Doping heteroatoms to form multiple hydrogen bond sites for enhanced interfacial reconstruction and separations.

Interfacial challenges in unconventional oil extraction include heavy oil-water-solid multiphase separation and corrosion inhibition. Herein, a novel strategy based on interfacial hydrogen bonding reconstruction is proposed for constructing multifunctional interfacially active materials (MIAMs) to address multi-interfacial separation needs. A simple one-pot method is applied to successfully synthesize four different MIAM varieties, integrating site groups (-NH2, OSO, -COOH, and Si-O-Si) with multiple hydrogen bonds (HBs) into allyl polyether chains. The results indicate that all synthesized MIAMs excel in demulsification, detergency, and corrosion inhibition simultaneously, even at 25 °C. Their dehydration efficiency for different water-in-oil emulsions (even heavy oil emulsion) surpasses 99.9 % even at 16 °C, showing their excellent energy-saving potential for field applications. Furthermore, they demonstrate effective, nondestructive static cleaning (up to 86 %) of adhered oil from solid surfaces at 25 °C and provide corrosion inhibition effects (up to 92.09 %) on mild steel immersed in saturated brine. Mechanistic tests reveal that incorporating multiple HB sites in MIAMs dramatically enhances their effectiveness in interfacial separations. Based on these findings, an HB-dominated noncovalent interaction reconstruction strategy is tentatively proposed to develop advanced materials for low-carbon, efficient interfacial separations.

Tartaric Acid Cross-Linking Polyvinyl Alcohol as Degradable Separators for Rechargeable Lithium Ion Batteries.

The escalating focus on environmental concerns and the swift advancement of eco-friendly biodegradable batteries raises a pressing demand for enhanced material design in the battery field. The traditional polypropylene (PP) that is monopolistically utilized in the commercial LIBs is hard to recycle. In this work, we prepare a novel water degradable separators via the cross-linking of polyvinyl alcohol (PVA) and dibasic acid (tartaric acid, TA). Through the integration of non-solvent liquid-phase separation, we successfully produced a thermally stable PVA-TA membrane with tunable thickness and a high level of porosity. These specially engineered PVA-TA separators were implemented in LiFePO4 (LFP)|separator|Li cells, resulting in superior multiplicative performance and achieving a capacity of 88 mAh g-1 under 5 C. Additionally, the straightforward small molecule cross-linking technique significantly reduced the crystalline region of the polymer, thereby enhancing ionic conductivity. Notably, after cycling, the PVA-TA separators can be easily dissolved in 95 °C hot water, enabling its reutilization for the production of new PVA-TA separators. Therefore, this work introduces a novel concept to design green and sustainable separators for recyclable lithium batteries.

New insights into interaction between oil and solid during hydrothermal treatment of oily sludge.

Hydrothermal treatment (HT) can effectively dehydrate and reduce oily sludge (OS) volume, but the resulting hydrothermal oily sludge (HOS) presents greater challenges for washing than the initial oily sludge (IOS). This study examines the effects of HT on OS by analyzing changes in water, oil, and solid. Results indicate that HT considerably decreases the water content in OS while increasing resin and asphaltenes contents. In addition, condensation, side-chain scission, and oxidation reactions occur during the HT process, resulting in coking, agglomeration, and an increase in oxygen-containing groups. This increase, further confirmed by X-ray photoelectron spectroscopy (XPS), enhances the interaction between oil and solids. Calcite, the most prevalent solid-phase component, may form a calcium bridge with the oxygen-containing groups. Moreover, HT reduces the solid particle size, thereby increasing the oil-solid contact area. Interestingly, the process of deasphalting diminishes the interaction between oil and solids, facilitating sludge washing. After washing, the residual oil content in HOS is reduced to less than 0.34%. This study elucidates why HOS is challenging to separate from oil and solids and introduces a novel method that combines dodecylbenzene sulfonic acid (DBSA)-assisted heptane deasphalting with conventional washing techniques. This method shows promise for applications in OS affected by weathering processes.

Suitability of inorganic coagulants for algae-laden water treatment: Trade-off between algae removal and cell viability, aggregate properties and coagulant residue.

