Multifunctional porous aramids (aerogels), fabrication thereof, and catalytic compositions derived therefrom

A process for carbonizing a carbonizable polymeric aerogel incorporating ferrocene in every repeating unit, wherein said polymeric aerogel comprises the following repeating units:

• wherein:
• G represents a group selected from awl, (aryl)-R-(aryl), and (aryl)-R-(aryl)2;
• where each aryl independently represents an optionally substituted aromatic ring;
• and where R is a bond or a C1-C6 straight chain or branched chain alkyl group;
• G2 represents a ferrocenyl moiety;
• (*) denotes a linkage point;
• and,
• wherein the polymeric aerogel includes a mixture of polyamide and polyurea;
• said process comprising the step of pyrolizing the polymeric aerogel at temperatures in the range 500-2300° C. to yield a nanoporous product that includes iron-doped carbon-monoliths containing Fe(0) nanoparticles in graphitic pockets dispersed throughout the 3D matrix of monolithic nanoporous carbon.

A composition of matter comprising M-doped carbon monoliths obtained by the following process steps:

• (a) carbonizing a polymeric aerogel incorporating ferrocene in every repeating unit by pyrolizing said polymeric aerogel at temperatures in the range 500-2300° C. to yield a nanoporous product that includes iron-doped carbon-monoliths containing Fe(0) nanoparticles in graphitic pockets dispersed throughout a 3D matrix of monolithic nanoporous carbon;
• and,
• (b) partially or completely transmetalating the iron-doped carbon-monoliths by dipping the nanoporous product that includes the iron-doped carbon monoliths in solutions of metal ions to produce the M-doped carbon monoliths;
• wherein M is one or more metals selected from the group of metals consisting of Fe, Au, Pt, Pd, Co, Ni, Ru, and Rh;
• wherein said polymeric aerogel comprises the following repeating units:
• wherein:
• G represents a group selected from aryl, (aryl)-R-(aryl), and (aryl)-R-(aryl)2;
• where each aryl independently represents an optionally substituted aromatic ring;
• and where R is a bond or a C1-C6 straight chain or branched chain alkyl group;
• G2 represents a ferrocenyl moiety;
• (*) denotes a linkage point and,
• wherein the polymeric aerogel includes a mixture of polyamide and polyurea.

A method of catalysis of a chemical reaction in a mixture, the method comprising the step of contacting the mixture with a catalytic amount of a composition of matter comprising M-doped carbon monoliths obtained by the following steps:

• (a) carbonizing a polymeric aerogel incorporating ferrocene in every repeating unit by pyrolizing said polymeric aerogel at temperatures in the range 500-2300° C. to yield a nanoporous product that includes iron-doped carbon-monoliths containing Fe(0) nanoparticles in graphitic pockets dispersed throughout a 3D matrix of monolithic nanoporous carbon;
• and,
• (b) partially or completely transmetalating the iron-doped carbon-monoliths by dipping the nanoporous product that includes the iron-doped carbon monoliths in solutions of metal ions to produce the M-doped carbon monoliths;
• wherein M is one or more metals selected from the group of metals consisting of Fe, Au, Pt, Pd, Co, Ni, Ru, and Rh;
• and, wherein said polymeric aerogel comprises the following repeating units:
• wherein:
• G represents a group selected from awl, (aryl)-R-(aryl), and (aryl)-R-(aryl)2;
• where each aryl independently represents an optionally substituted aromatic ring;
• and where R is a bond or a C1-C6 straight chain or branched chain alkyl group;
• G2 represents a ferrocenyl moiety;
• (*) denotes a linkage point and,
• wherein the polymeric aerogel includes a mixture of polyamide and polyurea.