Fast and Long‐Lasting Iron(III) Reduction by Boron Toward Green and Accelerated Fenton Chemistry

Generation of hydroxyl radicals in the Fenton system (FeII/H2O2) is seriously limited by the sluggish kinetics of FeIII reduction and fast FeIII precipitation. Here, boron crystals (C‐Boron) remarkably accelerate the FeIII/FeII circulation in Fenton‐like systems (C‐Boron/FeIII/H2O2) to produce a myriad of hydroxyl radicals with excellent efficiencies in oxidative degradation of various pollutants. The surface B−B bonds and interfacial suboxide boron in the surface B12 icosahedra are the active sites to donate electrons to promote fast FeIII reduction to FeII and further enhance hydroxyl radical production via Fenton chemistry. The C‐Boron/FeIII/H2O2 system outperforms the benchmark Fenton (FeII/H2O2) and FeIII‐based sulfate radical systems. The reactivity and stability of crystalline boron is much higher than the popular molecular reducing agents, nanocarbons, and other metal/metal‐free nanomaterials. The unique B12 unit of crystalline boron experiences step‐wise cleavage of B−B bond and rapidly provides electrons for FeIII reduction to FeII. This boosts the oxidation capability of the Fenton systems remarkably to oxidize a diversity of organic pollutants with exceptional stability.