium chlorate oxidation leaching. Finally, separation and purification are completed through solvent extraction, ion exchange, and chemical precipitation. However, this traditional process still has many drawbacks: the process flow is lengthy and complex, energy consumption is high, selectivity for the target precious metals is poor, and it easily generates large amounts of acidic waste liquid and toxic gases, posing significant environmental pollution risks. Furthermore, due to the limitations of the process itself, there are generally problems such as low metal recovery rates and the final product purity failing to meet the requirements of high-end applications. Therefore, developing efficient, highly selective, environmentally friendly, and easy-to-operate Pt, Rh, and Pd precious metal recovery and separation technologies has become key to breaking through the bottlenecks of traditional processes and promoting the green upgrading of the Pt, Rh, and Pd precious metal recovery industry.
[0004] Metal-organic frameworks (MOFs), also known as metal-organic coordination polymers or metal-organic network structures, are multidimensional structures with certain channels or cavities formed by the self-assembly of polydentate organic ligands and metal ions or ion clusters through coordination bonds. MOFs, as a novel material that emerged in the early 1990s, provided an opportunity for the design of high-performance adsorbents. MOFs were first reported in 1995 by Yaghhi et al., who first reported a MOF composed of the organic ligands pyromellitic acid and Co. 2+The synthesized coordination compound with a two-dimensional structure was named MOF. Adsorption separation methods have attracted widespread attention in the scientific research field due to their advantages such as low cost, simple operation, recyclable adsorbents, and the absence of harmful byproducts. For adsorption technology, developing structurally stable, reusable, and highly efficient adsorbents is currently a core research focus. Therefore, how to utilize MOFs as adsorbent materials to achieve the adsorption and separation of ternary noble metals Pt, Rh, and Pd is of great significance. Summary of the Invention
[0005] Based on the above-mentioned prior art, the purpose of this invention is to select zirconium-based MOFs as adsorbent materials, use zirconium oxide clusters formed by zirconium tetrachloride as metal nodes, and precisely and orderly graft them onto the structurally stable Zr-MOF framework through meso-2,3-dimercaptosuccinic acid (DMSA) as a "molecular bridge" to achieve a perfect combination of MOF and active sites, thereby realizing the separation and recovery of ternary noble metals Pt, Rh and Pd.
[0006] To achieve the above objectives, the technical solution of the present invention is as follows: The first aspect of the present invention provides a zirconium-based MOF adsorbent material, wherein the zirconium-based MOF adsorbent material is an adsorbent material synthesized using zirconium chloride as a metal source and meso-2,3-dimercaptosuccinic acid as an organic ligand.
[0007] The second aspect of this invention provides a method for preparing the zirconium-based MOF adsorbent material described in the first aspect, the method comprising the following steps: Zirconium chloride (ZrCl4), meso-2,3-dimercaptosuccinic acid (DMSA), and formic acid (FA) were mixed, and then deionized water was added. The mixture was stirred at room temperature and refluxed. The resulting solid was washed and dried to obtain the zirconium-based MOF adsorbent material, namely Zr-DMSA-SH MOF adsorbent material.
[0008] In one optional embodiment, the amount of zirconium chloride is 1.165 g; the amount of meso-2,3-dimercaptosuccinic acid is 0.91 g; and the amount of formic acid is 0.28~0.42 mL.
[0009] In one optional embodiment, the room temperature stirring time is 15-30 minutes.
[0010] In one optional implementation, the reflux temperature is 95°C and the time is 10-12 hours.
[0011] In one optional embodiment, the drying temperature is 100°C and the time is 24 hours.
[0012] The third aspect of this invention provides the application of the zirconium-based MOF adsorbent material described in the first aspect for the adsorption and separation of noble metals Pt, Rh, and Pd.
