Search Results (346)

The excessive emission of greenhouse gases (CO₂, CH₄, SF₆, and CF₄.) is a primary driver of global climate change, making the development of efficient adsorption and separation technologies critically important for achieving carbon reduction goals. Metal–organic frameworks (MOFs) have attracted considerable attention in this field due to their crystalline porous structures, ultrahigh surface areas, and tunable pore architectures. However, pristine MOFs face significant bottlenecks including poor water stability, high bed pressure drops caused by their powdered form, and limited mass transfer, which severely hinder their industrial application. The integration of MOFs with functional materials such as carbon materials, polymers, metal oxides, and porous SiO₂ offers a synergistic strategy to overcome these limitations. Carbon materials provide hydrophobic barriers and mesoporous transport channels, polymers enhance processability and mechanical strength, metal oxides introduce basic sites for enhanced chemisorption, and MOF-on-MOF heterostructures enable atomic-level interfacial integration and pore synergy. This review systematically summarizes recent advances in MOF composites for the separation of CO₂, CH₄, and fluorinated greenhouse gases (SF₆, CF₄.), with an emphasis on design strategies, structure–performance relationships, and synergistic mechanisms across different composite types. Finally, the current challenges including scalable synthesis, long-term stability, and separation performance under realistic conditions are discussed, and future directions toward rational design and functional synergy for industrial carbon capture and fluorinated gas emission reduction are envisioned. Full article

To enhance the temperature, salt and shear resistance of conventional polyacrylamide oil-displacing agents, a fluorinated hydrophobically associating polymer AM-AA-HDFDMA was synthesized by aqueous solution polymerization. Acrylic acid (AA) and acrylamide (AM) were utilized as comonomers, with perfluorooctylethyl methacrylate (HDFDMA) serving as the fluorinated hydrophobic functional monomer. The synthesis employed an ammonium persulfate-sodium bisulfite (APS-NaHSO₃) redox initiation system. The selected synthesis conditions were established as a total monomer mass fraction of 25%, an initiator dosage of 0.3 wt% of the total monomers, a reaction temperature of 40 °C, and a reaction time of 4.5 h. The chemical structure and micromorphology of the polymer were characterized by Fourier transform infrared spectroscopy (FT-IR), proton nuclear magnetic resonance (¹H-NMR), and scanning electron microscopy (SEM). Furthermore, its thickening performance, shear resistance, temperature resistance, salt tolerance, and oil displacement efficiency were systematically evaluated. Full article

A critical challenge in coalbed methane (CBM) extraction is the severe formation damage induced by conventional foam fracturing fluids, primarily through polymer retention and hydrogen bond disruption within the microporous matrix. This study presents a molecularly engineered, low-damage foam fracturing fluid that leverages synergistic nanoparticle–surfactant interactions to construct a robust interfacial pseudo-gel network, thereby decoupling effective fracture stimulation from adverse geochemical damage. The primary novelties of this work are threefold: (i) establishing a direct, quantitative cause-and-effect relationship between molecular interfacial architecture and reservoir protection, (ii) proposing a comprehensive “interfacial control” design paradigm that engineers viscoelasticity at the gas–liquid interface rather than through bulk polymer gelation, and (iii) demonstrating the complete decoupling of foam stability from formation damage in a polymer-free system. A systematic optimization methodology was employed: initial foaming agents were screened via the Waring Blender method, evaluating foam volume, half-life, and a derived comprehensive index; subsequently, synergistic binary surfactant mixtures and foam stabilizers were assessed to formulate the final systems. An optimized formulation, designated Foam System I (0.5 wt.% fluorosurfactant FK + 0.5 wt.% nano-silica RX + 2.0 wt.% KCl), demonstrated exceptional foam quality (Γ = 77.1 ± 1.5%) and kinetic stability (T₁/₂ > 350 s). Rheological characterization confirmed shear-thinning behavior conforming to the Herschel–Bulkley model (n = 0.38–0.42, R² > 0.98) and a structural recovery of 92.5 ± 2.1%—comparable to crosslinked polymer gels but achieved without any bulk viscosifier. Core flood analyses revealed that Foam System I induced a permeability damage of only 12.75 ± 1.8%, representing a 55–75% reduction compared to polyethylene glycol (PEG)-stabilized reference fluids (28.36–51.91%). X-ray photoelectron spectroscopy (XPS) correlated this enhanced reservoir compatibility with an 18.0 ± 2.0% suppression of oxygen-containing functional group adsorption, attributed to the steric hindrance conferred by the fluorinated hydrophobic moieties. This work establishes an “interfacial control” paradigm wherein gel-like stabilization for proppant transport is achieved via interfacial viscoelasticity rather than bulk polymer gelation, thereby directly addressing the critical imperative to harmonize fracture conductivity with reservoir protection in unconventional energy development. The findings are validated for shallow CBM reservoir conditions (25–35 °C), with extension to higher-temperature formations identified as a priority for future investigation. Full article

