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What is best used for that purpose - leather?
I think so. For one thing it is part of the "lexicon," if you will, of the shoemaker. For another thing, a leather toe puff can be, literally, scrap from the floor--it's not an extra expense. And just incidentally, it is a natural product and not petro-chemical based. On the other hand, for a leather toe puff to be effective, it almost certainly needs to be sandwiched between a lining and the vamp. It is perhaps wise to remind ourselves that shoemaking has been a Trade for a long time...some theories have it as old as ten thousand years old. Most of the techniques of the traditional, bespoke maker have evolved and been refined...and the unworkable or awkward discarded...over many centuries. Highly evolved and very functional, as well as beautiful, shoes were being produced before the Industrial Age and well before the Age of Carbon Offsets and Dying Corral Reefs. Most of the so-called "improvements" in shoemaking techniques, and more importantly, in shoemaking materials arose and exist for the sole purpose of making things faster and cheaper--expediency, in other words. And in my estimation, I can't think of a single technique or substance that, replacing traditional skills or sources, has been a significant or even noteworthy improvement. Not a one.