[0013] The fourth aspect of this invention provides a method for adsorbing and separating noble metals Pt, Rh, and Pd using the zirconium-based MOF adsorbent material described in the first aspect, wherein the method is any one of the paths (1)-(3): (1) Add zirconium-based MOF adsorbent to the solution to be treated. During the treatment time and temperature, Pt in the solution is selectively adsorbed. After solid-liquid separation, the zirconium-based MOF adsorbent that adsorbs Pt is placed in a thiourea hydrochloric acid solution for desorption treatment to obtain a thiourea hydrochloric acid solution containing Pt. Then, hydrazine hydrate is added to it, the precipitate is collected by filtration, and pure noble metal Pt is obtained by calcination. (2) Add zirconium-based MOF adsorbent to the solution to be treated. During the treatment time and temperature, Pd in the solution is selectively adsorbed. After solid-liquid separation, the zirconium-based MOF adsorbent that adsorbs Pd is placed in a thiourea hydrochloric acid solution for desorption treatment to obtain a thiourea hydrochloric acid solution containing Pd. Then, hydrazine hydrate is added to it, the precipitate is collected by filtration, and pure noble metal Pd is obtained by calcination. (3) Add zirconium-based MOF adsorbent to the solution to be treated. Under the treatment time and temperature, Pd and Pt in the solution are selectively adsorbed. After solid-liquid separation, adsorbent A containing Pd and Pt and solution B containing Pt and Rh are obtained. Adsorbent A containing Pd and Pt contains 100% Pd and 50% to 60% Pt. It is placed in thiourea hydrochloric acid solution for desorption treatment to obtain thiourea hydrochloric acid solution containing Pd and Pt. Then, resin is added to adsorb Pd to achieve the separation of Pd and Pt. Solution B containing Pt and Rh contains 40% to 50% Pt and 100% Rh. Zirconium-based MOF adsorbent is added to it again. Under the treatment time and temperature, adsorbent C containing Pt and solution D containing Rh are obtained. Solution D containing Rh is reduced with hydrazine hydrate to obtain metal Rh. Adsorbent C containing Pt is placed in thiourea hydrochloric acid solution for desorption treatment to obtain noble metal Pt.
[0014] In one optional embodiment, the processing temperature is 20~50°C.
[0015] In one optional implementation, the processing time is 12 hours.
[0016] Compared with the prior art, the beneficial effects of the present invention are as follows: (1) This invention successfully prepared Zr-DMSA-SH MOF adsorbent material for the first time. The preparation method is simple, easy to operate, and convenient for practical application.
[0017] (2) This invention explored the adsorption performance of Zr-DMSA-SH MOF adsorbent material for ternary noble metals Pt, Rh and Pd. It was found that it exhibited the strongest adsorption capacity for Pd, followed by the adsorption capacity for Pt, while it had almost no significant adsorption effect on Rh. This result provides a theoretical basis for the efficient separation of Pt, Rh and Pd.
[0018] (3) The Zr-DMSA-SH MOF adsorbent provided by this invention has excellent acid resistance and stability. It can be directly used for acidic liquid treatment without prior adjustment of the solution pH value, which greatly simplifies the precious metal separation process. It has strong engineering adaptability advantages in the separation and recovery of ternary precious metals Pt / Rh / Pd for industrial acidic hydrometallurgical waste liquid. Attached Figure Description
[0019] Figure 1 X-ray diffraction (XRD) patterns of Zr-DMSA-SH MOF adsorbents at different formic acid values. Figure 2 The attached diagram shows the N2 adsorption-desorption of the Zr-DMSA-SH MOF adsorbent material under different formic acid values. Figure 3 The infrared (FT-IR) spectra of the Zr-DMSA-SH MOF adsorbent material under different formic acid values. Figure 4 X-ray photoelectron spectroscopy (XPS) spectra of Zr-DMSA-SH MOF adsorbents at different formic acid values. Figure 5 The adsorption capacity of Zr-DMSA-SH MOF adsorbent for single-component noble metals Pt, Rh, and Pd at an initial concentration of 10 ppm. Figure 6 The adsorption capacity of Zr-DMSA-SH MOF adsorbent for single-component noble metals Pt, Rh, and Pd at an initial concentration of 100 ppm. Figure 7 Transmission electron microscopy (TEM) images and elemental energy dispersive spectroscopy (EDS) spectra of single-component noble metals such as Pt, Rh, or Pd after adsorption on Zr-DMSA-SH-0.38. Figure 8 The adsorption capacity of Zr-DMSA-SH MOF adsorbent for multi-component noble metals Pt, Rh, and Pd at an initial concentration of 100 ppm. Figure 9 The adsorption selectivity of Zr-DMSA-SH MOF adsorbent for multi-component noble metals Pd and Pt; Figure 10Transmission electron microscopy (TEM) images and elemental energy dispersive spectroscopy (EDS) spectra of multi-component noble metals such as Pt, Rh, or Pd after adsorption on Zr-DMSA-SH-0.38. Figure 11 X-ray diffraction (XRD) patterns of Zr-DMSA-SH-0.38 before and after impregnation in hydrochloric acid solutions of different pH values. Figure 12 This is a structural diagram of the Zr-DMSA-SH MOF adsorbent material. Detailed Implementation
[0020] To facilitate understanding of the present invention, a more comprehensive description will be given below. However, the present invention can be implemented in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided to provide a thorough and complete understanding of the disclosure of the present invention.
