Porous composite particulate materials, methods of making and using same, and related apparatuses

Abstract

In an embodiment, a porous composite particulate material includes a plurality of composite particles. Each composite particle includes an acid-base-resistant core particle at least partially surrounded by one or more layers of acid-base-resistant shell particles. The shell particles are adhered to the core particle by a polymeric layer. The shell particles and/or core particles may be made from an acid-base-resistant material that is stable in harsh chemical conditions. For example, the shell particles and/or core particles may be made from diamond, graphitic carbon, silicon carbide, boron nitride, tungsten carbide, niobium carbide, zirconia, noble metals, acid-base stable highly cross-linked polymers, acid-base stable at least partially cross-linked polymers, titania, alumina, thoria combinations of the foregoing, or other acid-base-resistant materials. The porous composite particulate materials disclosed herein and related methods and devices may be used in separation technologies, including, but not limited to, chromatography and solid phase extraction.

What is claimed is: 
     
         1 . A porous composite particulate material, comprising:
 a plurality of composite particles, at least some the plurality of composite particles including:   an acid-base-resistant core particle;   a plurality of acid-base-resistant shell particles at least partially surrounding the acid-base-resistant core particle, wherein the plurality of acid-base-resistant shell particles include at least one of diamond or graphitic carbon; and   at least one polymer that is acid-base-resistant and exhibits about 1% to about 99% cross-linking, the plurality of acid-base-resistant shell particles bonded together by the at least one polymer.   
     
     
         2 . The porous composite particulate material of  claim 1 , wherein each of the acid-base-resistant core particles of the at least some of the plurality of composite particles includes diamond or graphic carbon. 
     
     
         3 . The porous composite particulate material of  claim 1 , wherein each of the acid-base-resistant core particles of the at least some of the plurality of composite particles includes diamond, and wherein each of the plurality of acid-base-resistant shell particles of the at least some of the plurality of composite particles includes graphitic carbon. 
     
     
         4 . The porous composite particulate material of  claim 1 , wherein:
 at least a portion of the acid-base-resistant core particles of the at least some of the plurality of composite particles include an inner region that is acid-base unstable and a cladding that is acid-base resistant; and   the cladding includes diamond, graphitic carbon, silicon carbide, boron nitride, tungsten carbide, niobium carbide, or combinations thereof.   
     
     
         5 . The porous composite particulate material of  claim 1 , wherein the cross-linking includes a carbon-nitrogen bond. 
     
     
         6 . The porous composite particulate material of  claim 1 , wherein:
 the cross-linking includes a cross-linking agent having two or more functional groups, wherein at least one of the functional groups is selected from the group consisting of an isocyanate, an epoxide, an alkyl halide, and an acid halide; and   the two or more functional groups include at least one of diisocyanates, diisothiocyanates, dihalides, diglycidyl ethers, diepoxides, dianhydrides, dialdehydes, diacrylates, dimethacrylates, dimethylesters, diacrylates, triacrylates, dimethacrylates, trimethacrylates, or diesters.   
     
     
         7 . The porous composite particulate material of  claim 1 , wherein the at least one polymer exhibits less than 85% cross-linking. 
     
     
         8 . The porous composite particulate material of  claim 1 , wherein the cross-linking of the cross-linked polymer is about 55% to about 75%. 
     
     
         9 . The porous composite particulate material of  claim 1 , wherein the at least one polymer includes at least one amine polymer. 
     
     
         10 . The porous composite particulate material of  claim 1 , wherein at least one polymer includes polyallylamine, polyethylenimine, polylysine, polyvinylamine, chitosan, trimethylchitosan, polydiallydimethyl ammonium chloride, poly(N,N′-dimethylaminoethylmethacrylate), poly(2-vinylpyridine), poly(4-vinylpyridine), polyvinylimidazole, poly(2-(dimethylamino)ethyl acrylate), poly(2-aminoethyl methacrylate) hydrochloride, combinations of any of the foregoing, or derivatives of any of the foregoing. 
     
