Tailoring Interfaces for Enhanced Methanol Production from Photoelectrochemical CO2 Reduction.

Efficient and stable photoelectrochemical reduction of CO2 into highly reduced liquid fuels remains a formidable challenge, which requires an innovative semiconductor/catalyst interface to tackle. In this study, we introduce a strategy involving the fabrication of a silicon micropillar array structure coated with a superhydrophobic fluorinated carbon layer for the photoelectrochemical conversion of CO2 into methanol. The pillars increase the electrode surface area, improve catalyst loading and adhesion without compromising light absorption, and help confine gaseous intermediates near the catalyst surface. The superhydrophobic coating passivates parasitic side reactions and further enhances local accumulation of reaction intermediates. Upon one-electron reduction of the molecular catalyst, the semiconductor-catalyst interface changes from adaptive to buried junctions, providing a sufficient thermodynamic driving force for CO2 reduction. These structures together create a unique microenvironment for effective reduction of CO2 to methanol, leading to a remarkable Faradaic efficiency reaching 20% together with a partial current density of 3.4 mA cm-2, surpassing the previous record based on planar silicon photoelectrodes by a notable factor of 17. This work demonstrates a new pathway for enhancing photoelectrocatalytic CO2 reduction through meticulous interface and microenvironment tailoring and sets a benchmark for both Faradaic efficiency and current density in solar liquid fuel production.

Mobility of Condensed Counterions in Ion-Exchange Membranes: Application of Screening Length Scaling Relationship in Highly Charged Environments.

Ion-exchange membranes (IEMs) are widely used in water, energy, and environmental applications, but transport models to accurately simulate ion permeation are currently lacking. This study presents a theoretical framework to predict ionic conductivity of IEMs by introducing an analytical model for condensed counterion mobility to the Donnan-Manning model. Modeling of condensed counterion mobility is enabled by the novel utilization of a scaling relationship to describe screening lengths in the densely charged IEM matrices, which overcame the obstacle of traditional electrolyte chemistry theories breaking down at very high ionic strength environments. Ionic conductivities of commercial IEMs were experimentally characterized in different electrolyte solutions containing a range of mono-, di-, and trivalent counterions. Because the current Donnan-Manning model neglects the mobility of condensed counterions, it is inadequate for modeling ion transport and significantly underestimated membrane conductivities (by up to ≈5× difference between observed and modeled values). Using the new model to account for condensed counterion mobilities substantially improved the accuracy of predicting IEM conductivities in monovalent counterions (to as small as within 7% of experimental values), without any adjustable parameters. Further adjusting the power law exponent of the screen length scaling relationship yielded reasonable precision for membrane conductivities in multivalent counterions. Analysis reveals that counterions are significantly more mobile in the condensed phase than in the uncondensed phase because electrostatic interactions accelerate condensed counterions but retard uncondensed counterions. Condensed counterions still have lower mobilities than ions in bulk solutions due to impedance from spatial effects. The transport framework presented here can model ion migration a priori with adequate accuracy. The findings provide insights into the underlying phenomena governing ion transport in IEMs to facilitate the rational development of more selective membranes.

Mechanisms and models for water transport in reverse osmosis membranes: history, critical assessment, and recent developments.

Water scarcity is one of the greatest societal challenges facing humanity. Reverse osmosis (RO) desalination, a widely used membrane-based technology, has proven to be effective to augment water supply in water-stressed regions of our planet. However, progress in the design and development of RO membranes has been limited. To significantly enhance the performance of RO membranes, it is essential to acquire a deep understanding of the membrane separation and transport mechanisms. In this tutorial review, we cover the pivotal historical developments in RO technology, examine the chemical and physical properties of RO membrane materials, and critically review the models and mechanisms proposed for water transport in RO membranes. Based on recent experimental and computational findings, we conduct a thorough analysis of the key transport models-the solution-diffusion and pore-flow models-to assess their validity for accurately describing water transport in RO membranes. Our analysis involves examining the experimental evidence in favor of the solution-diffusion mechanism. Specifically, we explain whether the water content gradient within the membrane, cited as evidence for the key assumption in the solution-diffusion model, can drive a diffusive transport through RO membranes. Additionally, we review the recent molecular dynamics simulations which support the pore-flow mechanism for describing water transport in RO membranes. We conclude by providing future research directions aimed at addressing key knowledge gaps in water transport phenomena in RO membranes, with the goal of advancing the development of next-generation RO membranes.

