Carbon redirection via tunable Fenton-like reactions under nanoconfinement toward sustainable water treatment

The ongoing pattern shift in water treatment from pollution control to energy recovery challenges the energy-intensive chemical oxidation processes that have been developed for over a century. Redirecting the pathways of carbon evolution from molecular fragmentation to polymerization is critical for energy harvesting during chemical oxidation, yet the regulation means remain to be exploited. Herein, by confining the widely-studied oxidation system—Mn₃O₄ catalytic activation of peroxymonosulfate—inside amorphous carbon nanotubes (ACNTs), we demonstrate that the pathways of contaminant conversion can be readily modulated by spatial nanoconfinement. Reducing the pore size of ACNTs from 120 to 20 nm monotonously improves the pathway selectivity toward oligomers, with the yield one order of magnitude higher under 20-nm nanoconfinement than in bulk. The interactions of Mn₃O₄ with ACNTs, reactant enrichment, and pH lowering under nanoconfinement are evidenced to collectively account for the enhanced selectivity toward polymerization. This work provides an adaptive paradigm for carbon redirection in a variety of catalytic oxidation processes toward energy harvesting and sustainable water purification.