Polymeric complex supporter with zero-valent metals and manufacturing method thereof

Abstract

A zero-valent metal polymeric complex supporter (ZVM-PCS) is disclosed. The PCS possesses porous surface and internal coralloid-like channel structure that can accommodate high amount of iron-containing materials and derivatives thereof. The surface pore size, porosity, hydrophilicitv, and internal coralloid-like channel structure of PCS can be tailored through the manufacturing process, with which PCS can be functioned as a regulator for the releasing of produced hydrogen, and also control the adsorption and reactions toward heavy metals and chlorinated volatile organic compounds in water. The hydrogen released from the ZVM-PCS can be applied to anaerobic bioremediation. Moreover, the ZVM-PCS can be filter materials that can be installed in a column or any storage for water and wastewater treatment, or even in a groundwater cut-off barrier for the cleanup of contamination. While the ZVM-PCS is synthesized as a film without surface openings, it can be used as the electromagnetic interference (EMI) shielding material.

1 . A zerovalent metal-polymer complex supporter (ZVM-PCS), comprising:
 1 part to 92 parts by weight of iron-containing materials and derivatives thereof, wherein the iron-containing materials and derivatives thereof comprises zero-valent irons and has an averaged diameter from 1 nanometer (nm) to 10 micrometers μm); and   8 parts to 99 parts by weight of polymer complex supporter (PCS), wherein the PCS and the iron-containing materials and derivatives thereof are mixed well, the PCS possesses an internal coralloid-like channel structure and surface pores with an averaged pore size from 1 nm to 100 μm, and   wherein as the ZVM-PCS is delivered into a water-containing environment, water molecules and pollutants can diffuse into the internal coralloid-like channel structure through the surface pores and then react with the iron-containing materials and derivatives thereof, so as to adsorb and/or degrade the pollutants and continuously release out hydrogen through the surface pores, thereby enhancing anaerobic bioremediation process in the water-containing environment.   
     
     
         2 . The ZVM-PCS according to  claim 1 , wherein the iron-containing materials and derivatives thereof further comprises precious metals to coat on the zero-valent irons, and the precious metals are selected from the group consisting of platinum, palladium, rhodium, gold, silver, cobalt and any combination thereof. 
     
     
         3 . The ZVM-PCS according to  claim 1 , wherein the amount of the iron-containing materials and derivatives thereof in PCS is from 10 parts to 92 parts by weight. 
     
     
         4 . The ZVM-PCS according to  claim 1 , wherein the pollutants is heavy metal pollutants, organohalogen compounds or nitrates, and the heavy metal pollutants comprises arsenic or chromium, and the organohalogen compounds comprises chlorinated volatile organic compounds (CVOCs), trichloroethylene (TCE), perchloroethylene (PCE) or dioxins. 
     
     
         5 . The ZVM-PCS according to  claim 1 , wherein polymers belong to sulfone polymers or fluorine-containing polymers, and the amount of the polymers is 8 parts to 50 parts by weight. 
     
     
         6 . The ZVM-PCS according to  claim 5 , wherein the sulfone polymers are selected from the group consisting of polyethersulfone (PESF), polysulfone (PSF) and polyphenylene sulfone (PPSF). 
     
     
         7 . The ZVM-PCS according to  claim 6 , wherein the fluorine-containing polymer is polyvinylidene fluoride (PVDF). 
     
     
         8 . The ZVM-PCS according to  claim 1 , further comprising absorbent materials, wherein the amount of the absorbent materials in the ZVM-PCS is 0.01 part to 35 parts by weight, and the absorbent materials are selected from the group consisting of activated carbon, zeolite, molecular sieve and any combination thereof. 
     
     
         9 . The ZVM-PCS according to  claim 1 , further comprising heat dispersing materials, wherein the amount of the heat dispersing materials in the ZVM-PCS is 0.01. part to 35 parts by weight, and the heat dispersing materials are selected from the group consisting of boron nitride, carbon nanotubes and any combination thereof. 
     
     
         10 . The ZVM-PCS according to  claim 1 , further comprising bionutrients, wherein the amount of the bionutrients in the ZVM-PCS is 0.01 part to 35 parts by weight, and the bionutrients are selected from the group consisting of sugar, starch and any combination thereof. 
     
     
         11 . The ZVM-PCS according to  claim 1 , further comprising dispersants, wherein the amount of the dispersants in the ZVM-PCS is 0.1 part to 2 parts by weight, and the dispersants are selected from the group consisting of polycarbonate, polyvinyl alcohol, polyacrylamide and any combination thereof. 
     
     
         12 . The ZVM-PCS according to  claim 1 , wherein the water-containing environment refers to ocean, river, lake, sewerage, ditch, aquifer, cistern, sludge or soil. 
     
