A thermal protection system is disclosed herein. In various aspects, the thermal protection system includes an insert. The insert may include a first layer and a second layer bonded to one another. The insert may be removeably receivable within a cavity of a shoe to form a thermally insulating barrier between a plantar surface of a user's foot and a sole of the shoe with a side of the first layer oriented toward the sole and a side of the second layer oriented toward the plantar surface. The first layer may include an aerogel and the second layer may include a meta aramid polymer, in various aspects. Related compositions of matter disclosed herein, in various aspects, include a plurality of layers bonded to one another in the form of an insert removeably receivable within a cavity of a shoe to create a thermal barrier between a sole of the shoe and a plantar surface of a foot of a user. This Abstract is presented to meet requirements of 37 C.F.R. § 1.72(b) only, and is not intended to identify key elements of the apparatus, methods, and compositions of matter disclosed herein or to delineate the scope thereof.