This study provides the first comprehensive assessment of microplastic (MP) contamination within oyster bed ecosystems of the Kingdom of Bahrain. Sediment, water, and oyster samples were collected from six sites representing diverse environmental conditions. Raman spectroscopy identified the presence of 12 distinct polymer types, with polypropylene (PP), polyurethane (PU), poly(ethylene terephthalate)/diamine/multi-walled carbon nanotube (PET/diamine/MWCNT), and fluorinated ethylene propylene (FEP) being the most prevalent. MPs occurred predominantly as fragments, films, and pellets, with black being the most common color across all matrices. MP abundances ranged from 750 to 1850 MPs/kg dry weight in sediments, 2100–9600 MPs/L in water, and 1.78–5.25 MPs/individual in oysters, with particles (<50 µm) most frequent in oyster tissues. Although spatial variation was evident across regions, detected polymers included types associated with known ecotoxicological risks. No significant correlation was observed between sediment grain size and MP abundance, suggesting that additional hydrodynamic or anthropogenic factors may influence MP distribution. Overall, this study provides critical baseline data on MP contamination in Bahrain’s marine environments and highlights the need for continued monitoring to assess potential risks to marine ecosystems and seafood safety. It also contributes to the limited understanding of MPs in the Arabian Gulf, informing future monitoring, conservation and policy initiatives that support long-term environmental sustainability. Full article

As a green energy technology, triboelectric nanogenerators (TENGs) convert mechanical energy into electricity and have gained significant attention in response to growing global environmental concerns. However, the widespread use of petroleum-based polymers as triboelectric materials in high-performance TENGs raises concerns over plastic pollution. In this work, we report a high-performance biodegradable TENG utilizing chitosan/laser-induced graphene (LIG) composite films as triboelectric layers. Modified chitosan substrates were first converted into LIGs via a convenient one-step CO₂ laser engraving, subsequently incorporated into chitosan matrices to form homogeneous composite films. A TENG device was designed by pairing the LIG/chitosan composite film with the fluorinated ethylene propylene (FEP) film, and copper electrodes. The introduction of LIG effectively strengthens charge storage and dielectric properties of the chitosan matrix, thereby significantly boosting the triboelectric output performance. Experimental results demonstrate that the as-assembled TENG with an LIG concentration of 1 wt.% achieves a peak open-circuit voltage of 196 V and short-circuit current of 2.1 μA, with a maximum power density of 295 mW/m². It can drive LED lights and small low-power electronic devices. Furthermore, the designed TENG device exhibits good biodegradability, flexibility, and stability, serving as a self-powered sensor for monitoring human joint movements. This work provides a simple and scalable strategy for integrating laser-induced graphene with biomass-based polymers, offering new insights into the design of high-performance, biobased triboelectric materials. Full article