     
         11 . A separation apparatus, comprising:
 a vessel; and   a porous composite particulate material supported by the vessel, the porous composite particulate material including,
 a plurality of composite particles, at least some of the plurality of composite particles including,
 an acid-base-resistant core particle; 
 a plurality of acid-base-resistant shell particles, wherein the plurality of acid-base-resistant shell particles include at least one of diamond or graphitic carbon; and 
 at least one polymer that is acid-base-resistant and exhibits about 1% to about 99% cross-linking, the plurality of acid-base-resistant shell particles bonded together by the at least one polymer. 
 
   
     
     
         12 . The separation apparatus of  claim 11 , wherein each of the acid-base resistant core particles of the at least some of the plurality of composite particles includes graphitic carbon or diamond. 
     
     
         13 . The separation apparatus of  claim 11 , wherein each of the acid-base-resistant core particles of the at least some of the plurality of composite particles includes diamond, and wherein each of the plurality of acid-base-resistant shell particles of the at least some of the plurality of composite particles includes graphitic carbon. 
     
     
         14 . The separation apparatus of  claim 11 , wherein the at least one polymer exhibits less than 85% cross-linking. 
     
     
         15 . The separation apparatus of  claim 11 , wherein the at least one polymer exhibits about 55% to about 75% cross-linking. 
     
     
         16 . The separation apparatus of  claim 11 , wherein the at least one polymer includes at least one amine polymer. 
     
     
         17 . The separation apparatus of  claim 11 , wherein:
 the at least one polymer includes at least one of polyallylamine, polyethylenimine, polylysine, polyvinylamine, chitosan, trimethylchitosan, polydiallydimethyl ammonium chloride, poly(N,N′-dimethylaminoethylmethacrylate), poly(2-vinylpyridine), poly(4-vinylpyridine), polyvinylimidazole, poly(2-(dimethylamino)ethyl acrylate), poly(2-aminoethyl methacrylate) hydrochloride, combinations of any of the foregoing, or derivatives of any of the foregoing; and   the cross-linking includes a polymerized cross-linking agent having at least one of diisocyanates, diisothiocyanates, dihalides, diglycidyl ethers, diepoxides, dianhydrides, dialdehydes, diacrylates, dimethacrylates, dimethylesters, diacrylates, triacrylates, dimethacrylates, trimethacrylates, diesters, or combinations of any of the foregoing.   
     
     
         18 . A method for using a porous composite particulate material, the method comprising:
 providing a separation apparatus, the separation apparatus including:
 a vessel; and 
 a porous composite particulate material disposed in the vessel, the porous composite particulate material having a plurality of composite particles, at least some of the plurality of composite particles including:
 an acid-base-resistant core particle; 
 a plurality of acid-base-resistant shell particles, wherein the plurality of acid-base-resistant shell particles include at least one of diamond or graphitic carbon; and 
 at least one polymer that is acid-base-resistant and exhibits about 1% to about 99% cross-linking, the plurality of acid-base-resistant shell particles bonded together by the at least one polymer; and 
 
   flowing a mobile phase through the porous composite particulate material to physically separate at least two different components of the mobile phase.   
     
     
         19 . The method of  claim 18 , wherein the vessel is configured as a chromatography column. 
     
     
         20 . The method of  claim 18 , further comprising cleaning the porous composite particulate material by flowing a cleaning solvent through the porous composite particulate material. 
     
     
         21 . The method of  claim 20 , wherein at least one of the cleaning solvent or the mobile phase has a pH greater than about 10 or a pH less than about 2. 
     
     
         22 . The method of  claim 18 , wherein each of the acid-base-resistant core particles of the at least some of the plurality of composite particles includes diamond, wherein each of the plurality of acid-base-resistant shell particles of the at least some of the plurality of composite particles includes graphitic carbon, and wherein the at least one polymer includes at least one amine polymer.