A double-chain (gemini) fluorinated anionic surfactant, PFHT [(C6F13C2H2C3F7C2H4C3H6SO3-& sdot;Na+)2], was synthesized, and its interfacial activity, wetting, and foaming properties were systematically evaluated; synergistic interfacial behavior in blends with nano-SiO2 was further assessed. PFHT displays strong surface activity with a critical micelle concentration (CMC) of 0.437 mmol & sdot;L-1 and a minimum surface tension of 26.4 mN & sdot;m-1, lower than short-chain PFHxA (gamma CMC approximate to 28.9 mN & sdot;m-1) and intermediate between typical short-chain PFAS and legacy PFOA (gamma CMC approximate to 16.9 mN & sdot;m-1). At a nano-SiO2: PFHT mass ratio of 5:6, cooperative adsorption arises, increasing the initial foam height from 13 to 15 mL and maintaining a residual height of 6.5 mL at 10 min; the foam half-life (T1/2) is extended from 3.5 to 6.5 min, evidencing markedly enhanced foam stability. SEM reveals a compact, sponge-like lamellar film at this composition, which suppresses drainage and retards coarsening. On PTFE, the water contact angle decreases from 100 degrees to 68 degrees, indicating substantially improved wetting. Overall, the PFHT/ SiO2 co-formulation couples lower fluorine usage with high-efficacy interfacial control, highlighting its potential as a greener AFFF-class alternative.

Catalytic methane decomposition (CMD) is a promising route for the co-production of COx-free H-2 and value-added carbon, but its practical application is limited by catalyst deactivation caused by carbon deposition and Ni sintering. In this work, Ni catalysts supported on silica materials with different pore architectures, namely fibrous KCC-1, bimodal porous BPS-5, and channel-type MCM-41 and SBA-15, were systematically compared to clarify the role of support structure in Ni dispersion, carbon deposition, and CMD stability. Among them, Ni(30)/KCC-1 showed the best overall performance, reaching 81.3% CH4 conversion at 800 degrees C and maintaining >50% conversion for more than 180 min at 600 degrees C. The three-dimensional radially fibrous network of KCC-1 favored highly dispersed Ni species, alleviated pore blockage, and promoted the formation of highly graphitized multi-walled carbon nanotubes (I-D/I-G = 0.88). In contrast, MCM-41 and SBA-15 tended to form larger surface Ni particles and deactivated more rapidly, while BPS-5 only partly relieved diffusion limitations. Kinetic analysis over Ni(30)/KCC-1 gave an apparent reaction order of 1.29 and an apparent activation energy of 47.65 kJ mol(-1), indicating high intrinsic CMD activity. These results demonstrate the structural superiority of KCC-1 as a Ni support and provide guidance for designing durable catalysts for low-carbon hydrogen production with simultaneous carbon nanomaterial valorization.

ABSTRACT A fluorine‐free hydrophilic coating was fabricated on polytetrafluoroethylene (PTFE) membranes using sodium dodecylbenzenesulfonate (SDBS), nano‐silica (SiO 2 ), and ethylene‐vinyl alcohol copolymer (EVOH) through a simple immersion–drying process. The modification aimed to improve membrane wettability, permeability, and chemical stability. FTIR, XPS, SEM, and AFM analyses confirmed the formation of a uniform organic–inorganic composite coating. AFM further showed that the characteristic granular morphology and surface roughness changed little after immersion in acidic, alkaline, and oxidative solutions, indicating good nanoscale structural stability under harsh conditions. At the optimal composition (SDBS:SiO 2 :EVOH = 2:1:1), the water contact angle decreased from 124.8° for pristine PTFE to 60.6°, while the pure water flux reached 3727.99 L m −2 h −1 . The modified membrane also exhibited high flux recovery after bovine serum albumin fouling, with a flux recovery ratio of 92.3%. In oil–water separation tests, the membrane achieved separation efficiencies above 98% and maintained stable performance during three consecutive filtration cycles. In addition, stable wettability and permeation performance were retained after 1‐week immersion in solutions ranging from pH 1–14. The results indicate that the EVOH‐stabilized SiO 2 /SDBS coating provides an effective, PFAS‐free, and scalable strategy for preparing durable hydrophilic PTFE membranes under harsh operating conditions.

