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CN-121975076-A - Preparation of guanidinium ion type porous organic polymer and application of guanidinium ion type porous organic polymer in extraction of gold from water

CN121975076ACN 121975076 ACN121975076 ACN 121975076ACN-121975076-A

Abstract

Preparation of guanidyl ion type porous organic polymer and application of guanidyl ion type porous organic polymer in extracting gold from water belong to the relevant fields of porous organic polymer materials and the like. The organic connector based on ionic guanidine hydrochloride monomer reacts with the benzimidazole derivative ligand (BDBI) substituted by aromatic ring to obtain the guanidine-based porous ionic polymer material (PiP-1), and the guanidine-based porous ionic polymer material is respectively applied to adsorption removal of gold ions in solution, has extremely high saturated adsorption capacity, shows rapid adsorption kinetics, high selectivity and recyclability, and has potential of gold adsorption in practical application.

Inventors

  • WANG SHITAO
  • HE BINCHENG
  • CAO DAPENG

Assignees

  • 北京化工大学

Dates

Publication Date
20260505
Application Date
20240801

Claims (10)

  1. 1. A preparation method of a guanidino ion type porous organic polymer material is characterized by comprising the following steps of adding a triamino guanidine hydrochloride TG Cl and an aromatic ring substituted benzimidazole derivative ligand BDBI into a solvent for ultrasonic dispersion uniformly, then adding an AcOH aqueous solution as a catalyst for ultrasonic mixing uniformly, then carrying out freeze-vacuum-thawing circulation, heating up under a sealing condition to react completely, filtering, washing, carrying out cable extraction purification and vacuum drying on a product to obtain the guanidino ion type porous organic polymer material PiP-1; The aromatic ring substituted benzimidazole derivative ligand (BDBI) has the structural formula: wherein Represents an aromatic ring and an O/S/Se/N aromatic heterocycle, wherein the aromatic ring is benzene, biphenyl, naphthalene, anthracene or phenanthrene; the substituent X on PiP-1 is a different anion, F, cl, br, I or other anions.
  2. 2. The method according to claim 1, characterized in that: Selected from the group consisting of 。
  3. 3. The method of claim 1, wherein the three amino guanidine hydrochloride TG Cl is used as a connector, and the guanidine-based porous ionic polymer material has the following structural formula: 。
  4. 4. The method according to claim 1 or 2, characterized in that: The molar ratio of the triaminoguanidine hydrochloride TG Cl to the aromatic ring-substituted benzimidazole derivative ligand BDBI is 1-10:1, preferably 2:3; wherein the reaction solvent is a mixed solvent of N, N-dimethylacetamide and o-dichlorobenzene, and the volume ratio of the N, N-dimethylacetamide to the o-dichlorobenzene is 1-9: 9~1 (preferably 1:1); The concentration of the AcOH solution added is 3 mol/L to 12 mol/L, preferably 6 mol/L.
  5. 5. The method according to claim 1 or 2, wherein in the step (1), the ultrasonic time is 1-30 min, and the freezing-vacuum-thawing cycle is performed by freezing the reactant with liquid nitrogen, evacuating, and thawing with nitrogen gas, and the sealing reaction is performed under nitrogen atmosphere or vacuum condition.
  6. 6. The method according to claim 1 or 2, wherein the temperature is raised to 40-200 ℃ and the reaction time is 1-10 days.
  7. 7. The method according to claim 1 or 2, wherein after filtration, dichloromethane, 1, 4-dioxane and tetrahydrofuran are sequentially used for washing, then organic solvent is used for Soxhlet extraction for 1-5 days, and finally the guanidino ionic covalent organic framework material is obtained through vacuum drying.
  8. 8. A guanidinium ionic porous organic polymeric material obtainable by the process according to claim 1 or 2.
  9. 9. Use of a guanidinium-ion porous organic polymer material obtainable by a process according to claim 1 or 2 for the adsorptive removal of gold ions from a solution or for the separation of gold ions from a plurality of metal ions.
  10. 10. The method according to claim 9, wherein said guanidinium ionic porous organic polymer material is added to a composition comprising Au ) Mixing and stirring the solution and adsorbing gold ions therein.