Inorganic coagulants could effectively precipitate algae cells but might increase the potential risks of cell damage and coagulant residue. This study was conducted to critically investigate the suitability of polyaluminum (PAC), FeCl3 and TiCl4 for algae-laden water treatment in terms of the trade-off between algal substance removal, cell viability, and coagulant residue. The results showed that an appropriate increase in coagulant dosage contributed to better coagulation performance but severe cell damage and a higher risk of intracellular organic matter (IOM) release. TiCl4 was the most destructive, resulting in 60.85% of the algal cells presenting membrane damage after coagulation. Intense hydrolysis reaction of Ti salts was favorable for the formation of larger and more elongated, dendritic structured flocs than Al and Fe coagulants. TiCl4 exhibited the lowest residue level and remained in the effluents mainly in colloidal form. The study also identified charge neutralization, chemisorption, enmeshment, and complexation as the dominant mechanisms for algae water coagulation by metal coagulants. Overall, this study provides the trade-off analyses between maximizing algae substance removal and minimizing potential damage to cell integrity and is practically valuable to develop the most suitable and feasible technique for algae-laden water treatment.

CH4 control and nitrogen removal from constructed wetlands by plant combination.

Global warming trend is accelerating. This study proposes a green and economical methane (CH4) control strategy by plant combination in constructed wetlands (CWs). In this study, a single planting of Acorus calamus L. hybrid constructed wetland (HCW-A) and a mixed planting of Acorus calamus L. and Eichhornia crassipes (Mart.) Solms hybrid constructed wetland (HCW-EA) were constructed. The differences in nitrogen removal performance and CH4 emissions between HCW-A and HCW-EA were compared and analyzed. The findings indicated that HCW-EA demonstrated significant improvements over HCW-A, with NH4+-N and TN removal rates increasing by 21.61% and 16.38% respectively, and CH4 emissions decreased by 43.36%. The microbiological analysis results showed that plant combination promoted the enrichment of Proteobacteria, Alphaproteobacteria and Bacillus. More nitrifying bacteria carrying nxrA genes and denitrifying bacteria carrying nirK genes accelerated the nitrogen transformation process. In addition, the absolute abundance ratio of pmoA/mcrA increased, reducing the release of CH4.

Nanoemulsions Stable against Ostwald Ripening.

Ostwald ripening, the dominant mechanism of droplet size growth for an O/W nanoemulsion at high surfactant concentrations, depends on micelles in the water phase and high aqueous solubility of oil, especially for spontaneously formed nanoemulsions. In our study, O/W nanoemulsions were formed spontaneously by mixing a water phase with an oil phase containing fatty alcohol polyoxypropylene polyoxyethylene ether (APE). By monitoring periodically the droplet size of the nanoemulsions via dynamic light scattering, we demonstrated that the formed O/W nanoemulsions are stable against Ostwald ripening, i.e., droplet growth. In contrast, the nanoemulsion droplets grew with the addition of micelles, demonstrating the pivotal role of the presence of micelles in the water phase in the occurrence of Ostwald ripening. The influence of the initial phase of APE, the oil or water phase in which APE is present, on the micelle formation is discussed by the partition coefficient and interfacial adsorption of APE between the oil and water phase using a surface and interfacial tensiometer. In addition, the spontaneously formed O/W nanoemulsion, which is stable against Ostwald ripening, can be used as a nanocarrier for the delivery of water-insoluble pesticides. These results provide a novel approach for the preparation of stable nanoemulsions and contribute to elucidating the mechanism of instability of nanoemulsions.

Microstructure-dependent CO2-responsive microemulsions for deep-cleaning of oil-contaminated soils.