Structurally engineered perfluoropolyether (PFPE)-based silane coupling agents offer a compelling route to multifunctional surface coatings with low surface energy, high transparency, and robust mechanical durability. In light of emerging PFAS regulatory constraints, this work presents a modular molecular design strategy that leverages PFPE backbones via controllable Williamson etherification and terminal silanization to achieve high-performance yet compositionally streamlined coatings. By tuning the molecular weight (1800-3500 g/mol), terminal architecture (mono- vs. di-functional), and hydrolyzable group density (3, 6, or 12 per molecule), a systematic correlation between molecular parameters and interfacial performance was established. LiOH was identified as an efficient catalyst for etherification, yielding up to 78.2% conversion at 70 degrees C. Among the synthesized agents, the bifunctional DY3-6 exhibited optimal coating performance, achieving an initial water contact angle (WCA) of 114.7 degrees and maintaining 113.6 degrees after 3000 abrasion cycles. At an optimized spray concentration of 0.4 wt.%, coatings exhibited excellent transparency (>98%) and anti-fouling behavior on both glass and textiles. Surface analysis via XPS and EDS confirmed the homogeneous distribution of fluorinated, siloxane, and amine moieties. These findings underscore the importance of precision molecular architecture in advancing PFPE-based surface technologies for durable, optically clear, and contamination-resistant applications in electronics and advanced textiles.

Proton exchange membrane fuel cells (PEMFCs) are promising electrochemical energy-conversion devices, but their performance is limited by the sluggish kinetics of the oxygen reduction reaction (ORR). In this study, the effects of post-synthesis acid treatment on polyol-derived Pt/C catalysts supported on Vulcan XC-72 were systematically investigated. Eight chemically distinct acids, including citric, sulfuric, phosphoric, tartaric, oxalic, nitric, acetic, and hydrochloric acids, were compared under otherwise identical preparation conditions, followed by a separate citric-acid dosage series corresponding to final pH values of 2-5. The influences of acid chemistry and post-treatment pH on Pt retention, nanoparticle size and dispersion, Pt surface oxidation state, electrochemically active surface area (ECSA), ORR activity, and durability were evaluated. Thermogravimetric analysis showed that the citric-acid-treated catalyst exhibited a residual Pt fraction of 29.68wt.%, corresponding to approximately 99% of the nominal Pt loading. XRD and TEM analyses revealed Pt crystallite and particle sizes in the range of approximately 2.2–3.8nm, with the citric-acid-treated catalyst showing relatively small and uniformly dispersed Pt nanoparticles. At pH 2, the citric-acid-treated catalyst achieved the highest ECSA of 106.2 m2 gPt-1 and an ORR mass activity of 0.279A mgPt-1 at 0.9V vs. RHE, exceeding the values measured for commercial Johnson Matthey HiSPECTM 3000 Pt/C (91.1 m2 gPt-1 and 0.216A mgPt-1, respectively). XPS further showed that the citric-acid-treated catalyst retained a relatively high fraction of metallic Pt, consistent with its favorable electrochemical accessibility and surface state. After 30,000 potential cycles, the citric-acid-treated catalyst exhibited a lower ECSA loss than the commercial reference (25.3% vs. 42.3%) and less XRD-detectable crystallite coarsening. Single-cell measurements under matched cathode Pt loading also showed higher cell voltages for the citric-acid-treated catalyst over the investigated current-density range. These results indicate that post-synthesis citric acid treatment can improve Pt retention, nanoparticle dispersion, electrochemical accessibility, ORR activity, and structural durability through acid-dependent surface and Pt–carbon interfacial effects. The present protocol was demonstrated at a laboratory scale, yielding approximately 80mg of catalyst per batch.