To overcome the inherent drawbacks of poly(propylene carbonate) (PPC), such as poor thermal stability, low mechanical strength, and high surface energy, this study introduced, for the first time, 1,1,1-trifluoro-2,3-epoxypropane (TF-PO) as a third monomer into the metal-free TEB/PPNCl catalytic system for the terpolymerization with carbon dioxide (CO₂) and propylene oxide (PO), successfully synthesizing a series of fluorinated PPC (PPCF). The optimal polymerization conditions ($60 °C$, 2.0 MPa, 12 h, n(PO):n(TF-PO) = 100:4) were determined through systematic optimization. Comprehensive structural characterization (FT-IR, NMR, XPS) confirmed the successful incorporation of TF-PO into the polymer backbone. Property evaluation revealed that the PPCF materials exhibited substantial improvements in thermal stability, mechanical strength, hydrophobicity, and dielectric properties compared to unmodified PPC. The optimal sample, PPCF4, achieved a $5\%$ weight-loss temperature ($T_{d,-5\%}$) of $242 °C$, a glass transition temperature ($T_{\mathrm{g}}$) of $42 °C$, a tensile strength of 21.5 MPa, and a Young modulus of 296 MPa. With a $5\%$ TF-PO feed ratio, the material’s water contact angle increased to 102°, and its dielectric constant reached 6.01 at ${10}^4$ Hz. Furthermore, density functional theory (DFT) calculations elucidated the Lewis acidity of the TEB catalyst and the reactive sites of the monomers, leading to a proposed mechanism for the ternary alternating copolymerization. This work provides an effective synthetic strategy and theoretical foundation for preparing high-performance and functionalized PPC materials through molecular structure design. Full article

Graphite remains the predominant negative electrode material in commercial lithium-ion batteries (LIBs); however, its practical performance is increasingly limited by interface-driven degradation rather than bulk intercalation. This review examines the interconnected electrochemical, mechanical, and safety challenges associated with uncoated and coated graphite, with particular focus on how solid electrolyte interphase (SEI) formation and evolution deplete cyclable lithium, increase interfacial resistance, and induce polarization that leads to lithium plating and dendritic growth during rapid charging and low-temperature operation. Electrolyte and solvation engineering are highlighted as coating-free strategies to mitigate these issues by reducing Li⁺ desolvation barriers and directing interphase chemistry toward thinner, more ion-conductive, fluorinated SEI films that inhibit plating while maintaining high-rate capability. Coated graphite approaches are compared, including carbon, inorganic, and polymer coatings that function as artificial SEI layers to minimize direct electrolyte contact, stabilize interphase composition, and enhance mechanical durability. Key trade-offs are discussed, including decreased first-cycle coulombic efficiency (FCCE) due to increased surface area, transport limitations arising from excessively thick coatings, nonuniform coverage leading to local current hotspots, and side reactions induced by the coatings. The discussion is further extended to sodium and potassium systems, explaining how larger ion sizes, unfavorable thermodynamics, and significant lattice expansion hinder their insertion into graphite, and summarizing strategies such as interlayer expansion and alternative carbon architectures that improve reversibility for larger ions. This review concludes that achieving durable, safe, and fast-charging graphite electrodes requires an integrated interfacial design that combines optimized graphite morphology, electrode architecture, and electrolyte chemistry. Full article

Stone heritage deteriorates through physical, chemical, and biological processes driven by water, climate, and microbial colonization. Multifunctional polymeric coatings combining hydrophobic and antimicrobial moieties have emerged as a promising conservation strategy, yet a substantial gap remains between laboratory innovation and real-world performance. This review critically examines advances from 2021 to 2026, covering wetting theory, antimicrobial mechanisms, and material architectures, including molecularly integrated systems, Sol–Gel hybrids, nanocomposites, and layered systems. Long-term studies on the Aurelian Walls in Rome and stone in Reims show that biocidal efficacy typically declines within one to two years despite the chemical persistence of the coatings. In parallel, hydrophobic performance often deteriorates over time due to UV exposure, particulate deposition, and surface chemical changes, leading to increased wettability and reduced protective efficiency. Substrate porosity governs durability and visual compatibility (ΔE* < 5 threshold), while treatments can reshape microbial communities, favoring stress-tolerant meristematic fungi. Regulatory pressure on fluorinated compounds drives the development of more sustainable alternatives. Emerging directions include stimuli-responsive systems, self-healing materials, slippery interfaces, and precision polymer architectures. However, future progress will depend on tailoring formulations to major lithotypes, improving compatibility with porous substrates, and validating performance through standardized accelerated aging and multi-year field trials. Bridging laboratory design with environmental exposure data and conservation practice will be essential for achieving durable and culturally acceptable protection strategies. Full article