CO2-responsive microemulsion (ME) is considered a promising candidate for deep-cleaning and oil recovery from oil-contaminated soils. Understanding the responsive nature of different microstructures (i.e., oil-in-water (O/W), bicontinuous (B.C.) and water-in-oil (W/O)) is essential for unlocking the potential and mechanisms of CO2-responsive emulsions in complex multiphase systems and providing comprehensive guidance for remediation of oil-contaminated soils. Herein, the responsiveness of microstructures of ME to CO2 trigger was investigated using experimental designs and coarse-grained molecular dynamic simulations. MEs were formed for the first time by a weakly associated pseudo-Gemini surfactant of indigenous organic acids (naphthenic acids, NAs are a class of natural surface-active molecules in crude oil) and tetraethylenepentamine (TEPA) through fine tuning of co-solvent of dodecyl benzene sulfonic acid (DBSA) and butanol. The O/W ME exhibited an optimal CO2-responsive character due to easier proton migration in the continuous aqueous phase and more pronounced dependence of configuration on deprotonated NA ions. Conversely, the ME with W/O microstructure exhibited a weak to none responsive characteristic, most likely attributed to its high viscosity and strong oil-NA interactions. The O/W ME also showed superior cleaning efficiency and oil recovery from oil-contaminated soils. The results from this study provide insights for the design of CO2-responsive MEs with desired performance and guidance for choosing the favorable operating conditions in various industrial applications, such as oily solid waste treatment, enhanced oil recovery (EOR), and pipeline transportation. The insights from this work allow more efficient and tailored design of switchable MEs for manufacturing advanced responsive materials in various industrial sectors and formulation of household products.

Nanoscale Transport during Liquid Film Thinning Inhibits Bubble Coalescing Behavior in Electrolyte Solutions.

The long-standing puzzle of why two colliding bubbles in an electrolyte solution do not coalesce immediately upon contact is resolved. The water film between the bubbles needs to be drained out first before its rupture, i.e., coalescence. Experiments reveal clearly that the film thinning exhibits a rather sudden slowdown (around 30-50 nm), which is orders of magnitude smaller than similar experiments involving surfactants. A critical step in explaining this phenomenon is to realize that the solute concentration is different in bulk and at the surface. During thinning, this will generate an electrolyte concentration difference in film solution along the interacting region, which in turn causes a Marangoni stress to resist film thinning. We develop a film drainage model that explains the experimentally observed phenomena well. The underlying physical mechanism, that confused the scientific community for decades, is now finally revealed.

Ultrafast Strategy to Fabricate Sulfur Cathodes for High-Performance Lithium-Sulfur Batteries.

Based on the different dielectric properties of materials and the selective heating property of microwaves, the ultrafast (30 s) preparation of S-NiS2@SP@Bitu as a cathode material for lithium-sulfur batteries was achieved using bitumen, sulfur, Super P, and nickel naphthenate as raw materials for the first time, under microwave treatment. NiS2@SP@Bitu forms Li-N, Li-O, Li-S, and Ni-S bonds with polysulfide, which contributes to promoting the adsorption of polysulfide, reducing the precipitation and decomposition energy barrier of Li2S, and accelerating the catalytic conversion of polysulfide, as result of inhibiting the "shuttle effect" and improving the electrochemical performance. S-NiS2@SP@Bitu as the sulfur cathode material demonstrates outstanding rate performance (518.6 mAh g-1 at 4C), and stable cycling performance. The lithium-sulfur battery with a sulfur loading of 4.8 mg cm-2 shows an areal capacity of 4.6 mAh cm-2. Based on the advantages of microwave selective and rapid heating, this method creatively realized that the sulfur carrier material was prepared and sulfur was fixed in it at the same time. Therefore, this method would have implications for the preparation of sulfur cathode materials.

Green synthesis of mesoporous and biodegradable iron silicide nanoparticles for photothermal cancer therapy.

Photothermal nanomaterials have shown great potential for photothermal therapy. In this study, we developed a simple green method of magnesiothermic co-reduction for the synthesis of mesoporous, magnetic and biodegradable iron silicide nanoparticles (FeSi NPs) as applied to photothermal therapy (PTT). Starting from biogenic tabasheer extracted from bamboo and Fe2O3, the resultant FeSi NPs with a much lower band gap exhibited excellent optical absorption with a photothermal conversion efficiency of 76.2%, indicating a good photothermal performance. The weight extinction coefficient was measured to be 13.3 L g-1 cm-1 at 1064 nm (second near-infrared window, NIR-II), which surpassed the performance of other competitive Si-based and Fe-based photothermal agents. Results of the cell viability assay showed that cells could be killed by NIR-II laser irradiation with the synthesized FeSi NPs. In vivo results on mice showed clearly an efficient suppression of tumour growth by photothermal treatment with FeSi NPs. FeSi NPs were found to be biodegradable in simulated body fluids. The results from our work indicate that FeSi NPs are a new class of promising photothermal agents (PTAs) for application in cancer therapy.