ABSTRACTThis study employed short fluorocarbon chain perfluorohexylethyl methacrylate (PFOL, R f = 6) and long hydrocarbon chain Stearyl acrylate (SA, R = 18) to synthesize a series of fluorinated acrylate polymers (FAP) via solution polymerization. The copolymerization rates of PFOL and SA were calculated, and the copolymer composition curves were plotted to produce FAP with uniform composition and varying PFOL ratios. Experiments revealed that these FAP demonstrated significant dissolution and migration behaviors during the processing of fluoroelastomers, influenced by the PFOL to SA ratio. The optimized FAP (PFOL ratio of 0.7), with a weight‐average molecular weight between 23,000 and 26,000, significantly reduced the demolding force of fluoroelastomer O‐rings from 49 to 20 N. Water contact angle and demolding force tests further verified the internal mold release effects of the FAP. Predictions from the CISOC‐PSAT program indicate that the FAP synthesized in this study is less toxic compared to the copolymer of perfluorooctylethyl methacrylate (POEMA) and SA, with negative results for carcinogenic and mutagenic toxicity, demonstrating its potential as an environmentally friendly, green fluorine‐containing internal mold release agent.

The widespread use of fluorinated silane coupling agents in hydrophobic textile coatings has raised increasing concerns due to their bioaccumulation and environmental persistence. In this study, a series of fluorine-free, POSS-based silane coupling agents were synthesized via hydrosilylation between octavinyl polyhedral oligomeric silsesquioxane (OV-POSS) and two functional silanes-trimethoxyhydrosilane (MTMS) and bis(trimethylsiloxy)methylsilane (MDHM)-with tunable molar ratios. These hybrid silanes were applied to cotton fabric using a simple one-step dip-coating method. Among them, the POSS-4MTMS-4MDHM formulation, at a concentration of 0.2 wt%, imparted superhydrophobicity with a water contact angle (WCA) of 151 degrees and a sliding angle (SA) of 8 degrees. The modified fabric exhibited outstanding mechanical durability, maintaining a WCA of 147 degrees after 100 abrasion cycles under 200 g loading, and retained excellent water repellency after ultrasonic washing and tape-peeling tests. Furthermore, the coating demonstrated chemical resistance over a wide pH range, while preserving the inherent softness and improving the surface smoothness of the fabric. In oil-water separation tests, the coated fabric achieved a separation efficiency of 98.5% and an oil flux of 11.59 L m(-2) s(-1), with efficiency remaining above 97% after 30 reuse cycles. This scalable, fluorine-free strategy enables the fabrication of multifunctional, robust textile coatings with hydrophobic, antifouling, and separation properties.

To address the issues of low yield, high cost, and poor recyclability associated with conventional Pt-based catalysts in the hydrosilylation of fluorinated olefins, this study develops an efficient, stable, and economically sustainable RuCl3-FeCl3/C supported catalytic system. Through a systematic comparison of different supports (activated carbon, alpha-Al2O3, gamma-Al2O3, and ZSM-5) and metal loadings, it was found that 5 wt% RuCl3 supported on activated carbon achieved a perfluorohexylethyltrimethoxysilane (PFOT) yield of 58 % in the first cycle and maintained over 51 % after three cycles. Introducing FeCl3 at a Ru:Fe molar ratio of 1:3 further enhanced catalytic performance, increasing the first-cycle yield to 79 % and maintaining over 76 % in subsequent cycles. XPS analysis revealed that Fe3+ effectively suppresses the reduction of Ru3+ to Ru0 by forming an electronic buffer zone, thereby stabilizing the oxidation state of the active center and prolonging catalyst lifetime and selectivity. Kinetic studies confirmed that this synergistic effect reduced the apparent activation energy from 31 kJ/mol to 21 kJ/mol. Compared to existing Pt-based systems, the Ru-Fe bimetallic catalyst demonstrates a superior balance of catalytic activity, operational stability, economic feasibility, and industrial scalability.