[0021] Example 1: Preparation of Zr-DMSA-SH-0.28 adsorbent material (1) In a 25mL round-bottom flask, add 1.165g ZrCl4, 0.91g DMSA and 0.28mL FA in sequence, and then add 10mL deionized water.
[0022] (2) After stirring at room temperature for 15 min, the mixture was refluxed at 95℃ for 12 h. The resulting solid was washed with deionized water and methanol respectively. The final white product was dried at 100℃ for 24 h to obtain Zr-DMSA-SH MOF adsorbent material, labeled as Zr-DMSA-SH-0.28.
[0023] Example 2: Preparation of Zr-DMSA-SH-0.34 adsorbent material (1) In a 25mL round-bottom flask, add 1.165g ZrCl4, 0.91g DMSA and 0.34mL FA in sequence, and then add 10mL deionized water.
[0024] (2) After stirring at room temperature for 15 min, the mixture was refluxed at 95℃ for 12 h. The resulting solid was washed with deionized water and methanol respectively. The final white product was dried at 100℃ for 24 h to obtain Zr-DMSA-SH MOF adsorbent material, labeled as Zr-DMSA-SH-0.34.
[0025] Example 3: Preparation of Zr-DMSA-SH-0.38 adsorbent material (1) In a 25 mL round-bottom flask, add 1.165 g ZrCl4, 0.91 g DMSA and 0.38 mL FA in sequence, and then add 10 mL of deionized water.
[0026] (2) After stirring at room temperature for 15 min, the mixture was refluxed at 95℃ for 12 h. The resulting solid was washed with deionized water and methanol respectively. The final white product was dried at 100℃ for 24 h to obtain Zr-DMSA-SH MOF adsorbent material, labeled as Zr-DMSA-SH-0.38.
[0027] Example 4: Preparation of Zr-DMSA-SH-0.42 adsorbent material (1) In a 25mL round-bottom flask, add 1.165g ZrCl4, 0.91g DMSA and 0.42mL FA in sequence, and then add 10mL deionized water.
[0028] (2) After stirring at room temperature for 15 min, the mixture was refluxed at 95℃ for 12 h. The resulting solid was washed with deionized water and methanol respectively. The final white product was dried at 100℃ for 24 h to obtain Zr-DMSA-SH MOF adsorbent material, labeled as Zr-DMSA-SH-0.42.
[0029] Figure 1 The XRD patterns of the Zr-DMSA-SH MOF adsorbents prepared in Examples 1-4 show that all adsorbents possess ideal crystal structures, indicating successful synthesis. The N2 adsorption-desorption diagrams of Zr-DMSA-SH MOFs are shown below. Figure 2 As shown, it can be clearly observed that the synthesized adsorbent materials all belong to typical Type I isotherms; Figure 3 FT-IR spectra show that all synthesized adsorbent materials contain thiol groups (-SH); Figure 4 The XPS spectra clearly show that the synthesized adsorbent material contains C, O, Zr, and S, which fully proves that the Zr-DMSA-SH MOF adsorbent material has been successfully synthesized.
