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The acceleration of Fe(III)/Fe(II) conversion in Fenton systems is the critical route to achieve the long-lasting generation of reactive oxygen species towards the oxidation of refractory contaminants. Here, we found that waste leather derived porous carbon materials (LPC), as a simple and readily available metal-free biochar material, can promote the Fe(III)/H 2 O 2 system to generate hydroxyl radicals (•OH) for oxidizing a broad spectrum of contaminants. Results of characterizations, theoretical calculations, and electrochemical tests show that the surface carbonyl groups of LPC can provide electron for direct Fe(III) reduction. More importantly, the graphitic-N on surface of LPC can enhance the reactivity of Fe(III) for accelerating H 2 O 2 induced Fe(III) reduction. The presence of LPC accelerates the Fe(III)/Fe(II) redox cycle in the Fe(III)/H 2 O 2 system, sustainable Fenton chain reactions is thus initiated for long-lasting generation of hydroxyl radicals without adding Fe(II). The continuous flow mode that couples in-situ Fenton-like oxidation and LPC with excellent adsorption catalytic properties, anti-coexisting substances interference and reusability performance enables efficient, green and sustainable degradation of trace organic pollutants. Therefore, the application of metal-free carbon materials in Fenton-like system can solve its rate-limiting problem, reduce the production of iron sludge, achieve green Fenton chemistry, and facilitate the actual engineering application of economic and ecological methods to efficiently remove trace organic contaminants from actual water sources. [Display omitted] • Waste leather-derived porous carbon can effectively boost Fenton oxidation. • H 2 O 2 can act as an electron donor for green and sustainable Fenton oxidation. • Surface nitrogen of LPC can elevate the reactivity of Fe(III) species. • Sustainable removal of trace refractory organic pollutants was achieved. • Hydroxyl radical induced oxidation pathway of DEP was proposed. [ABSTRACT FROM AUTHOR]