Polytetrafluoroethylene (PTFE) membranes are renowned for their excellent thermal stability, resistance to strong acids and alkalis, and superior mechanical stability. However, its inherent strong hydrophobicity significantly limits its use in water treatment. In this study, a SiO2 coating was successfully deposited in-situ on the surface of PTFE membranes using a hydrolyzed solution of tetraethyl orthosilicate (TEOS) compounded with the commercial fluorinated polyoxyethylene ether surfactant FS-31 (C6F13CH2CH2O(CH2CH2O)nH). The modification mechanism involves using the low surface energy nonionic fluorocarbon surfactant FS-31, which interacts hydrophobically with the PTFE substrate, serving as an "anchor" point around which the TEOS hydrolyzes and condenses around the fibers and nodes of the PTFE membrane, forming a complete and stable chemical network structure. The results show that the initial water contact angle of the modified membrane dropped to 36.5 degrees, and the water flux reached 537.9 L m- 2 h-1. After being continuously immersed in strong acid (5 wt% HCl), strong alkali (4 wt% NaOH), and oxidizing agent (5 wt% NaClO) for one week, the membrane maintained excellent hydrophilicity and stability. This study proposes a mild and efficient modification method to prepare durable hydrophilic PTFE membranes, portending great potential for applications in harsh environments.

The catalytic decomposition of methane (CDM) is a plausible means to convert methane to turquoise hydrogen with simultaneous carbon sequestration, in the form of solid carbon nanomaterials (CNMs). The key to a cost-effective CDM process is a high-performance and low-cost catalysts. Mg-Fe-O CDM catalysts have shown outstanding CDM performance in comparison with Fe, whilst being affordable and easy to produce. By optimizing the Fe: Mg ratios (3: 1, 2: 1, 1: 1, 1: 2, 1: 3) of Mg-Fe-O catalysts to render the best activation and exsolution behavior of fresh catalysts containing partial solid solutions. The structural–functional relationships relevant to CDM are established by characterizing the fresh catalysts, the spent catalysts, as well as catalysts sampled at various stages of CDM by using BET, XRD, TEM-EDS, H2-TPR, Raman and TG. The results are interpreted with the help of computationally calculated phase diagrams of the Mg-Fe-O system at the operating conditions of interest. Notably, the catalyst with a Fe: Mg ratio of 1 offers the optimal CDM performance in terms of methane conversion (maximum 48%) and carbon yield (8.6 gC/gFe), attributed to the efficient exsolution of well dispersed Fe0 particles from the MgO-FeO solid solution matrix. As the CDM reaction proceeded, Fe/MgO catalysts gradually become coated with deposited CNMs, ultimately leading to the CDM process cessation. The results exemplify the importance of understanding the redox behavior of solid solutions for designing cost-effective CDM catalysts with superior catalytic performance.

The oxygen evolution reaction (OER) is a pivotal process in water electrolysis systems, yet developing costeffective and highly active OER electrocatalysts from earth -abundant materials through straightforward methods remains a formidable challenge. In this study, FeCo oxides and their fluorides are synthesized using a one-step room -temperature process followed by fluorination with fluorine gas. We compared the OER performance of Fe, Co, and FeCo oxides and investigated the impact of fluorine doping on their physical properties and OER efficiency. Results revealed that the FeCo - O bimetallic oxide exhibited an overpotential of 370 mV in an alkaline electrolyte at a current density of 10 mA/cm 2 , significantly surpassing the performance of monometallic Fe - O (1 V) and Co - O (467 mV). Fluorine modification markedly enhanced the OER activity of these materials, with Fe -OF at 570 mV, Co -OF at 330 mV, and FeCo-OF at 285 mV. Notably, FeCo-OF demonstrated a stable overpotential lower than commercial RuO 2 (289 mV) during a continuous 12 h OER test. Electrochemical analyses and spectral characterizations indicated that fluorine ion electronic regulation facilitated efficient electrocatalytic active sites in the spent FeCo-OF catalyst through in situ self -reconstruction, leading to its stable and superior OER performance. Density functional theory (DFT) calculations confirmed that fluorine modification of the bimetallic oxides decreased the O* Gibbs free energy from 4.86 to 2.44 eV, thereby enhancing the kinetics of the OER reaction.

