Colloidal aggregation and structural assembly of aspect ratio variant goethite (α-FeOOH) with nC60 fullerene in environmental media

Environmental mobility of C60 fullerene can be significantly affected in the presence of naturally abundant α-FeOOH. However, α-FeOOH vary significantly in sizes, shapes and associated properties that can greatly influence the fate and transport of C60 fullerene in environmental media. Therefore, colloidal hetero-association between well crystallized low aspect (LAsp) α-FeOOH and nC60 fullerene may differ substantially to weakly crystallized high-aspect (HAsp) counterpart. In contrast to LAsp α-FeOOH, inherent crystal defects and surface charge generation in HAsp α-FeOOH facilitated strong Coulombic attraction and aggregation with fullerene in acidic pH. However, LAsp α-FeOOH demonstrated subtle entropic depletion mediated interaction with fullerene prevalent in hard rods. Humic acid (HA) encapsulation of HAsp α-FeOOH substantially blocked fullerene attachment. Minute enhancement in colloidal stability was detected for HA-coated HAsp α-FeOOH and fullerene mixture to HA-coated HAsp α-FeOOH alone. To investigate the interfacial assembly of α-FeOOH with fullerene “in situ” differential interference contrast (DIC) microscopic investigations were employed. This study showed significantly different interface behavior of the binary mixtures of fullerene and HAsp α-FeOOH NPs, and LAsp particles. On air-water interface, bare HAsp α-FeOOH displayed liquid crystalline packing. However, addition of fullerene to HAsp α-FeOOH suspension at pH5 produced closed-loop polygonal and circular ring structures. Head-to-tail alignment of magnetic dipoles as well as fullerene hydrophobicity facilitated such assembly formation. “Ex situ” AFM investigation revealed further the presence of magnetically derived ring structure which asserts that the formed “in situ” ensembles were not transient, hence, may abate fullerene transport through environmental interfaces. Barring hydrophobicity assisted attachment of fullerene to LAsp α-FeOOHs, the absence of any close-packed structures may unlikely abate fullerene transport as envisaged in case of HAsp α-FeOOH. Thus, aspect ratio variation and associated material properties of naturally abundant α-FeOOH may significantly impact fullerene transport through environmental media.