Detection of organic dyes using Ag NPAs/SMP SERS substrate produced via sandpaper template-assisted lithography and liquid-liquid interface self-assembly.

Surface-enhanced Raman spectroscopy (SERS) is a highly sensitive and reliable fingerprinting technique. However, its analytical capability is closely related to the quality of a SERS substrate used for the analysis. In particular, conventional colloidal substrates possess disadvantages in terms of controllability, stability, and reproducibility, which limit their application. In order to address these issues, a simple, cost-effective, and efficient SERS substrate based on silver nanoparticle arrays (Ag NPAs) and sandpaper-molded polydimethylsiloxane (SMP) was proposed in this work. Successfully prepared via template lithography and liquid-liquid interface self-assembly (LLISA), the substrate can be applied to the specific detection of organic dyes in the environment. The substrate exhibited good SERS performance, and the limit of detection (LOD) of rhodamine 6G (R6G) was shown to be 10-7 M under the optimal conditions (1000 grit sandpaper) with a relative standard deviation (RSD) of 7.76%. Moreover, the SERS signal intensity was maintained at 60% of the initial intensity after the substrate was stored for 30 days. In addition, the Ag NPAs/SMP SERS substrate was also employed to detect crystal violet (CV) and methylene blue (MB) with the LODs of 10-6 M and 10-7 M, respectively. In summary, the Ag NPAs/SMP SERS substrate prepared in this study has great potential for the detection of organic dyes in ecological environments.

Stretchable and Flexible Micro-Nano Substrates for SERS Detection of Organic Dyes.

Surface-enhanced Raman spectroscopy (SERS) is a precise and noninvasive analytical technique to identify vibrational fingerprints of trace analytes with sensitivity down to the single-molecule level. However, substrates can influence this capability, and current SERS techniques lack uniform, reproducible, and stable substrates to control plasma hot spots over a wide spectral range. Herein, we demonstrate a flexible SERS substrate via longitudinal stretching of a polydimethylsiloxane (PDMS) film. This substrate, after stretching and shrinking, exhibits an irregular wrinkled structure with abundant gaps and grooves that function as hot spots, thereby improving the hydrophobic properties of the material. To investigate the enhancement effect of Raman signals, silver nanoparticles (AgNPs) were mixed with Rhodamine 6G (R6G) solution, and the obtained blend was dropped onto the PDMS film to form a coffee ring pattern. According to the results, the hydrophobicity of the substrate increases with the degree of PDMS stretching, achieving the optimal level at 150% stretching. Moreover, the increase in hydrophobicity makes the measured molecules more aggregated, which enhances the Raman signal. The stretching and shrinkage of the PDMS film lead to a much higher density of nanogaps among nanoparticles and nanogrooves, which serve as multiple hot spots. Being highly localized regions of intense local fields, these hot spots make a significant contribution to SERS performance, improving the sensitivity and reproducibility of the method. In particular, the relative standard deviation (RSD) was found to be 2.5544%, and the detection limit was 1 × 10-7 M. Therefore, SERS using stretchable and flexible micro-nano substrates is a promising way for detecting dyes in wastewater.

One-Step Hydrothermal Strategy for Preparation of a Self-Cleaning TiO2/SiO2 Fiber Membrane toward Oil-Water Separation in a Complex Environment.

Oil pollution caused by a large number of industrial activities and oil spill accidents has posed serious harm to the environment and human health. However, some challenges remain with the existing separation materials, such as poor stability and fouling resistance. Herein, a TiO2/SiO2 fiber membrane (TSFM) was prepared by a one-step hydrothermal method for oil-water separation in acid, alkali, and salt environments. The TiO2 nanoparticles were successfully grown on the fiber surface, endowing the membrane with superhydrophilicity/underwater superoleophobicity. The as-prepared TSFM exhibits high separation efficiency (above 98%) and separation fluxes (3016.38-3263.45 L·m-2·h-1) for various oil-water mixtures. Importantly, the membrane shows good corrosion resistance in acid, alkaline, and salt solutions and still maintains underwater superoleophobicity and high separation performance. The TSFM displays good performance after repeated separation, demonstrating its excellent antifouling ability. Importantly, the pollutants on the membrane surface can be effectively degraded under light radiation to restore its underwater superoleophobicity, showing the unique self-cleaning ability of the membrane. In view of its good self-cleaning ability and environmental stability, the membrane can be used for wastewater treatment and oil spill recovery and has a broad application prospect in water treatment in complex environments.

Coordination-driven interfacial cross-linked graphene oxide-alginate nacre mesh with underwater superoleophobicity for oil-water separation.

Inspired by the seashell nacre and seaweed, a novel GO-Ca2+-SA nacre-inspired hybrid mesh was prepared via an interfacial layer-by-layer self-assembly and cross-linking, using graphene oxide (GO) and sodium alginate (SA) as the building blocks and calcium chloride as the coordination agent, respectively. Hybrid mesh was characterized by FTIR, XPS, XRD, SEM and contact angel instrument, showing superhydrophilic and underwater superoleophobic property and low oil adhesion, due to its wrinkle and rough surface, and high hydration ability of GO-Ca-alginate nanohydrogels. The separation efficiencies of various oil-water mixtures were above 99 %, with a highest flux of 119,426 L m-2 h-1. Hybrid mesh showed an orderly layered "brick and mortar" microstructure with many ultrasmall nanoscaled protuberances. Ca2+ ions could chelate with SA to form the "egg-box" structure, and interact with GO nanosheets. Hybrid mesh possessed high salt/acid/alkaline tolerance, abrasion resistance, mechanical property with Young's modulus of 35.8 ± 4.9 GPa, and excellent cycling stability.