Carbon materials have a very wide range of applications in the field of electrocatalysis, both as catalyst bodies and as excellent supports for catalysts. In this work, we obtained a graphitic-like orange-peel derived carbon (OPC) material through pre-carbonization and KOH activation strategies using discarded orange-peel as a raw material. OPC has good graphitization characteristics and a few-layer structure, making it very suitable as a support for nanoparticle catalysts. In order to compare the performance of OPC, we used commercial graphene as the benchmark, made two carbon materials uniformly loaded with ruthenium nanoparticles under the same conditions, and obtained two HER catalysts (Ru/OPC and Ru/rGO). The results indicate that Ru/OPC has excellent HER catalytic performance under alkaline conditions, not only superior to Ru/rGO, but also surpassing commercial Pt/C. In 1 M KOH; the overpotential of Ru/OPC is only 3 mV at -10 mA cm-2, greatly exceeding those of Ru/rGO (100 mV) and Pt/C (31 mV). Under high current density (j), the performance of Ru/OPC is even better; the overpotential is 79 mV and 136 mV at -100 mA cm-2 and -200 mA cm-2, respectively. More importantly, Ru/OPC also has a very high TOF and long-term stability, with a TOF of up to 10.62 H2 s-1 at an overpotential of 100 mV and almost no attenuation after 72 h of operation at -50 mA cm-2. Ru/OPC also exhibits good catalytic performance under acidic conditions, significantly superior to that of Ru/rGO. For Ru/OPC, the overpotential is 86 mV, 167 mV and 214 mV at -10 mA cm-2, -100 mA cm-2 and -200 mA cm-2, respectively. Under the same conditions, the overpotential of Ru/rGO is 143 mV, 253 mV and 306 mV at -10 mA cm-2, -100 mA cm-2 and -200 mA cm-2, respectively.

A structurally stable and antibacterial biomaterial used for temporary cranioplasty with guided bone regeneration (GBR) effects is an urgent clinical requirement. Herein, we reported the design of a biomimetic Ag/bacterial cellulose/hydroxyapatite (Ag/BC@HAp) hydrogel mesh with a double-sided functionalized structure, in which one layer was dense and covered with Ag nanoparticles and the other layer was porous and anchored with hydroxyapatite (HAp) via mineralization for different durations. Such a double-sided functionalized design endowed the hydrogel with distinguished antibacterial activities for inhibiting potential infections and GBR effects that could prevent endothelial cells and fibroblasts from migrating to a defected area and meanwhile show biocompatibility to MC3T3-E1 preosteoblasts. Furthermore, it was found from in vivo experimental results that the Ag/BC@HAp hydrogel with 7-day mineralization achieved optimal GBR effects by improving barrier functions toward these undesired cells. Moreover, this BC-based hydrogel mesh showed an extremely low swelling ratio and strong mechanical strength, which facilitated the protection of soft brain tissues without gaining the risk of intracranial pressure increase. In a word, this study offers a new approach to double-sided functionalized hydrogels and provides effective and safe biomaterials used for temporary cranioplasty with antibacterial abilities and GBR effects.

Synthesization of 1H,1H,2H,2H-Perfluorooctyltrimethoxysilane through solvent-free hydrosilylation of 1H,1H,2H-perfluoro-1-octene with trimethoxysilane was efficiently conducted over the RuCl3 center dot 3H2O catalyst. The synergistic action of Ru3+ as the active center and the strong electronegativity of Cl- to attract the electron of the electron-donating group -OCH3 in trimethoxysilane, activated the Si-H and thus promoted the reaction. The influences of different reaction conditions including feed order, feed ratio, catalyst dosage, reaction temperature and reaction time on the reaction yield were fully investigated, to conclude the optimized condition to achieve a yield of 86.80% was the feed of 1.2 mol trimethoxysilane per mole of 1H,1H,2H-perfluoro-1-octene, together with the addition of 9.56 x 10-4 mol RuCl3 center dot 3H2O per mole of trimethoxysilane, at 80 degrees C for 4 h; while the additive of CuCl to RuCl3 center dot 3H2O catalyst could further improve the reaction yield at 50celcius. Finally, after understanding the activity of Ru with different valence state, the reaction mechanism was also proposed. CO 2022 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved.