Effecting pattern study of SO2 on Hg0 removal over α-MnO2 in-situ supported magnetic composite.

α-MnO2 was in-situ supported onto silica coated magnetite nanoparticles (MagS-Mn) to study the adsorption and oxidation of Hg0 as well as the effecting patterns of SO2 and O2 on Hg0 removal. MagS-Mn showed Hg0 removal capacity of 1122.6 µg/g at 150 °C with the presence of SO2. Hg0 adsorption and oxidation efficiencies were 2.4% and 90.6%, respectively. Hg0 removal capability deteriorated at elevated temperatures. Surface oxygen and manganese chemistry analysis indicated that SO2 inhibited the Hg0 removal through consumption of adsorbed oxygen and reduction of high valence manganese. This inhibiting effect was observed to be counteracted by O2 at lower temperatures. O2 tended to compete with SO2 for active sites and further create additional adsorbed oxygen sites for Hg0 surface reaction via surface dissociative adsorption rather than replenish the active sites consumed by SO2. The high valence manganese was also preserved by O2 which was essential to Hg0 oxidation. The intervention of O2 in the inhibition of SO2 on Hg0 removal was weakened at temperatures higher than 250 °C. Aa a result, Hg0 tends to be catalytic oxidized in the condition of low reaction temperatures and with the presence of O2 over α-MnO2 oriented composites.

Hydraulic characteristics of small-scale constructed wetland based on residence time distribution.

This paper designs and builds a small constructed wetland test site to study the internal hydraulic characteristics of different types of constructed wetlands, conducts NaCl pulse tracing experiments, and fits the residence time distribution (RTD) with the CSTRs+PFD model (Continuous Stirred-Tank Reactor model in parallel with Plug Flow with Dispersion model). The results showed that, among the six types of constructed wetlands, hydraulic parameters of horizontal subsurface flow constructed wetlands with baffles had the best performance, with a tracer recovery rate (F(t)) reaching 43.67% and hydraulic efficiency (λ) reaching 0.81. The addition of baffles slowed flow velocity, increased mean hydraulic retention time (Tm) and peak residence time (Tp), and reduced the short circuits phenomenon. The velocity of internal water flow increased during the horizontal and vertical deflections, which could well avoid the stagnation phenomenon caused by complicated flow state, thereby improving the hydraulic efficiency (λ). The CSTRs+PFD model can better fit the RTD of 6 different types of constructed wetlands. The peak value of the fitted curve, the time to reach the peak and the slope of the curve are all very similar to the measured RTD.

Chemical looping based ammonia production-A promising pathway for production of the noncarbon fuel.

Ammonia, primarily made with Haber-Bosch process developed in 1909 and winning two Nobel prizes, is a promising noncarbon fuel for preventing global warming of 1.5 °C above pre-industrial levels. However, the undesired characteristics of the process, including high carbon footprint, necessitate alternative ammonia synthesis methods, and among them is chemical looping ammonia production (CLAP) that uses nitrogen carrier materials and operates at atmospheric pressure with high product selectivity and energy efficiency. To date, neither a systematic review nor a perspective in nitrogen carriers and CLAP has been reported in the critical area. Thus, this work not only assesses the previous results of CLAP but also provides perspectives towards the future of CLAP. It classifies, characterizes, and holistically analyzes the fundamentally different CLAP pathways and discusses the ways of further improving the CLAP performance with the assistance of plasma technology and artificial intelligence (AI).

Assessment of a Multifunctional River Using Fuzzy Comprehensive Evaluation Model in Xiaoqing River, Eastern China.

