Carbon Materials on Promoting Reductive Degradation of Nitro-/Halo-substituted Organic Pollutants:A Review
YUE Xianhui1,JIN Xin1,2,GU Cheng1,
1 State Key Laboratory of Pollution Control and Resource Reuse,School of the Environment of Nanjing University,Nanjing 210023,China 2 Key Laboratory of Soil Environment and Pollution Remediation,Institute of Soil Science,Chinese Academy of Sciences,Nanjing 210008,China
Abstract: Due to the advantages of high surface area, heterogeneous surface properties, excellent electron conductivity and electron storage capacity, carbon materials, including nano-carbon (e.g. graphene, carbon nano-tube, etc.) and amorphous carbon (including active carbon, biochar and black carbon, etc.) has been largely used in chemical industry, energy conservation, and environmental protection. In environmental application, carbon materials were mostly used as adsorbents. While in the last decade, carbon materials as the electron shuttle or redox mediator to facilitate electron transfer from electron donors (e.g. sulfide, iron/sulfide-reducing bacteria, etc) to electron acceptors (e.g. organic compounds, ≡FeIII, etc) has received increasingly concern. The electron transfer mechanisms by carbon materials are essential to the understanding of the environmental processes of organic pollutants and to the development of environmental remediation technologies for those compounds. Current researches mostly focused on the performance of carbon materials to the reductive transformation of nitro-aromatic compounds (NACs) and halo-substituted organic compounds (R-X). However, the mechanisms are varied depending on the properties of electron donors, organic compounds and carbon materials. Generally, three mechanisms have been accepted in different systems: Ⅰ. The oxygen functional groups on carbon surface play as the redox mediators to facilitate electron transfer. Ⅱ. The graphitic region and defect sites of carbon surface are highly conductive for electron transfer. Ⅲ. In the sulfide reduction conditions, carbon-sulfide intermediates would be the reactive sites for reductive degradation. In addition, surface area, porous structure and surface electric heterogeneous of carbon materials, as well as the structural properties of organic pollutants, the biotic/abiotic reaction systems would directly or indirectly influence the principle mechanisms. Since the matrix and surface of carbon materials have heterogeneous and complicated properties, the properties which control the electron transfer process have not yet fully understood. This review summarizes the reaction mechanisms that carbon materials mediated reductive transformation of NACs and R-X, upon which basis, modifications of carbon materials to further enhance the catalytic performance are also mentioned with the aim of application purposes. For the nano-carbon materials, surface modification and surface doping usually can facilitate the mass transfer efficiency and energy utilizing efficiency. For the porous carbon, chemical activation (by H3PO4 or ZnCl2) and thermal activation would induce porous structure, large surface area, high electric conductivity and electron storage capacity. All of those modifications make the carbon materials more efficiently to catalyst NACs and R-X reduction degradation. It provides theoretical guidelines for the extensive requirement in groundwater remediation. The environmental significance of this process stands on first, multi-forms of carbon in nature would directly or indirectly influence the environmental fate of organic compounds and element cycling. Second, carbon materials have great potential for the application in environmental reme-diation as for its environmental friendliness. It is expected that carbon materials could play more significant roles as the environmentally functional materials, for the elimination of NACs and R-X in anoxic groundwater.
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