Water transport in reverse osmosis membranes is governed by pore flow, not a solution-diffusion mechanism.

We performed nonequilibrium molecular dynamics (NEMD) simulations and solvent permeation experiments to unravel the mechanism of water transport in reverse osmosis (RO) membranes. The NEMD simulations reveal that water transport is driven by a pressure gradient within the membranes, not by a water concentration gradient, in marked contrast to the classic solution-diffusion model. We further show that water molecules travel as clusters through a network of pores that are transiently connected. Permeation experiments with water and organic solvents using polyamide and cellulose triacetate RO membranes showed that solvent permeance depends on the membrane pore size, kinetic diameter of solvent molecules, and solvent viscosity. This observation is not consistent with the solution-diffusion model, where permeance depends on the solvent solubility. Motivated by these observations, we demonstrate that the solution-friction model, in which transport is driven by a pressure gradient, can describe water and solvent transport in RO membranes.

Precise Cation Separations with Composite Cation-Exchange Membranes: Role of Base Layer Properties.

Separation of specific ions from water could enable recovery and reuse of essential metals and nutrients, but established membrane technologies lack the high-precision selectivity needed to facilitate a circular resource economy. In this work, we investigate whether the cation/cation selectivity of a composite cation-exchange membrane (CEM), or a thin polymer selective layer on top of a CEM, may be limited by the mass transfer resistance of the underlying CEM. In our analysis, we utilize a layer-by-layer technique to modify CEMs with a thin polymer selective layer (∼50 nm) that has previously shown high selectivity toward copper over similarly sized metals. While these composite membranes have a CuCl2/MgCl2 selectivity up to 33 times larger than unmodified CEMs in diffusion dialysis, our estimates suggest that eliminating resistance from the underlying CEM could further increase selectivity twofold. In contrast, the CEM base layer has a smaller effect on the selectivity of these composite membranes in electrodialysis, although these effects could become more pronounced for ultrathin or highly conductive selective layers. Our results highlight that base layer resistance prevents selectivity factors from being comparable across diffusion dialysis and electrodialysis, and CEMs with low resistance are necessary for providing highly precise separations with composite CEMs.

Donnan dialysis for phosphate recovery from diverted urine.

There is a critical need to shift from existing linear phosphorous management practices to a more sustainable circular P economy. Closing the nutrient loop can reduce our reliance on phosphate mining, which has well-documented environmental impacts, while simultaneously alleviating P pollution of aquatic environments from wastewater discharges that are not completely treated. The high orthophosphate, HxPO4(3-x)-, content in source-separated urine offers propitious opportunities for P recovery. This study examines the use of Donnan dialysis (DD), an ion-exchange membrane-based process, for the recovery of orthophosphates from fresh and hydrolyzed urine matrixes. H2PO4- transport against an orthophosphate concentration gradient was demonstrated and orthophosphate recovery yields up to 93% were achieved. By adopting higher feed to receiver volume ratios, DD enriched orthophosphate in the product stream as high as ≈2.5 × the initial urine feed concentration. However, flux, selectivity, and yield of orthophosphate recovery were detrimentally impacted by the presence of SO42- and Cl- in fresh urine, and the large amount of HCO3- rendered hydrolyzed urine practically unsuitable for P recovery using DD. The detrimental effects of sulfate ions can be mitigated by utilizing a monovalent ion permselective membrane, improving selectivity for H2PO4- transport over SO42- by 3.1 × relative to DD with a conventional membrane; but the enhancement was at the expense of reduced orthophosphate flux. Critically, widely available and low-cost/waste resources with sufficiently high Cl- content, such as seawater and waste water softening regenerant rinse, can be employed to improve the economic viability of orthophosphate recovery. This study shows the promising potential of DD for P recovery and enrichment from source-separated urine.