Rivers are beneficial to humans due to their multiple functions. However, human meddling substantially degrades the functions of rivers and constitutes a threat to river health. Therefore, it is vital to assess and maintain river function. This study used the Xiaoqing River in Shandong Province, China, as a case study and established a multilayered multifunctional river evaluation indicator system consisting of environmental function, ecological function, social function, and economic function. The weights of indicators were calculated using the analytic hierarchy process (AHP) and the entropy method. Furthermore, a fuzzy comprehensive evaluation model based on the Cauchy distribution function was developed to assess the operation status of each function in each river segment. The results of the indicator and criterion layers in different river sections varied. The multifunctionality of the river decreased from upstream to downstream. The Jinan section was the most multifunctional, followed by the Binzhou, Zibo, and Dongying sections, and finally the Weifang section. Through additional analysis, this study determined the constraint indicators and functions of each river section. Overall, the results reveal that the idea of a "multifunctional river" can advance the theoretical understanding of a river's function, and the fuzzy comprehensive evaluation model is demonstrated to provide fresh perspectives for evaluating river function.

N, S-Coordinated Co Single Atomic Catalyst Boosting Adsorption and Conversion of Lithium Polysulfides for Lithium-Sulfur Batteries.

Boosting reversible solid-liquid phase transformation from lithium polysulfides to Li2 S and suppressing the shuttling of lithium polysulfides from the cathode to the lithium anode are critical challenges in lithium-sulfur batteries. Here, sulfiphilic single atomic cobalt implanted in lithiophilic heteroatoms-dopped carbon (SACo@HC) matrix with a CoN3 S structure for high-performance lithium-sulfur batteries is reported. Density functional theory calculation and in situ experiments demonstrate that the optimal CoN3 S structure in SACo@HC can effectively improve the adsorption and redox conversion efficiency of lithium polysulfides. Consequently, the S-SACo@HC composite with sulfur loading of 80 wt% delivers a high capacity of 1425.1 mAh g-1 at 0.05 C and outstanding rate performance with 745.9 mAh g-1 at 4 C. Furthermore, a capacity of 680.8 mAh g-1 at 0.5 C with a low electrolyte/sulfur ratio (6 µL mg-1 ) can be achieved even after 300 cycles. With the harsh conditions of lean electrolyte (E/S = 4 µL mg-1 ) and high sulfur loading (5.4 mg cm-2 ), a superior area capacity of 5.8 mAh cm-2 can be obtained. This work contributes to building a profound understanding of the adsorption and interface engineering of lithium polysulfides and provides ideas to tackle the long-standing polysulfide shuttle problem of lithium-sulfur batteries.

Bitumen-Derived Onion-Like Soft Carbon as High-Performance Potassium-Ion Battery Anode.

Potassium-ion batteries (PIBs) have been regarded as a competitive alternative for lithium-ion batteries, owing to the natural abundance, low cost, and similar rocking-chair working mechanism of potassium element. However, it is challenging to simultaneously prepare suitable potassium ion anode materials of low voltage plateau, high capacity, and long cycle life. In this work, onion-like soft carbon (OLSC) of high heteroatom content is prepared by using solvent-sensitive self-assembly properties of asphaltene molecules. The OLSC electrode exhibits a low voltage plateau because of a high degree of graphitization. Meanwhile, it possesses excellent cycling stability and rate capability due to the high stability of the onion-like structure and fast transport of potassium ions, the latter of which is caused by heteroatom-induced expanded interlayers as found by first-principle calculations. Compared with existing carbon materials, the OLSC synthesized in this study exhibits a high reversible capacity of 466 mAh g-1 at 20 mA g-1 , a reversible capacity of 222 mAh g-1 and capacity retention of 95% after 1600 cycles at 1 A g-1 . This work connects the nanostructure of carbon materials and electrochemical performance and provides new insights in improving carbon-based anodes for PIBs.

A Hierarchical Si/C Nanocomposite of Stable Conductive Network Formed Through Thermal Phase Separation of Asphaltenes for High-Performance Li-Ion Batteries.

