A coupled experimental and mathematical modeling investigation was undertaken to explore nanoscale fullerene aggregate (nC60) transport and deposition in water-saturated porous media. Column experiments were conducted with four different size fractions of Ottawa sand at two pore-water velocities. A mathematical model that incorporates nonequilibrium attachment kinetics and a maximum retention capacity was used to simulate experimental nC60 effluent breakthrough curves and deposition profiles. Fitted maximum retention capacities (S(max)), which ranged from 0.44 to 13.99 microg/g, are found to be correlated to normalized mass flux. The developed correlation provides a means to estimate S(max) as a function of flow velocity, nanoparticle size, and mean grain size of the porous medium. Collision efficiency factors, estimated from fitted attachment rate coefficients, are relatively constant (approximately 0.14) over the range of conditions considered. These fitted values, however, are more than 1 order of magnitude larger than the theoretical collision efficiency factor computed from Derjaguin-Landau-Verwey-Overbeek (DLVO) theory (0.009). Data analyses suggest that neither physical straining nor attraction to the secondary minimum is responsible for this discrepancy. Patch-wise surface charge heterogeneity on the sand grains is shown to be the likely contributor to the observed deviations from classical DLVO theory. These findings indicate that modifications to clean-bed filtration theory and consideration of surface heterogeneity are necessary to accurately predict nC60 transport behavior in saturated porous media.

Experimental and mathematical modeling studies were performed to investigate the transport and retention of nanoscale fullerene aggregates (nC60) in water-saturated porous media. Aqueous suspensions of nC60 aggregates (95 nm diameter, 1 to 3 mg/L) were introduced into columns packed with either glass beads or Ottawa sand at a Darcy velocity of 2.8 m/d. In the presence of 1.0 mM CaCl2, nC60 effluent breakthrough curves (BTCs) gradually increased to a maximum value and then declined sharply upon reintroduction of nC60-free solution. Retention of nC60 in glass bead columns ranged from 8 to 49% of the introduced mass, while up to 77% of the mass was retained in Ottawa sand columns. When nC60 suspensions were prepared in deionized water alone, effluent nC60 BTCs coincided with those of a nonreactive tracer (Br-), with minimal nC60 retention. Observed differences in nC60 transport and retention behavior in glass beads and Ottawa sand were consistent with independent batch retention data and theoretical calculations of electrostatic interactions between nC60 and the solid surfaces. Effluent concentration and retention profile data were accurately simulated using a numerical model that accounted for nC60 attachment kinetics and a limiting retention capacity.

Single-metal site catalysts have exhibited highly efficient electrocatalytic properties due to their unique coordination environments and adjustable local structures for reactant adsorption and electron transfer. They have been widely studied for many electrochemical reactions, including oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). However, it remains a significant challenge to realize high-efficiency bifunctional catalysis (ORR/OER) with single-metal-type active sites. Herein, we report atomically dispersed Fe–Co dual metal sites (FeCo–NC) derived from Fe and Co co-doped zeolitic imidazolate frameworks (ZIF-8s), aiming to build up multiple active sites for bifunctional ORR/OER catalysts. The atomically dispersed FeCo–NC catalyst shows excellent bifunctional catalytic activity in alkaline media for the ORR (E 1/2 = 0.877 V) and the OER (E j=10 = 1.579 V). Moreover, its outstanding stability during the ORR and the OER is comparable to noble-metal catalysts (Pt/C and RuO2). The atomic dispersion state, coordination structure, and the charge density difference of the dual metal site FeCo–NC were characterized and determined using advanced physical characterization and density functional theory (DFT) calculations. The FeCo–N6 moieties are likely the main active sites simultaneously for the ORR and the OER with improved performance relative to the traditional single Fe and Co site catalysts. We further incorporated the FeCo–NC catalyst into an air electrode for fabricating rechargeable and flexible Zn–air batteries, generating a superior power density (372 mW cm–2) and long-cycle (over 190 h) stability. This work would provide a method to design and synthesize atomically dispersed multi-metal site catalysts for advanced electrocatalysis.

The potential toxicity of nanoscale particles has received considerable attention, but the fate of engineered nanomaterials in the environment has been studied only under a limited set of conditions. In the present study, batch and column experiments were performed to assess the aggregation and transport of nanoscale fullerene (nC60) particles in water-saturated quartz sands as a function of electrolyte concentration and species. As the electrolyte concentration increased from 1 to 100 mM, the change in nC60 particle diameter was minimal in the presence of NaCl but increased by more than sevenfold in the presence of CaCl2. The latter effect was attributed to the agglomeration of individual nC60 particles, consistent with a net attractive force between particles and suppression of the electrical double layer. At low ionic strength (3.05 mM), nC60 particles were readily transported through 40- to 50-mesh quartz sand, appearing in the column effluent after introducing less than 1.5 pore volumes of nC60 suspension, with approximately 30% and less than 10% of the injected mass retained in the presence of CaCl2 or NaCl, respectively. At higher ionic strength (30.05 mM) and in finer Ottawa sand (100-140 mesh), greater than 95% of the introduced nC60 particles were retained in the column regardless of the electrolyte species. Approximately 50% of the deposited nC60 particles were recovered from 100- to 140-mesh Ottawa sand after sequential introduction of deionized water adjusted the pH to 10 and 12. These findings demonstrate that nC60 transport and retention in water-saturated sand is strongly dependent on electrolyte conditions and that release of deposited nC60 requires substantial changes in surface charge, consistent with retention in a primary energy minimum.