Robust Nacrelike Graphene Oxide-Calcium Carbonate Hybrid Mesh with Underwater Superoleophobic Property for Highly Efficient Oil/Water Separation.

Inspired by the mastoid structure of the lotus leaf and the robust layered structure of the nacre, a novel nacrelike graphene oxide-calcium carbonate (GO-CaCO3) hybrid mesh with superhydrophilic and underwater superoleophobic property was prepared for the first time, via a facile, economical, and environmentally friendly layer-by-layer (LBL) self-assembly method using commercially available stainless steel mesh (SSM) as a ready-made mask. Interestingly, GO nanosheets played a threefold role, regulating the growth of CaCO3 nanocrystals between the GO interlamination for constructing a "brick-and-mortar" structure, improving the interface stability via coordination assembly onto SSM, and creating strong hydration derived from rich oxygen-containing functional groups. The surface hydrophilicity and hierarchically micro/nanoscale structure of GO-CaCO3 artificial pearls imbed on the SSM, contributing to outstanding superhydrophilicity and underwater superoleophobicity. The biomimetic hybrid mesh exhibited a strong mechanical property with a Young's modulus of 25.4 ± 2.6 GPa. The optimized hybrid mesh showed a high separation efficiency of more than 99% toward a series of oil/water mixtures with high flux. The low oil-adhesion force, high fatigue-resistance, chemical stability (acid/alkali/salt resistance), and excellent recycling performance enlighten the great prospects of GO-based nacrelike material for application in oily wastewater treatment.

Facile synthesis of degradable CA/CS imprinted membrane by hydrolysis polymerization for effective separation and recovery of Li.

Lithium resources are attractive for different applications because of their specific properties. Therefore, it is more significant to find a cost-effective and environment-friendly method to selective adsorption and recovery of Li+. In this work, a renewable and easy degradable CA/CS hybrid membrane was modified with polydopamine as adhesion layer to anchored TiO2. The simple imprinting process could be realized by hydrolysis polymerization. The adsorption process followed Langmuir isotherm model and pseudo-second-order kinetic equation were researched in detail. The results displayed the maximum adsorption capacity is 20.08 mg g-1 for Li+. The selectivity factors of Li+ to Na+, K+, Mg2+ and Ca2+ are 1.78, 2.43, 2.60 and 3.61, respectively, which mainly attributed to imprinting effect. The LIICMs also exhibited the superior reusability and durability. Thus, the LIICMs provide a powerful tool for selective separation and recovery of Li+ from mixed solutions.

Development of composite membranes with irregular rod-like structure via atom transfer radical polymerization for efficient oil-water emulsion separation.

Development of superhydrophilic, stable and cost-effective composite membranes for efficient oil-water emulsion separation is highly desirable. Herein, an irregular rod-like composite membrane was prepared through 3-aminopropyltriethoxysilane (APTES) modification, followed by acrylamide polymerization with atomic transfer radical polymerization (ATRP). The as-prepared membrane exhibits superhydrophilicity/underwater superoleophobicity due to its irregular rod-like structure and pores-induced capillary actions. The composite membrane has demonstrated sufficient stability in acidic, alkaline and salty environments due to the polymerization of acrylamide. Moreover, the as-prepared composite membrane has effectively separated various oil-water emulsions and demonstrated high permeation and superior flux recovery. The present work demonstrates that the ATRP-assisted composite membrane is a promising material in a wide range of applications, such as industrial wastewater recovery and drinking water treatment.

Facile preparation of intercrossed-stacked porous carbon originated from potassium citrate and their highly effective adsorption performance for chloramphenicol.

Recently, antibiotics pollution has attracted more interests from many researches which causes potential risks on the ecosystem and human health. Herein, the porous carbons (PCs) was prepared by directly simultaneous carbonization/self-activation of potassium citrate at 750-900°C for chloramphenicol (CAP) removal from aqueous solution. The batch experiments were studied, which indicated that PCs prepared at 850°C, namely PCPCs-850, possessed excellent adsorption ability for CAP with a maximum adsorption amount of 506.1mgg-1. Additionally, PCPCs-850 showed a large BET surface area of 2337.06m2g-1 and microporosity of 89.11% by N2 adsorption-desorption experiment. The Langmuir and pseudo-second-order model could more precisely describe the experimental data. And thermodynamic analysis illustrated that CAP adsorption onto PCPCs-850 was an endothermic and spontaneous process. Importantly, the adsorbent exhibited good stability and regeneration after four times cycles. Based on these excellent performance, it is potential that PCPCs-850 can be used as a promising adsorbent for treating contaminants in wastewater.