     
         13 . A method for manufacturing ZVM-PCS, comprising:
 preparing a mixture, wherein the mixture comprises:
 1 part to 99 parts by weight of iron-containing materials and derivatives thereof, wherein the iron-containing materials and derivatives thereof comprise zero-valent irons and have an averaged diameter from 1 nm to 10 μm; and 
 8 parts to 99 parts by weight of polymers, wherein the polymers belong to sulfone polymers or fluorine-containing polymers; and 
 an organic solvent to dissolve the polymers and to disperse the iron-containing materials and derivatives thereof uniformly wherein the organic solvent is selected from the group consisting of N,N-dimethyl formamide (DMF), 1-methyl 2 pyrrolidione (NMP) and N,N-dimethylacetamide (DMAc); 
   conducting a vacuuming step to remove air bubbles in the mixture; and   conducting a forming and functionalizing step, wherein the forming and functionalizing step comprises:
 performing a wet-forming and functionalizing step, the as-synthesized material is performed in a coagulating solvent in a temperature range from 0° C. to 40° C. for 0.5 minute to 5 minutes, which removes part of the organic solvent and forms a complex. The coagulating solvents are selected from the group consisting of methanol, ethanol, propanol, acetone, water and any combination thereof; and 
 performing a dry-forming and functionalizing step, to keep the composite material to be dried in a temperature of 90° C. to 150° C. for 15 minutes to 30 minutes, so as to remove a residue of the organic solvent and the coagulant and to form the ZVM-PCS that accommodates the iron-containing materials and derivatives thereof, and the ZVM-PCS has a thickness of 1 μm to 1000 μm. 
   
     
     
         14 . The method for manufacturing ZVM-PCS according to  claim 13 , wherein an amount of the iron-containing materials and derivatives thereof in the ZVM-PCS is 50 parts to 92 parts by weight. 
     
     
         15 . The method for manufacturing ZVM-PCS according to  claim 13 , wherein the iron-containing materials and derivatives thereof further comprises precious metals to coat on the zero-valent irons, and the precious metals are selected from the group consisting of platinum, palladium, rhodium, gold, silver, cobalt and an combination thereof. 
     
     
         16 . The method for manufacturing ZVM-PCS according to  claim 13 , wherein the sulfone polymer is selected from the group consisting of PESF, PSF and PPSF, and an amount of the sulfone polymer in the ZVM-PCS is 8 parts to 50 parts by weight. 
     
     
         17 . The method for manufacturing ZVM-PCS according to  claim 13 , wherein the fluorine-containing polymer is PVDF, and an amount of the fluorine-containing polymer in the ZVM-PCS is 8 parts to 50 parts by weight. 
     
     
         18 . The method for manufacturing ZVM-PCS according to  claim 13 , wherein the mixture further comprises an absorbent material, an amount of the absorbent materials in the ZVM-PCS is 0.01 part to 35 parts by weight, and the absorbent material is selected from the group consisting of activated carbon, zeolite, molecular sieve and any combination thereof. 
     
     
         19 . The method for manufacturing ZVM-PCS according, to  claim 13 , wherein the mixture further comprises a heat dispersing material, an amount of the heat dispersing material in the ZVM-PCS is 0.01 part to 35 parts by weight, and the heat dispersing material is selected from the group consisting of boron nitride, carbon nanotubes and any combination thereof. 
     
     
         20 . The method for manufacturing ZVM-PCS according to  claim 13 , wherein the mixture further comprises a bionutrient, an amount of the bionutrients in the ZVM-PCS is 0.01 part to 35 parts by weight, and the bionutrients is selected from the group consisting of sugar, starch, phosphate and any combination thereof. 
     
     
         21 . The method for manufacturing ZVM-PCS according to  claim 13 , wherein the mixture further comprises a dispersant, an amount of the dispersant in the ZVM-PCS is 0.1 part to 2 parts by weight, and the dispersant is selected from the group consisting of polycarbonate, polyvinyl alcohol, polyacrylamide and any combination thereof. 
     
     
         22 . The method for manufacturing ZVM-PCS according to  claim 13 , wherein the ZVM-PCS has a flake-like, granule-like, a hollow tube-like or a rod-like shape. 
     
     
         23 . The method for manufacturing ZVM-PCS according to  claim 13 , further comprising:
 conducting a coating step to keep the mixture being formed on a substrate, wherein the coating step is a spin-on coating step or a blade coating step.   
     
     
         24 . The method for manufacturing ZVM-PCS according to  claim 23 , wherein the ZVM-PCS is shaped as a thin film, a granule, a hollow tube or a rod. 
     
     
         25 . The method for manufacturing ZVM-PCS according to  claim 13 , wherein the vacuuming step is performed for 10 minutes to 30 minutes. 
     
     
         26 . The method for manufacturing ZVM-PCS according to  claim 13 , wherein the method for manufacturing the ZVM-PCS is performed in a batch process or an automatically continuous process. 
     