Description

Preparation of guanidinium ion type porous organic polymer and application of guanidinium ion type porous organic polymer in extraction of gold from water Technical Field The invention belongs to the field of porous organic polymer materials, and particularly relates to preparation of a novel guanidinium ion type porous organic polymer material, wherein the porous organic polymer can be used for adsorbing and removing gold ions in water. Background Gold (Au) is a rare noble metal, and has been widely used in the fields of electronic devices, catalysis, and the like due to its excellent physicochemical properties. The separation of gold from ores is complex and generally requires the use of highly toxic cyanide which can cause serious environmental pollution and high energy consumption (angel. Chem. Int. Ed. 2017, 56, 9331-9335). The recovery of gold from waste electronic devices can avoid great waste of resources and is beneficial to environmental protection. The traditional pyrometallurgy has high energy consumption and serious pollution, the recovery of gold from waste electronic equipment by adopting hydrometallurgy is simpler, gold in the electronic equipment is leached into Au (III) ions by acid liquor or alkali liquor, and then separation and purification are carried out by a coprecipitation method, a solvent extraction method, an ion exchange method, an adsorption method and the like. The coprecipitation method and the solvent extraction method are easy to produce secondary pollution, the ion exchange method is complex in operation and high in cost, the adsorption method is simple in operation and low in cost, and the method is widely applied to the field of precious metal recovery. Many adsorbents such as activated carbon and ion exchange resins have been developed. However, these adsorbents have problems of slow adsorption kinetics, poor selectivity, poor recoverability, and the like (macromol. Mater. Eng. 2022, 307, 2100761). Metal organic framework Materials (MOFs) have also been used as adsorbents, but have poor water stability and may leach out metal ions causing secondary pollution (angel. Chem. Int. Ed. 2024, e 202402205). Therefore, the development of a novel adsorbent with high selectivity, high stability and fast adsorption kinetics is of great significance for removing hardware fittings in wastewater. The porous organic polymer (Porous organic polymers, POPs) is an organic material with a regular pore structure, which is formed by connecting light elements such as C, H, O, N, S through covalent bonds, has good stability and strong designability, and is widely applied to the fields of adsorption separation, sensing, semiconductors, catalysis and the like. The ionic covalent organic frameworks (Ionic covalent organic frameworks, iCOFs) and the porous ionic polymers (Porous ionic polymers, piPs) are used as important branches of POPs, positive/negative charges of the ionic covalent organic frameworks are fixed on the frameworks, target ions are absorbed and captured through electrostatic interaction, and the specific surface area, the pore structure and the pore channel internal environment of the ionic covalent organic frameworks can be changed by adjusting the counter ions of the ionic covalent organic frameworks, so that the ionic covalent organic frameworks have high designability, and are widely applied to the fields of noble metal recovery, pollutant absorption removal and the like. However, there are few reports of the application of iCOFs and PiPs materials to capture gold ions. The three nitrogen atoms of guanidine are combined with the central carbon atom of cation, so that the guanidine has positive delocalized charge and strong anion combination capacity. By introducing guanidine groups into the backbone, its ability to capture Au can be effectively enhanced. Therefore, two types of guanidinium ionic porous organic polymer materials, namely cationic covalent organic framework materials Ionic-COFs and porous ionic polymer PiP-1, are synthesized by taking ionic guanidine hydrochloride as an organic connector and utilizing charged active N + sites of the ionic guanidine hydrochloride. Ionic-COFs show extremely high gold adsorption capacity, have rapid adsorption kinetics, excellent selectivity and recyclability, and can successfully recover gold from a CPU with high efficiency. This work shows that Ionic-COFs can be a useful platform for high performance gold recovery. Compared with Ionic-COFs, the PiP-1 material skeleton has higher charge density and thus higher adsorption capacity. So far, few researches on the PiPs material applied to gold ion capture are reported, and the invention provides a new idea for the PiPs material applied to the gold recovery field. At present, no research report or patent disclosure is found at home and abroad on the application of the guanidyl ion type porous organic polymer material in adsorbing and removing gold ions in wastewater. Disclosure of Inv