There is a need to create next-generation polymer composites having high property, unique function, and intelligent behaviors, such as shape memory effect (SME) and self-healing (SH) capability. Rare earth complexes can provide luminescence for polymers, and their dispersion is highly affected by ligand structures. Here, we created three different REOCs with different ligands before studying the effects of ligands on REOC dispersion in polyurea–urethane (PUU) with disulfide bonds in main chains. In addition, the effects of different REOCs on mechanical properties, luminescent functions, and intelligent behaviors of PUU composites were studied. The results showed that REOC I (Sm(TTA)3phen: TTA, thenoyltrifluoroacetone; phen, 1,10-phenanthroline) has incompatible ligands with the PUU matrix. REOC I and REOC III (Sm(BUBA)3phen: BUBA, 4-benzylurea-benzoic acid) with amine and urea groups facilitate their dispersion. It was REOC III that helped the maintenance of mechanical properties of PUU composites due to the good dispersion and the needle-like morphologies. Due to more organic ligands of REOC III, the fluorescence intensity of composite materials is reduced. The shape recovery ratio of the composite was not as good as that of pure PUU when a large amount of fillers was added. Besides, REOC I reduced the self-healing efficiency of PUU composites due to poor dispersion, and the other two REOCs increased the self-healing efficiency. The results showed that ligands in REOCs are important for their dispersion in the PUU matrix. The poor dispersion of REOC I is unbeneficial for mechanical properties and intelligent behavior. The high miscibility of REOC II (Sm(PABA)3phen: PABA, 4-aminobenzoic acid) decreases mechanical properties as well but ensures the good shape recovery ratio and self-healing efficiency. The mediate miscibility and needle-like morphology of REOC III are good for mechanical properties. The shape recovery ratio, however, was decreased.

To overcome severe issues of photothermal effect from sunlight irradiation onto bionic leaves, natural-inspired bionic leaves with three layers, that is, high near-infrared reflection layer, absorption composite layer, and cilia layers are created. The front layer presents a high near-infrared light reflection and reduces photothermal effect from the sunlight. The mediate layer contributes to water transpiration and absorption, facilitating heat dissipation. The bottom layer has artificial cilia arrays that enhance air convection to reduce heat accumulation . More specifically, modified chromium trioxide (Cr2O3) is added into polyvinyl alcohol (PVA), and the optimal concentration is achieved based on investigations on photothermal effects. Carbon-fiber (CF) mat with calcium chloride (CaCl2) is used as absorption composite layers. The water absorption and loss rates under different temperature and humidity are studied and fitted using different equations. Cilia arrays are created using a magnetic field induction method, and their heat convection effects are studied based on simulation. Finally, the three layers are assembled and their temperature reduction effects are studied. The results show that the average surface temperatures of tri-layered leaves are close to natural leaves andthe difference is 0.6 degrees C in a week.

采用熔融法以铁、钼、铜和钨硝酸盐为原料,制备出一系列的FexMy(M=Mo、Cu、W)双金属催化剂.首先考察了一系列的Fe15M1(M=Mo、Cu、W)双金属催化剂的甲烷催化裂解(CDM)活性,Fe15Mo1的催化活性远高于Fe15Cu1和Fe15W1.通过比表面积测试(BET)、X射线衍射(XRD)、H2程序升温还原(H2-TPR)和拉曼光谱(Raman)等分析方法对Fe15M1的物理特性、结构组成、还原特性和副产物碳纳米材料(CNMs)的石墨化度等进行表征.进一步考察了金属Mo的掺杂量和焙烧温度对FexMoy双金属催化剂的甲烷转化率和碳产率的影响.Fe1Mo1表现出优异的催化性能,其碳产率(6gC/gcat)高于纯Fe的碳产率(4.35gC/gcat).XRD和X射线光电子能谱(XPS)分析表明,Fe1Mo1双金属形成Fe2(MoO4)3相,提高了其催化活性和稳定性;透射电镜(TEM)结果表明,Fe1Mo1催化剂CDM反应后的CNMs为竹节状的碳纳米管.