Tetrahydrofuran aided self-assembly synthesis of nZVI@gBC composite as persulfate activator for degradation of 2,4-dichlorophenol

Abstract

• nZVI@gBC were synthesized by one-step carbothermal reduction method aided by Tetrahydrofuran. • The formation of graphene nano-shells greatly enhanced the stability of nZVI in the air environment. • The nZVI@gBC exhibited superior degradation performance to 2,4-DCP by activating PS. • Four active free radicals (SO 4 •− , •OH, O 2 •− and 1 O 2 ) were produced and participated in the degradation of 2,4-DCP. The defects of easy agglomeration and oxidation of nano zero valent iron (nZVI) limit its large-scale application in industry, especially in the field of environmental remediation. In this study, the iron nanoparticles encapsulated by graphene nano-shells which anchored on the surface of carbon substrate (nZVI@gBC) were synthesized by a one-step carbothermal reduction method aided by Tetrahydrofuran. When the mass ratio of carbon source to iron source is 2:3 and the carbothermic reduction temperature is 700 °C, stabilized nZVI @gBC can be successfully synthesized with a high iron loading rate of 32.5%. The multilayer graphene shell can effectively prevent the rapid passivation and agglomeration of the nZVI core, and the electronic interaction between the iron nanoparticles core and the graphene carbon shell further enhances the catalytic activity and stability of nZVI@gBC. Therefore, due to the unique structure of graphene nano-shells, nZVI@gBC can be stably stored in the air for more than 80 days. In addition, nZVI@gBC exhibited superior catalytic activity in the experiment of removing 2,4-dichlorophenol (2,4-DCP) in groundwater as a persulfate activator. Notably, both the electron paramagnetic resonance (EPR) and quenching tests showed that SO 4 •− , •OH, O 2 •− and 1 O 2 were both involved in the degradation process of 2,4-DCP, and SO 4 •− were the major active species. Simultaneously, three possible degradation pathways of 2,4-DCP were deduced by GC/MS, which were caused by dechlorination, dehydrogenation or carbon–carbon bond cleavage under the attack of SO 4 •− , •OH, O 2 •− and 1 O 2 . Besides, nZVI@gBC can use the dissolved oxygen in the liquid to generate hydroxyl radicals to effectively remove 2,4-DCP without persulfate. This kind of multifunctional nZVI@gBC may become a promising iron-carbon catalyst for large-scale applications in the field of environmental remediation.