Silica surface modification reactions with aluminum and boron alkyls and (alkyl) chlorides: reactivities and surface nanostructures.
The functionalization of nanoporous and nanoparticulate silica surfaces requires a molecular level understanding of the chemistry and structures which result from surface reactions. Various types of reactive groups on silica can participate, giving rise to different nanostructures. It is necessary to devise methods to alter the reactive nature of silica surfaces to control the nanoscale chemical structure. Various silica pretreatments are utilized to alter the silica surface prior to reaction with AlEt3, AlEtxCl(3-x), BEt3, BCl3, and TiCl4. Reactivities of these surface reactive reagents are compared. Aluminum compounds preferentially react with loss of alkane rather than HCl, in a thermodynamically controlled reaction as determined by ab initio computational methods. Consideration of the structures resulting from reaction of the boron and aluminum compounds above with silica surface diols has been taken into account. Particular attention has been paid to the possibility of forming a cyclic 4-membered ring structure. While this is unlikely to form from reactions with MCl3, such structures may be possible when reacting silicas with MMe3.
Blitz
Jonathan P
JP
Department of Chemistry, Eastern Illinois University, Charleston, IL 61920, USA.
Christensen
Jeannine M
JM
Deakyne
Carol A
CA
Gunko
Vladimir M
VM