Ambient PM Toxicity Is Correlated with Expression Levels of Specific MicroRNAs.

Uncertainties regarding optimized air pollution control remain as the underlying mechanisms of city-specific ambient particulate matter (PM)-induced health effects are unknown. Here, water-soluble extracts of PMs collected from four global cities via automobile air-conditioning filters were consecutively injected three times by an amount of 1, 2, and 2 mg into the blood circulation of Wistar rats after filtration by a 0.45 µm pore size membrane. Acute health effects, such as immune and inflammatory responses and hemorrhage in alveoli, were observed right after the PM extraction injection. Significant differences between cities in biomarker tumor necrosis factor-α (TNF-α) and monocyte chemoattractant protein-1 (MCP-1) levels were detected following the second and third PM injections. Rats' inflammatory responses varied substantially with the injections of city-specific PMs. Repeated PM extract exposure rendered the rats more vulnerable to subsequent challenges, and downregulation of certain microRNAs was observed in rats. Among the studied miRNAs, miR-125b, and miR-21 were most sensitive to the PM exposure, exhibiting a negative dose-response-type relationship with a source-specific PM (oxidative potential) toxicity (r2 = 0.63 and 0.57; p-values < 0.05). The results indicated that city-specific PMs could induce different health effects by selectively regulating different miRNAs, and that certain microRNAs, e.g., miR-125b and miR-21, may be externally mediated to neutralize PM-related health damages.

Ubiquity of polystyrene digestion and biodegradation within yellow mealworms, larvae of Tenebrio molitor Linnaeus (Coleoptera: Tenebrionidae).

Academics researchers and "citizen scientists" from 22 countries confirmed that yellow mealworms, the larvae of Tenebrio molitor Linnaeus, can survive by eating polystyrene (PS) foam. More detailed assessments of this capability for mealworms were carried out by12 sources: five from the USA, six from China, and one from Northern Ireland. All of these mealworms digested PS foam. PS mass decreased and depolymerization was observed, with appearance of lower molecular weight residuals and functional groups indicative of oxidative transformations in extracts from the frass (insect excrement). An addition of gentamycin (30 mg g-1), a bactericidal antibiotic, inhibited depolymerization, implicating the gut microbiome in the biodegradation process. Microbial community analyses demonstrated significant taxonomic shifts for mealworms fed diets of PS plus bran and PS alone. The results indicate that mealworms from diverse locations eat and metabolize PS and support the hypothesis that this capacity is independent of the geographic origin of the mealworms, and is likely ubiquitous to members of this species.

Global Survey of Antibiotic Resistance Genes in Air.

Despite its emerging significant public health concern, the presence of antibiotic resistance genes (ARGs) in urban air has not received significant attention. Here, we profiled relative abundances (as a fraction, normalized by 16S rRNA gene) of 30 ARG subtypes resistant to seven common classes of antibiotics, which are quinolones, ß-lactams, macrolides, tetracyclines, sulfonamides, aminoglycosides, and vancomycins, in ambient total particulate matter (PM) using a novel protocol across 19 world cities. In addition, their longitudinal changes in PM2.5 samples in Xi'an, China as an example were also studied. Geographically, the ARGs were detected to vary by nearly 100-fold in their abundances, for example, from 0.07 (Bandung, Indonesia) to 5.6 (San Francisco, USA). The ß-lactam resistance gene blaTEM was found to be most abundant, seconded by quinolone resistance gene qepA; and their corresponding relative abundances have increased by 178% and 26%, respectively, from 2004 to 2014 in Xi'an. Independent of cities, gene network analysis indicates that airborne ARGs were differentially contributed by bacterial taxa. Results here reveal that urban air is being polluted by ARGs, and different cities are challenged with varying health risks associated with airborne ARG exposure. This work highlights the threat of urban airborne transmission of ARGs and the need of redefining our current air quality standards in terms with public health.

