A possible solution to solve the restacking issue of graphene oxide (GO) nanosheets during large-scale production is to turn the two-dimensional (2D) nanosheets into three-dimensional (3D) crumpled balls that have excellent compressive properties but still maintain high free volumes. An aerosol-based process has been proven to be a rational method for this purpose, in which, the crumpling phenomenon, however, has hitherto remained unclear. Here we present a detailed understanding of the crumpling of GO nanosheets by a systematic investigation conducted in aerosolized droplets by means of in-line (e.g., scanning mobility particle sizer) and off-line (e.g., electron microscopy) measurements. Correlations between the confinement force and various parameters, such as evaporation rate and precursor concentration were established to derive a universally applicable equation. Both calculation and experimental results revealed that the evaporation rate plays an important role in controlling the crumpling process.

The important role of natural organic matter (NOM)-Fe colloids in influencing contaminant transport, and this role can be influenced by the formation, aggregation, and particle deposition dynamics of NOM-Fe colloids. In this work, NOM-Fe colloids at different C/Fe ratios were prepared by mixing different concentrations of humic acid (HA) with 10 mg/L Fe(II) under anoxic conditions. The colloids were characterized by an array of techniques and their aggregation and deposition behaviors were examined under both anoxic and oxic conditions. The colloids are composed of HA-Fe(II) at anoxic conditions, while they are made up of HA-Fe(III) at oxic conditions until the C/Fe molar ratio exceeds 1.6. For C/Fe molar ratios above 1.6, the aggregation and deposition kinetics of HA-Fe(II) colloids under anoxic conditions are slower than those of HA-Fe(III) colloids under oxic conditions. Further, the aggregation of HA-Fe colloids under both anoxic and oxic conditions decreases with increasing C/Fe molar ratio from 1.6 to 23.3. This study highlights the importance of the redox transformation of Fe(II) to Fe(III) and the C/Fe ratio for the formation and stability of NOM-Fe colloids that occur in subsurface environments with anoxic-oxic interfaces.

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Aqueous aggregation processes can significantly impact function, effective toxicity, environmental transport, and ultimate fate of advanced nanoscale materials, including graphene and graphene oxide (GO). In this work, we have synthesized flat graphene oxide (GO) and five physically crumpled GOs (CGO, with different degrees of thermal reduction, and thus oxygen functionality) using an aerosol method, and characterized the evolution of surface chemistry and morphology using a suite of spectroscopic (UV-vis, FTIR, XPS) and microscopic (AFM, SEM, and TEM) techniques. For each of these materials, critical coagulation concentrations (CCC) were determined for NaCl, CaCl2, and MgCl2 electrolytes. The CCCs were correlated with material ζ-potentials (R(2) = 0.94-0.99), which were observed to be mathematically consistent with classic DLVO theory. We further correlated CCC values with CGO chemical properties including C/O ratios, carboxyl group concentrations, and C-C fractions. For all cases, edge-based carboxyl functional groups are highly correlated to observed CCC values (R(2) = 0.89-0.95). Observations support the deprotonation of carboxyl groups with low acid dissociation constants (pKa) as the main contributors to ζ-potentials and thus material aqueous stability. We also observe CCC values to significantly increase (by 18-80%) when GO is physically crumpled as CGO. Taken together, the findings from both physical and chemical analyses clearly indicate that both GO shape and surface functionality are critical to consider with regard to understanding fundamental material behavior in water.

A 3D-printing technology and printed 3D lithium-ion batteries (3D-printed LIBs) based on LiMn 0.21 Fe 0.79 PO 4 @C (LMFP) nanocrystal cathodes are developed to achieve both ultrahigh rate and high capacity. Coin cells with 3D-printed cathodes show impressive electrochemical performance: a capacity of 108.45 mAh g −1 at 100 C and a reversible capacity of 150.21 mAh g −1 at 10 C after 1000 cycles. In combination with simulation using a pseudo 2D hidden Markov model and experimental data of 3D-printed and traditional electrodes, for the fi rst time deep insight into how to achieve the ultrahigh rate performance for a cathode with LMFP nanocrystals is obtained. It is estimated that the Li-ion diffusion in LMFP nanocrystal is not the rate-limitation step for the rate to 100 C, however, that the electrolyte diffusion factors, such as solution intrinsic diffusion coeffi cient, effi ciency porosity, and electrode thickness, will dominate ultrahigh rate performance of the cathode. Furthermore, the calculations indicate that the above factors play important roles in the equivalent diffusion coeffi cient with the electrode beyond a certain thickness, which determines the whole kinetic process in LIBs. This fundamental study should provide helpful guidance for future design of LIBs with superior electrochemical performance.

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In this work, we describe multifunctional, crumpled graphene oxide (CGO) porous nanocomposites that are assembled as advanced, reactive water treatment membranes. Crumpled 3D graphene oxide based materials fundamentally differ from 2D flat graphene oxide analogues in that they are highly aggregation and compression-resistant (i.e., π-π stacking resistant) and allow for the incorporation (wrapping) of other, multifunctional particles inside the 3D, composite structure. Here, assemblies of nanoscale, monomeric CGO with encapsulated (as a quasi core-shell structure) TiO2 (GOTI) and Ag (GOAg) nanoparticles, not only allow high water flux via vertically tortuous nanochannels (achieving water flux of 246 ± 11 L/(m(2)·h·bar) with 5.4 μm thick assembly, 7.4 g/m(2)), outperforming comparable commercial ultrafiltration membranes, but also demonstrate excellent separation efficiencies for model organic and biological foulants. Further, multifunctionality is demonstrated through the in situ photocatalytic degradation of methyl orange (MO), as a model organic, under fast flow conditions (tres < 0.1 s); while superior antimicrobial properties, evaluated with GOAg, are observed for both biofilm (contact) and suspended growth scenarios (>3 log effective removal, Escherichia coli). This is the first demonstration of 3D, crumpled graphene oxide based nanocomposite structures applied specifically as (re)active membrane assemblies and highlights the material's platform potential for a truly tailored approach for next generation water treatment and separation technologies.

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