Hydrogen is increasingly adopted as a clean energy carrier for storing and transporting low-carbon energy. Achieving a practical volumetric energy density for real-world deployment typically requires compression to several hundred bar, which in turn demands dedicated high-pressure infrastructure. Because valves are indispensable for isolation and flow control within this infrastructure, durable sealing valve materials become a key reliability and safety requirement. This assembly-level screening study compares two valve configurations with different polymer assemblies: EPDM O-rings with PEEK seats/bushing and NBR O-rings with POM seats/bushing. Four new identical 500-bar ball valves were tested (two EPDM/PEEK and two NBR/POM). For each seal configuration, one valve was cycled 5000 times at 500 bar in helium (inert baseline), and a second identical valve was cycled 5000 times at 500 bar in hydrogen to isolate hydrogen effects from mechanical/metallic wear. Leakage was tracked during cycling, and seals were analyzed by SEM/EDX after testing. The EPDM/PEEK configuration remained leak-tight in both gases, with no cracking observed in the elastomer or thermoplastic components. The NBR/POM configuration exhibited POM bushing fracture during cycling and minor external leakage at the stem during the hydrogen phase, accompanied by micro-fissures on the NBR O-ring surface. EDX indicated composition changes after cycling, including oxygen and fluorine enrichment and occasional metallic transfer species, consistent with surface films and deposits. Under the present valve geometry and cycling protocol, EPDM/PEEK provided robust sealing, whereas NBR/POM showed failure modes relevant to high-pressure service. These findings are intended as configuration-level screening evidence to be used in valves rather than as a full qualification of the individual materials. Full article

In this work, poly(3-dodecylthiophene) (P3DDT) thin films were electrochemically synthesized onto fluorine-doped tin oxide (FTO) substrates via cyclic voltammetry using tetraethylammonium tetrafluoroborate (Et₄NBF₄) as the supporting electrolyte. Optical analyses were performed using ultraviolet–visible absorption spectroscopy (UV-Vis), photoluminescence spectroscopy (PL), emission ellipsometry (EE) and Raman spectroscopy. The results revealed the formation of distinct structures during the electropolymerization process, which significantly affected the optical behavior observed in the UV–Vis and PL spectra. Furthermore, the EE measurements provided insights into the impact of these structures on the polarization states of emitted and transmitted light on energy and charge transfer mechanisms and on the photophysical behavior of P3DDT. Variations in the degree of polarization (P), anisotropy factor (r), and asymmetry factor (g) were analyzed as a function of the emission wavelength. The results confirm the potential of P3DDT as an active layer in electroluminescent devices, as the emissive material used in the active layer consisted exclusively of this polymer. Full article

Phosphogypsum (PG) is a byproduct of wet-process phosphoric acid production and contains soluble phosphorus (P), fluorine (F), and other harmful impurities in addition to calcium sulfate. Its acidic leachate enriched with P and F poses long-term risks to soil and surrounding water bodies. Owing to the incorporation of soluble P and F within calcium sulfate crystal interlayers, these contaminants are gradually released during storage, making it difficult to achieve an economically efficient and environmentally benign treatment of PG at an industrial scale. In this study, a low-cost and sustainable process for the effective and long-term immobilization of soluble P and F in PG was developed using sulfuric acid-activated red mud (RM), an industrial waste rich in Fe and Al. After pulping PG with water, activated RM was added, followed by pH adjustment with Ca(OH)₂, leading to the in situ formation of amorphous calcium aluminate and calcium ferrite polymers with strong adsorption affinity toward soluble P and F. The immobilization mechanism and phase evolution were systematically investigated using inductively coupled plasma optical emission spectroscopy (ICP-OES, PS-6PLASMA SPECTROVAC, BAIRD, USA), on a Rigaku Miniflex diffractometer (Rigaku Corporation, Tokyo, Japan), scanning electron microscopy coupled with energy-dispersive spectroscopy (SEM-EDS), and zeta potential analysis. The leachate of PG treated with activated RM and Ca(OH)₂ contained P < 0.5 mg/L and F < 10 mg/L at pH 8.5–9.0, meeting environmental requirements (pH = 6–9, P ≤ 0.5 mg/L, F ≤ 10 mg/L). Moreover, the immobilized P and F exhibited enhanced stability during long-term stacking, indicating the formation of durable immobilization products. This study demonstrates an effective “treating waste with waste” strategy for the large-scale, environmentally safe utilization of phosphogypsum. Full article