The effects of facemasks on airway inflammation and endothelial dysfunction in healthy young adults: a double-blind, randomized, controlled crossover study.

BACKGROUND: Facemasks are increasingly worn during air pollution episodes in China, but their protective effects are poorly understood. We aimed to evaluate the filtration efficiencies of N95 facemasks and the cardiopulmonary benefits associated with wearing facemasks during episodes of pollution. RESULTS: We measured the filtration efficiencies of particles in ambient air of six types of N95 facemasks with a manikin headform. The most effective one was used in a double-blind, randomized, controlled crossover study, involving 15 healthy young adults, conducted during 2 days of severe pollution in Beijing, China. Subjects were asked to walk along a busy-traffic road for 2 h wearing authentic or sham N95 facemasks. Clinical tests were performed four times to determine changes in the levels of biomarkers of airway inflammation, endothelial dysfunction, and oxidative stress within 24 h after exposure. The facemasks removed 48-75% of number concentrations of ambient air particles between 5.6 and 560 nm in diameter. After adjustments for multiple comparison, the exhaled nitric oxide level and the levels of interleukin-1α, interleukin-1ß, and interleukin-6 in exhaled breath condensate increased significantly in all subjects; however, the increases in those wearing authentic facemasks were statistically significantly lower than in the sham group. No significant between-group difference was evident in the urinary creatinine-corrected malondialdehyde level. In arterial stiffness indicators, the ejection duration of subjects wearing authentic facemasks was higher after exposure compared to the sham group; no significant between-group difference was found in augmentation pressure or the augmentation index. CONCLUSIONS: In young healthy adults, N95 facemasks partially reduced acute particle-associated airway inflammation, but neither systemic oxidative stress nor endothelial dysfunction improved significantly. The clinical significance of these findings long-term remains to be determined. TRIAL REGISTRATION: The trial registration number (TRN) for this study is ChiCTR1800016099 , which was retrospectively registered on May 11, 2018.

Biodegradation of polystyrene wastes in yellow mealworms (larvae of Tenebrio molitor Linnaeus): Factors affecting biodegradation rates and the ability of polystyrene-fed larvae to complete their life cycle.

Commercial production of polystyrene (PS) -a persistent plastic that is not biodegradable at appreciable rates in most environments-has led to its accumulation as a major contaminant of land, rivers, lakes, and oceans. Recently, however, an environment was identified in which PS is susceptible to rapid biodegradation: the larval gut of Tenebrio molitor Linnaeus (yellow mealworms). In this study, we evaluate PS degradation capabilities of a previously untested strain of T. molitor and assess its survival and PS biodegradation rates for a range of conditions (two simulated food wastes, three temperatures, seven PS waste types). For larvae fed PS alone, the %PS removed in the short (12-15 h) residence time of the mealworm gut gradually increased for 2-3 weeks then stabilized at values up to 65%. Thirty two-day survival rates were >85% versus 54% for unfed larvae. For mealworms fed ∼10% w/w PS and ∼90% bran, an agricultural byproduct, rates of PS degradation at 25 °C nearly doubled compared to mealworms fed PS alone. Polymer residues in the frass showed evidence of partial depolymerization and oxidation. All of the tested PS wastes degraded, with the less dense foams degrading most rapidly. Mealworms fed bran and PS completed all life cycle stages (larvae, pupae, beetles, egg), and the second generation had favorable PS degradation, opening the door for selective breeding.