     
         27 . The method for manufacturing ZVM-PCS according to  claim 13 , wherein the PCS possesses an internal coralloid-like channel structure and a porous surface with an averaged pore size from 1 nm to 100 μm, and as the ZVM-PCS is immersed in a water-containing environment, water molecules and pollutants can diffuse into the internal coralloid-like channel structure through the surface pores and then contact with the iron-containing materials and derivatives thereof, so as to adsorb and/or degrade the pollutants and continuously release out hydrogen through the surface pores, thereby enhancing anaerobic bioremediation process in the water-containing environment. 
     
     
         28 . The method for manufacturing ZVM-PCS according to  claim 27 , wherein the water-containing environment refers to ocean, river, lake, sewerage, ditch, aquifer, cistern, sludge or soil. 
     
     
         29 . The method for manufacturing LVM-PCS according to  claim 27 , wherein the pollutants is heavy metal pollutants, organohalogen compounds or nitrates, and the heavy metal pollutants comprises arsenic or chromium, and the organohalogen compounds comprises chlorinated volatile organic compounds (CVOCs), trichloroethylene (TCE), perchloroethylene (PCE) or dioxins. 
     
     
         30 . A method for manufacturing ZVM-PCS, comprising:
 preparing a mixture, wherein the mixture comprises:
 1 part to 99 parts by weight of iron-containing materials and derivatives thereof, wherein the iron-containing materials and derivatives thereof comprise zero-valent irons and have an averaged diameter from 1 nm to 10 μm; and 
 8 parts to 99 parts by weight of polymers, wherein the polymers belong to sulfone polymers or fluorine-containing polymers; and 
 an organic solvent to dissolve the polymers and to disperse the iron-containing materials and derivatives thereof uniformly wherein the organic solvent is selected from the group consisting of N,N-dimethyl formamide (DMF), 1-methyl 2 pyrrolidione (NMP) and N,N-dimethylacetamide (DMAc); 
   conducting a vacuuming step to remove air bubbles in the mixture; and   performing a dry-forming and functionalizing step, to keep the composite material to be dried in a temperature of 90° C. to 150° C. for 15 minutes to 30 minutes, so as to remove a residue of the organic solvent and the coagulant and to form the ZVM-PCS that accommodates the iron-containing materials and derivatives thereof, and the ZVM-PCS is flexible and has a dense non-porous structure with thickness from 1 μm to 1000 μm.   
     
     
         31 . The method for manufacturing ZVM-PCS according to  claim 30 , wherein an amount of the iron-containing materials and derivatives thereof in the ZVM-PCS is 50 parts to 92 parts by weight. 
     
     
         32 . The method for manufacturing ZVM-PCS according to  claim 30 , wherein the iron-containing materials and derivatives thereof further comprises precious metals to coat on the zero-valent irons, and the precious metals are selected from the group consisting of platinum, palladium, rhodium, gold, silver, cobalt and any combination thereof. 
     
     
         33 . The method for manufacturing ZVM-PCS according to  claim 30 , wherein the sulfone polymer is selected from the group consisting of PESF, PSF and PPSF, and an amount of the sulfone polymer in the ZVM-PCS is 8 parts to 50 parts by weight. 
     
     
         34 . The method for manufacturing ZVM-PCS according to  claim 30 , wherein the fluorine-containing polymer is PVDF, and an amount of the fluorine-containing polymer in the ZVM-PCS is 8 parts to 50 parts by weight. 
     
     
         35 . The method for manufacturing ZVM-PCS according to  claim 30 , wherein the mixture further comprises a heat dispersing material, an amount of the heat dispersing material in the ZVM-PCS is 0.01 part to 35 parts by weight, and the heat dispersing material is selected from the group consisting of boron nitride, carbon nanotubes and any combination thereof. 
     
     
         36 . The method for manufacturing ZVM-PCS according to  claim 30 , wherein the mixture further comprises a dispersant, an amount of the dispersant in the ZVM-PCS is 0.1 part to 2 parts by weight, and the dispersant is selected from the group consisting of polycarbonate, polyvinyl alcohol, polyacrylamide and any combination thereof. 
     
     
         37 . The method for manufacturing ZVM-PCS according to claim.  30 , wherein the ZVM-PCS has a flake-like shape. 
     
     
         38 . The method for manufacturing ZVM-PCS according to  claim 30 , further comprising:
 conducting a coating step to keep the mixture being formed on a substrate, wherein the coating step is a spin-on coating step or a blade coating step.   
     
     
         39 . The method for manufacturing ZVM-PCS according to  claim 38 , wherein the ZVM-PCS is shaped as a thin film, a granule, a hollow tube or a rod. 
     
     
         40 . The method for manufacturing ZVM-PCS according to  claim 30 , wherein the vacuuming step is performed for 10 minutes to 30 minutes. 
     
     
         41 . The method for manufacturing ZVM-PCS according to  claim 30 , wherein the method for manufacturing ZVM-PCS is performed in a batch process or an automatically continuous process. 
     
     
         42 . An electromagnetic interference (EMI) shielding material obtained by the method of  claims 30 .