Surface decoration of amine-rich carbon nitride with iron nanoparticles for arsenite (As(III)) uptake: The evolution of the Fe-phases under ambient conditions.

A novel hybrid material (gC3N4-rFe) consisting of amine-rich graphitic carbon nitride (gC3N4), decorated with reduced iron nanoparticles (rFe) is presented. XRD and TEM show that gC3N4-rFe bears aggregation-free Fe-nanoparticles (10nm) uniformly dispersed over the gC3N4 surface. In contrast, non-supported iron nanoparticles are strongly aggregated, with non-uniform size distribution (20-100nm). (57)Fe-Mössbauer spectroscopy, dual-mode electron paramagnetic resonance (EPR) and magnetization measurements, allow a detailed mapping of the evolution of the Fe-phases after exposure to ambient O2. The as-prepared gC3N4-rFe bears Fe(2+) and Fe° phases, however only after long exposure to ambient O2, a Fe-oxide layer is formed around the Fe° core. In this [Fe°/Fe-oxide] core-shell configuration, the gC3N4-rFe hybrid shows enhanced As(III) uptake capacity of 76.5mgg(-1), i.e., ca 90% higher than the unmodified carbonaceous support, and 300% higher than the non-supported Fe-nanoparticles. gC3N4-rFe is a superior As(III) sorbent i.e., compared to its single counterparts or vs. graphite/graphite oxide or activated carbon analogues (11-36mgg(-1)). The present results demonstrate that the gC3N4 matrix is not simply a net that holds the particles, but rather an active component that determines particle formation dynamics and ultimately their redox profile, size and surface dispersion homogeneity.