It’s hard to choose just one substance, mainly due to the idea of “more flammable” being poorly defined. But there are some strong contenders.
Pure hydrogen peroxide is flammable enough to burst into flames without any heat source needed. Pure sodium added to water will sizzle and throw off heat even if the water was cold. Methane is highly flammable, but there is a similar silicon-based gas called silane that is more flammable.
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