[0030] Example 5: Adsorption of single-component noble metals Pt, Rh, and Pd by Zr-DMSA-SH MOF adsorbent material 5 mg of Zr-DMSA-SH MOF adsorbent was weighed and placed in a sample vial. 10 mL of a hydrochloric acid mixture containing one component of noble metal Pt, Rh, or Pd (10 ppm or 100 ppm, pH=3) was added. The material was then sonicated to ensure uniform dispersion in the solution. The sample vial was then placed in a shaker (30 ℃) and the reaction was carried out for 12 h to complete the single-component adsorption experiments for Pt, Rh, and Pd. Adsorption performance was tested using ICP-OES. The adsorption capacity (C0, 10 ppm or 100 ppm) of the synthesized adsorbent for Pt, Rh, or Pd was obtained after testing. (See attached table). Figure 5 and Figure 6 .from Figure 5 and Figure 6 It can be seen that the adsorbent material exhibits excellent adsorption capacity for Pt and Pd, but has virtually no adsorption effect on Rh. Furthermore, it can be observed that Zr-DMSA-SH-0.38 shows the best adsorption performance among all samples. Figure 7 The TEM and EDS results can further verify the above experimental results.
[0031] After adsorption, the MOF adsorbent material containing the single-component noble metal was separated and then placed in 10 mL of 0.1 g / mL thiourea hydrochloric acid solution for desorption. After static treatment for 3-5 days, the adsorbed single-component noble metal dissolved in the thiourea hydrochloric acid solution. After the thiourea hydrochloric acid solution separated from the MOF adsorbent material, 10 mL of hydrazine hydrate was added to the filtrate, and the resulting noble metal precipitate was collected by filtration. The precipitate, along with the filter paper, was placed in a muffle furnace and calcined at 500 °C for 2 h. This process effectively removed the filter paper, ultimately yielding pure noble metal.
[0032] Example 6: Adsorption of multi-component noble metals Pt, Rh, and Pd by Zr-DMSA-SH MOF adsorbent material A 10 mL multi-component (100 ppm, pH=3) mixed solution containing three noble metals, Pt, Rh, and Pd, was weighed and placed in a sample vial. 5 mg of Zr-DMSA-SH MOF adsorbent was added, and the material was ultrasonically dispersed uniformly in the solution. The sample vial was then placed in a shaker at 30 °C and the reaction was carried out for 12 h to complete the adsorption experiment for Pt, Rh, and Pd. The adsorption performance was tested using ICP-OES. Figure 8 The adsorption capacity of the Zr-DMSA-SH MOF adsorbent for the multi-component noble metals Pt, Rh, and Pd is given by... Figure 8 It is evident that Zr-DMSA-SH-0.38 exhibits the best adsorption effect, while... Figure 9 This also indicates that it has the highest adsorption selectivity for Pd and Pt. Figure 10 The TEM and EDS results can further verify the above experimental results.
[0033] After adsorption, solid-liquid separation yielded Zr-DMSA-SH MOF adsorbent A and solution B containing the remaining noble metal. In this step, the adsorbent adsorbed 100% of Pd and 60% of Pt, leaving solution B containing 40% Pt and 100% Rh. Solution B was placed back into a sample vial, and 5 mg of Zr-DMSA-SH MOF adsorbent was added. After sonication, the sample vial was placed in a shaker and shaken for 12 hours to complete the adsorption experiment of the remaining Pt, yielding adsorbent C containing Pt and solution D containing Rh. Hydrazine hydrate was directly added to solution D to directly reduce and obtain metal Rh. Adsorbent C containing Pt was desorbed in 10 mL of 0.1 g / mL thiourea hydrochloric acid solution and then treated to obtain noble metal Pt. Adsorbent A was desorbed in 10 mL of 0.1 g / mL thiourea hydrochloric acid solution. After the thiourea hydrochloric acid solution was separated from the MOF adsorbent, resin was added to adsorb Pd, achieving the separation of Pd and Pt.
