Trace Water Effects on Crystalline 1-Ethyl-3-methylimidazolium Acetate.

Spontaneous room-temperature crystallization of 1-ethyl-3-methylimidazolium acetate ([C2mim][OAc]) was observed upon removal of trace water. Sample purity was confirmed using analytical nuclear magnetic resonance spectroscopy to ensure that trace water or other contaminants did not produce this observation. Raman spectroscopy and simultaneous quartz crystal microbalance/infrared spectroscopy measurements were used to study molecular reorganization during crystallization and decrystallization using trace water in the form of atmospheric moisture. These experimental results were supplemented with density functional theory calculations that indicate imidazolium cation ring stacking and side chain clustering with an exclusive arrangement of the acetate anion in the cation ring plane upon water removal. Crystal structure formation was confirmed using two-dimensional wide-angle X-ray scattering. This natural crystallization is attributed to the removal of trace water over extended periods of time and calls attention to the molecular-level role of water in the structure of hygroscopic ionic liquid systems.

Mesoporous xerogel cellulose composites from biorenewable natural cotton fibers.

All-cellulose xerogel composites were fabricated using a facile, scalable three-step process-(1) partial ionic liquid dissolution, (2) non-solvent rinsing, and (3) drying. The xerogel composites are composed of two phases where the yarn center is non-porous highly crystalline cellulose I surrounded by mesoporous amorphous regenerated cellulose. The composite had high 149 m2 g-1 Brunauer-Emmett-Teller (BET) surface area with 11.7 nm average pore diameter. The porosity was calculated using density-based (ϕρ = 0.49) and volume-based (ϕV = 0.52) methods. The porosity evolution mechanism is attributed to non-solvent-induced polarity shifts, and these results are compared with non-porous morphologies produced by varying the choice in non-solvents. Although similar decrystallization behavior was measured for all samples, non-porous yarns had a smaller diameter and significantly reduced BET surface area (0.03 m2 g-1). The presented fabrication method offers controllable mesoporous phase formation along with freestanding structural capability towards the development of advanced functional cellulosic materials.

Radical-Driven Decomposition of Graphitic Carbon Nitride Nanosheets: Light Exposure Matters.

Understanding the transformation of graphitic carbon nitride (g-C3N4) is essential to assess nanomaterial robustness and environmental risks. Using an integrated experimental and simulation approach, our work has demonstrated that the photoinduced hole (h+) on g-C3N4 nanosheets significantly enhances nanomaterial decomposition under •OH attack. Two g-C3N4 nanosheet samples D and M2 were synthesized, among which M2 had more pores, defects, and edges, and they were subjected to treatments with •OH alone and both •OH and h+. Both D and M2 were oxidized and released nitrate and soluble organic fragments, and M2 was more susceptible to oxidation. Particularly, h+ increased the nitrate release rate by 3.37-6.33 times even though the steady-state concentration of •OH was similar. Molecular simulations highlighted that •OH only attacked a limited number of edge-site heptazines on g-C3N4 nanosheets and resulted in peripheral etching and slow degradation, whereas h+ decreased the activation energy barrier of C-N bond breaking between heptazines, shifted the degradation pathway to bulk fragmentation, and thus led to much faster degradation. This discovery not only sheds light on the unique environmental transformation of emerging photoreactive nanomaterials but also provides guidelines for designing robust nanomaterials for engineering applications.

Fe-based single-atom catalysis for oxidizing contaminants of emerging concern by activating peroxides.

