A process for gas-phase synthesis of titanium dioxide aerosol gels with controlled monomer size and crystalline phase using a diffusion flame aerosol reactor operated in a buoyancy-opposed configuration is disclosed. The process includes introducing a precursor stream into a diffusion flame aerosol reactor, introducing a fuel stream into the reactor, combusting the precursor stream and the fuel stream in a flame to form at least one nanoparticle, and operating the reactor in a down-fired buoyancy-opposed configuration to produce the aerosol gel.