Response to Extreme Temperatures of Mesoporous Silica MCM-41: Porous Structure Transformation Simulation and Modification of Gas Adsorption Properties.

Molecular dynamics (MD) and Monte Carlo (MC) simulations were applied together for the first time to reveal the porous structure transformation mechanisms of mesoporous silica MCM-41 subjected to temperatures up to 2885 K. Silica was experimentally characterized to inform the models and enable prediction of changes in gas adsorption/separation properties. MD simulations suggest that the pore closure process is activated by a collective diffusion of matrix atoms into the porous region, accompanied by bond reformation at the surface. Degradation is kinetically limited, such that complete pore closure is postponed at high heating rates. We experimentally observe decreased gas adsorption with increasing temperature in mesoporous silica heated at fixed rates, due to pore closure and structural degradation consistent with simulation predictions. Applying the Kissinger equation, we find a strong correlation between the simulated pore collapse temperatures and the experimental values which implies an activation energy of 416 ± 17 kJ/mol for pore closure. MC simulations give the adsorption and selectivity for thermally treated MCM-41, for N2, Ar, Kr, and Xe at room temperature within the 1-10 000 kPa pressure range. Relative to pristine MCM-41, we observe that increased surface roughness due to decreasing pore size amplifies the difference of the absolute adsorption amount differently for different adsorbate molecules. In particular, we find that adsorption of strongly interacting molecules can be enhanced in the low-pressure region while adsorption of weakly interacting molecules is inhibited. This then results in higher selectivity in binary mixture adsorption in mesoporous silica.

Template-based syntheses for shape controlled nanostructures.

A variety of nanostructured materials are produced through template-based synthesis methods, including zero-dimensional, one-dimensional, and two-dimensional structures. These span different forms such as nanoparticles, nanowires, nanotubes, nanoflakes, and nanosheets. Many physical characteristics of these materials such as the shape and size can be finely controlled through template selection and as a result, their properties as well. Reviewed here are several examples of these nanomaterials, with emphasis specifically on the templates and synthesis routes used to produce the final nanostructures. In the first section, the templates have been discussed while in the second section, their corresponding synthesis methods have been briefly reviewed, and lastly in the third section, applications of the materials themselves are highlighted. Some examples of the templates frequently encountered are organic structure directing agents, surfactants, polymers, carbon frameworks, colloidal sol-gels, inorganic frameworks, and nanoporous membranes. Synthesis methods that adopt these templates include emulsion-based routes and template-filling approaches, such as self-assembly, electrodeposition, electroless deposition, vapor deposition, and other methods including layer-by-layer and lithography. Template-based synthesized nanomaterials are frequently encountered in select fields such as solar energy, thermoelectric materials, catalysis, biomedical applications, and magnetowetting of surfaces.