We prepared a single-atom Fe catalyst supported on an oxygen-doped, nitrogen-rich carbon support (SAFe-OCN) for degrading a broad spectrum of contaminants of emerging concern (CECs) by activating peroxides such as peroxymonosulfate (PMS). In the SAFe-OCN/PMS system, most selected CECs were amenable to degradation and high-valent Fe species were present for oxidation. Moreover, SAFe-OCN showed excellent performance for contaminant degradation in complex water matrices and high stability in oxidation. Specifically, SAFe-OCN, with a catalytic center of Fe coordinated with both nitrogen and oxygen (FeNxO4-x), showed 5.13-times increased phenol degradation kinetics upon activating PMS compared to the catalyst where Fe was only coordinated with nitrogen (FeN4). Molecular simulations suggested that FeNxO4-x, compared to FeN4, was an excellent multiple-electron donor and it could potential-readily form high-valent Fe species upon oxidation. In summary, the single-atom Fe catalyst enables efficient, robust, and sustainable water and wastewater treatment, and molecular simulations highlight that the electronic nature of Fe could play a key role in determining the activity of the single-atom catalyst.

A percolation theory for designing corrosion-resistant alloys.

Iron-chromium and nickel-chromium binary alloys containing sufficient quantities of chromium serve as the prototypical corrosion-resistant metals owing to the presence of a nanometre-thick protective passive oxide film1-8. Should this film be compromised by a scratch or abrasive wear, it reforms with little accompanying metal dissolution, a key criterion for good passive behaviour. This is a principal reason that stainless steels and other chromium-containing alloys are used in critical applications ranging from biomedical implants to nuclear reactor components9,10. Unravelling the compositional dependence of this electrochemical behaviour is a long-standing unanswered question in corrosion science. Herein, we develop a percolation theory of alloy passivation based on two-dimensional to three-dimensional crossover effects that accounts for selective dissolution and the quantity of metal dissolved during the initial stage of passive film formation. We validate this theory both experimentally and by kinetic Monte Carlo simulation. Our results reveal a path forward for the design of corrosion-resistant metallic alloys.

Photocatalytic graphitic carbon nitride-chitosan composites for pathogenic biofilm control under visible light irradiation.

Photocatalysis holds promise for inactivating environmental pathogens. Visible-light-responsive composites of carbon-doped graphitic carbon nitride and chitosan with high reactivity and processability were fabricated, and they can control pathogenic biofilms for environmental, food, biomedical, and building applications. The broad-spectrum biofilm inhibition and eradication of the photocatalytic composites against Staphylococcus epidermidis, Pseudomonas aeruginosa PAO1, and Escherichia coli O157: H7 under visible light irradiation were demonstrated. Extracellular polymeric substances in Escherichia coli O157: H7 biofilms were most resistant to photocatalytic oxidation, which led to reduced performance for biofilm removal. 1O2 produced by the composites was believed to dominate biofilm inactivation. Moreover, the composites exhibited excellent performance for inhibiting biofilm development in urine, highlighting the promise for inactivating environmental biofilms developed from multiple bacterial species. Our study provides fundamental insights into the development of new photocatalytic composites, and elucidates the mechanism of how the photocatalyst reacts with a microbiological system.

3D printed photoreactor with immobilized graphitic carbon nitride: A sustainable platform for solar water purification.

Solar-energy-enabled photocatalysis is promising for sustainable water purification. However, photoreactor design, especially immobilizing nano-sized photocatalysts, remains a major barrier preventing industrial-scale application of photocatalysis. In this study, we immobilized photocatalytic graphitic carbon nitride on chitosan to produce g-C3N4/chitosan hydrogel beads (GCHBs), and evaluated GCHB photoreactivity for degrading phenol and emerging persistent micropollutants in a 3D printed compound parabolic collector (CPC) reactor. The CPC photocatalytic system showed comparable performance with slurry reactors for sulfamethoxazole and carbamazepine degradation under simulated sunlight, and it maintained the performance for contaminant removal in real water samples collected from water/wastewater treatment plants or under outdoor sunlight irradiation. Global drinking water production was estimated for the CPC system, and it holds promise for small-scale sustainable water treatment, including, but not limited to, the production of high-quality potable water for single houses, small communities, rural areas, and areas impacted by natural disasters in both developed and developing countries.