Silicon is one of the most promising anode materials for lithium-ion batteries. However, the huge volume change of silicon during lithiation/delithiation triggers continuous growth of solid-electrolyte interphase, loss of conductive contacts and structural collapse of the electrode, which causes a rapid deterioration of battery capacities. Inspired by the polyaromatic molecular nature and phase separation of asphaltenes in bitumen during thermal cracking, a hierarchical Si/C nanocomposite of robust carbon coatings and a firmly connected carbon framework on the silicon surface is synthesized by controlling the concentration of asphaltenes as carbon source and hence desired phase separation during the subsequent carbonization. The electrode made using this special Si/C nanocomposite exhibits a high reversible capacity of 1149 mAh g-1 after 600 cycles with a capacity retention of 98.5% and the operation ability at a high mass loading over 10 mg cm-2 or an area capacity of 23.8 mAh cm-2 , which represents one of the highest area capacities reported in open literature but with much more stable and prolonged operations. This simple and efficient strategy is easy to scale up for commercial production to meet the rapid growth of the electric vehicle industry.

Molecular structure-tuned stability and switchability of CO2-responsive oil-in-water emulsions.

HYPOTHESIS: Pseudo-Gemini surfactants (PGS) possessing switchable and recyclable features have drawn increasing attention on generating high-performance CO2-responsive emulsions for wide range and versatile applications. However, there is a lack of fundamental understanding on how the molecular structure of PGS affects the stability and switchability of emulsions. We hypothesize that the length and type of the spacer in PGS play a decisive role in controlling interfacial and switching properties. EXPERIMENTS: Two series of PGS with different spacers were prepared through electrostatic association between amines and oleic acid. The interfacial activity and CO2-responsive properties of corresponding emulsions were systematically investigated by well-designed experiments and molecular dynamics simulations. FINDINGS: Increasing the spacer length to allow the bent configuration leads to more tight arrangement of oleic molecules, consequently improving the interfacial activity. In addition, the introduction of amino group into the spacer dramatically promotes CO2 response of resulting PGS due to ehanced migration of the spacer from the interface to the aqueous phase after CO2 addition. These results are inspiring in designing controllable CO2-responsive emulsions for a wide range of industrial applications (e.g., enhanced oil recovery and oil-contaminated soil remediation).

Enhancing low-temperature thermal remediation of petroleum sludge by solvent deasphalting.

Thermal treatment is a promising technique for treating petroleum sludge (PS). However, asphaltenes as a recalcitrant fraction of PS induce strong bounding between petroleum and minerals, and therefore lead to the need for high temperature and hence high energy consumption in thermal treatment of PS. In this study, a novel method combining a deasphalting pretreatment of PS with low-temperature thermal desorption (LTTD) was developed. The efficiency of deasphalting was found to be positively correlated to the ability of n-alkanes and asphaltene dispersants in dispersing asphaltenes. In treating six different kinds of PS, the residual oil contents were all below 2.5% after the deasphalting alone. Compared with direct thermal desorption at 600 °C for 1 h, dodecyl benzene sulfonic acid (DBSA)-assisted heptane deasphalting made thermal desorption at 350 °C for 1 h sufficient to treat these APS. The residual oil content of sludge after LTTD is lower than 0.45%. FT-IR, Raman spectra and XPS analysis confirmed that the carbon residue in APS after LTTD is primarily graphite state, which is extremely stable and does not migrate to the surrounding environment as compared with the crude oil in the APS. Hence, solvent deasphalting results in effective treatment of PS by LTTD, while the solvent can be recycled by distillation and crude oil recovered as value-added petroleum resource. The LTTD represents therefore a novel green strategy for treating PS and resource utilization.

A novel highly specific colorimetric fluorescent probe for the detection of nitrite in aqueous solution.

Developing an effective method for the detection of nitrite (NO2 - ) ions in the natural environment especially in environmental waters and soils is very necessary, since they will cause serious damage to human health once excess NO2 - ions enters the human body. Therefore, a new colorimetric fluorescent probe NB-NO2 - for determining NO2 - ions was designed, which possesses good water-solubility and satisfactory selectivity over other common ions for NO2 - ions. The addition of NO2 - ions changed the color of solution from blue to colorless seen by the naked-eye. Furthermore, through test and calculation, the detection limit of the probe NB-NO2 - is 129 nM. Based on the earlier excellent characteristics, the probe NB-NO2 - was successfully used for monitoring NO2 - ions in environmental waters and soils.