[0034] In the single-component adsorption experiment, according to the experimental results, when the initial concentration was 10 ppm, the adsorption rates of Zr-DMSA-SH-0.28, Zr-DMSA-SH-0.34, Zr-DMSA-SH-0.38, and Zr-DMSA-SH-0.42 for Pd were 100%; the adsorption rate for Rh was 0%; and the adsorption rates for Pt were 98.12%, 99.82%, 99.97%, and 99.32%, respectively. When the initial concentration was 100 ppm, the adsorption rates of Pd by Zr-DMSA-SH-0.28, Zr-DMSA-SH-0.34, Zr-DMSA-SH-0.38, and Zr-DMSA-SH-0.42 were 89.09%, 88.06%, 93.79%, and 78.92%, respectively; the adsorption rate of Rh was 0%; and the adsorption rates of Pt were 46.19%, 30.51%, 47.50%, and 31.85%, respectively. In multi-component adsorption experiments, based on the results, when the initial concentration was 100 ppm, the adsorption rates of Pd by Zr-DMSA-SH-0.28, Zr-DMSA-SH-0.34, Zr-DMSA-SH-0.38, and Zr-DMSA-SH-0.42 were 80.21%, 78.05%, 82.75%, and 59.84%, respectively; the adsorption rate of Rh was 0%; and the adsorption rates of Pt were 23.43%, 11.70%, 14.30%, and 9.44%, respectively. The experimental results indicate that the adsorption effect was optimal when the formic acid content was 0.38%. Under acidic conditions (pH=3), the Zr-DMSA-SH MOF adsorbent is a positively charged metal-organic framework material with soft basic thiol functional groups. Rh exists in the system as the cationic Rh(III) form, which generates electrostatic repulsion with the positively charged organic framework material; therefore, the material hardly adsorbs Rh. According to the hard and soft acid-base theory, the acidic chloride salt system exists in the form of anionic chloride complex ions. Pd(II) and Pt(IV) are both classified as soft acids, which can undergo strong coordination with the soft basic thiol groups on the framework, enabling the material to adsorb both metals. In comparison, Pd(II) has more pronounced soft acid characteristics and stronger affinity for thiol groups. Therefore, the adsorption capacity of this material for Pd is better than that for Pt.
[0035] Example 7: Acid stability of Zr-DMSA-SH MOF adsorbent material The Zr-DMSA-SH MOF adsorbent exhibits excellent stability; after immersion in hydrochloric acid solutions with different pH values (-1, -0.5, 0, 0.5, 1) for 24 hours, as shown... Figure 11As shown, the main characteristic diffraction peaks in the XRD pattern of the material did not shift significantly, only the crystallinity decreased slightly, indicating that its core structure remained intact and maintained its structural integrity. This demonstrates its strong acid resistance, stability in highly acidic precious metal solutions, and adaptability to the application conditions of acidic hydrometallurgical wastewater.
[0036] Figure 12 The diagram shows the structure of the Zr-DMSA-SH MOF adsorbent material. The Zr6O4(OH)4 hexanuclear zirconium oxide cluster serves as the secondary building block, with difunctional dimercaptosuccinic acid (DMSA) as the organic linker ligand. The carboxyl groups at both ends of the ligand form stable coordination bonds with the Zr metal center, constructing a rigid three-dimensional porous framework. The ligand side chains carry a large number of exposed thiol groups (-SH) uniformly distributed on the inner walls of the pores. Formic acid-regulated lattice defects widen the original ultraporous channels, generating macroporous and mesoporous structures, shortening the diffusion path of noble metal ions and providing abundant sulfur chelation sites. Based on the interaction of hard and soft acids and bases, the thiol groups within the pores can specifically bind Pd(II) and Pt(IV) noble metal ions. Simultaneously, the highly stable Zr-O framework endows the material with excellent acid resistance, making it suitable for the cyclic adsorption and separation of practical noble metal solutions.
[0037] The above analysis demonstrates that the Zr-DMSA-SH MOF adsorbent material synthesized using the technical solution of this invention exhibits high crystallinity. Furthermore, the adsorbent material demonstrates superior adsorption performance in both single-component and multi-component adsorption of noble metals Pt, Rh, and Pd, making it a highly promising adsorbent material for various applications.
[0038] The above description is only for better explaining the embodiments of the present invention and is not intended to limit them. Any modifications or equivalent substitutions that do not depart from the spirit and scope of the present invention shall fall within the scope of the present invention.
