Metal-free materials, manufacturing thereof, method using thereof for (in-situ or ex-situ) catalytically treating contaminated soil or waters, including remediation of groundwater contaminated by haloalkenes, haloalkanes, nitro-compounds, and nitrophenol using sulfide as a reductant. Metal-free materials are manufactured with industrial scrap syrup or biomass. Method using the metal-free materials for in-situ treatment consists with the processes of adding materials into the contaminated medium, introducing sulfide into the contaminated medium, and reductive reacting contaminants with sulfide catalyzed by the metal-free materials. Specially, the formation of in-situ reaction zone is the key point of in situ treatment by retaining the catalyst in the contaminated medium. Method using the metal-free materials for ex-situ treatment consists steps of adding materials and sulfide into the contaminated fluid, intermingling the contaminated fluid with materials in a vessel, reacting contaminants with sulfide catalyzed by the metal-free material.