Claims
1. A zirconium-based MOF adsorbent material, characterized in that, The zirconium-based MOF adsorbent material is an adsorbent material synthesized using zirconium chloride as the metal source and meso-2,3-dimercaptosuccinic acid as the organic ligand.
2. A method for preparing the zirconium-based MOF adsorbent material according to claim 1, characterized in that, The preparation method includes the following steps: Zirconium chloride, meso-2,3-dimercaptosuccinic acid, and formic acid were mixed, and then deionized water was added. The mixture was stirred at room temperature and refluxed. The resulting solid was washed and dried to obtain the zirconium-based MOF adsorbent material.
3. The method for preparing the zirconium-based MOF adsorbent material according to claim 2, characterized in that, The amount of zirconium chloride used is 1.165 g; the amount of meso-2,3-dimercaptosuccinic acid used is 0.91 g; and the amount of formic acid used is 0.28~0.42 mL.
4. The method for preparing the zirconium-based MOF adsorbent material according to claim 2, characterized in that, The stirring time at room temperature is 15-30 minutes.
5. The method for preparing the zirconium-based MOF adsorbent material according to claim 2, characterized in that, The reflux temperature is 95°C, and the time is 10~12h.
6. The method for preparing the zirconium-based MOF adsorbent material according to claim 2, characterized in that, The drying temperature is 100℃ and the time is 24 hours.
7. An application of the zirconium-based MOF adsorbent material according to claim 1, characterized in that, Used for the adsorption and separation of precious metals Pt, Rh, and Pd.
8. A method for adsorbing and separating noble metals Pt, Rh, and Pd using the zirconium-based MOF adsorbent material as described in claim 1, characterized in that, The method is any one of paths (1)-(3): (1) Add zirconium-based MOF adsorbent to the solution to be treated. During the treatment time and temperature, Pt in the solution is selectively adsorbed. After solid-liquid separation, the zirconium-based MOF adsorbent that adsorbs Pt is placed in a thiourea hydrochloric acid solution for desorption treatment to obtain a thiourea hydrochloric acid solution containing Pt. Then, hydrazine hydrate is added to it, the precipitate is collected by filtration, and pure noble metal Pt is obtained by calcination. (2) Add zirconium-based MOF adsorbent to the solution to be treated. During the treatment time and temperature, Pd in the solution is selectively adsorbed. After solid-liquid separation, the zirconium-based MOF adsorbent that adsorbs Pd is placed in a thiourea hydrochloric acid solution for desorption treatment to obtain a thiourea hydrochloric acid solution containing Pd. Then, hydrazine hydrate is added to it, the precipitate is collected by filtration, and pure noble metal Pd is obtained by calcination. (3) Add zirconium-based MOF adsorbent to the solution to be treated. Under the treatment time and temperature, Pd and Pt in the solution are selectively adsorbed. After solid-liquid separation, adsorbent A containing Pd and Pt and solution B containing Pt and Rh are obtained. Adsorbent A containing Pd and Pt contains 100% Pd and 50% to 60% Pt. It is placed in thiourea hydrochloric acid solution for desorption treatment to obtain thiourea hydrochloric acid solution containing Pd and Pt. Then, resin is added to adsorb Pd to achieve the separation of Pd and Pt. Solution B containing Pt and Rh contains 40% to 50% Pt and 100% Rh. Zirconium-based MOF adsorbent is added to it again. Under the treatment time and temperature, adsorbent C containing Pt and solution D containing Rh are obtained. Solution D containing Rh is reduced with hydrazine hydrate to obtain metal Rh. Adsorbent C containing Pt is placed in thiourea hydrochloric acid solution for desorption treatment to obtain noble metal Pt.
9. The method for adsorbing and separating noble metals Pt, Rh, and Pd using zirconium-based MOF adsorbent materials according to claim 8, characterized in that, The processing temperature is 20~50℃.
10. The method for adsorbing and separating noble metals Pt, Rh, and Pd using zirconium-based MOF adsorbent materials according to claim 8, characterized in that, The processing time is 12 hours.