The trade-off between the ionic conductivity and the stability of the proton exchange membrane (PEM) is a major concern in the development of PEM water electrolysis (PEMWE). This review focuses on the design and fabrication of homogeneous and composite PEMs for water electrolysis and establishes the structure–performance relationships between the membrane chemical/physical structures and their efficiency metrics—specifically, proton conductivity, hydrogen permeability, and chemical and mechanical stability. A special focus is placed on the fundamental connection between the microstructure and performance of membrane materials. At the molecular level, we systematically illustrate the design principles for main chains, side chains, and sulfonate groups, covering both fluorinated PEMs (encompassing perfluorinated and partially fluorinated membranes) and non-fluorinated PEMs (including aromatic polymers with heteroatom backbones and all-carbon backbones). At the macroscopic level, the review provides an in-depth exploration of two primary modification strategies: creating composites with organic polymers and with inorganic nanofillers. In summary, this review elucidates how these composite approaches leverage material synergies to improve the membrane’s mechanical integrity, proton conduction efficiency, and chemical resistance and offers a theoretical framework for the rational design of next-generation, high-performance PEMs to advance the commercialization of PEMWE technology. Full article

Fluorine-containing polyarylates (F-PARs) were synthesized via interfacial polycondensation of hexafluorobisphenol A (BPAF), bisphenol A (BPA), and two acyl chloride monomers under four feeding strategies. Sequential feeding affords the highest M_w (2.02 × 10⁵ g/mol) and high alternating sequence content; the one-pot method gives intermediate M_w and a random sequence; and segmented and parallel methods yield lower-M_w polymers and pseudo-block sequences. Time-resolved GPC results reveal that the concentration of -CF₃-activated acyl chloride termini during chain propagation controls the subsequent chain propagation and, thus, the final M_w. Consequently, sequential feeding delivers the highest T_g (215 °C) and stiffness (2.51 GPa) for thermal–mechanical loads; the one-pot protocol maximizes optical clarity (T₄₅₀ = 85%) for transparent films. Systematic variation in the BPAF/BPA ratio via sequential feeding further reveals that higher BPAF content increases M_w, enhances thermal stability, and blue-shifts UV absorption, whereas BPA-rich compositions improve the tensile strength and modulus. These findings provide a quantitative roadmap for the rational design of F-PAR chain architectures, enabling on-demand tuning of thermal, mechanical, and optical properties without additional synthetic complexity. Full article

A novel fluorinated diamine monomer, 4,4′-((bicyclo[2.2.1]hept- 5-ene-2,3-diylbis (methylene)) bis(oxy))bis(3- (trifluoromethyl) aniline) (NFDA), featuring a tailored alicyclic norbornane core, flexible ether linkages, and pendant trifluoromethyl groups, was successfully synthesized. This monomer was polymerized with six commercial dianhydrides to produce a series of poly(amic acid) precursors, which were subsequently converted into high-performance polyimide (PI) films via a thermal imidization process. The strategic integration of the alicyclic, ether, and fluorinated motifs within the polymer backbone resulted in materials with an exceptional combination of properties. These PI films display outstanding solubility in a wide range of organic solvents, including low-boiling options like chloroform and tetrahydrofuran, highlighting their superior solution processability. The films are amorphous and exhibit remarkable hydrophobicity, evidenced by high water contact angles (up to 109.4°) and minimal water absorption (as low as 0.26%). Furthermore, they possess excellent optical transparency, with a maximum transmittance of 86.7% in the visible region. The materials also maintain robust thermal stability, with 5% mass loss temperatures exceeding 416 °C, and offer a desirable balance of mechanical strength and flexibility. This unique set of attributes, stemming from a rational molecular design, positions these polyimides as highly promising candidates for next-generation flexible electronics and advanced photovoltaics. Full article

Near-infrared organic photodetectors (NIR-OPDs) are emerging as versatile platforms for flexible and low-cost optical sensing, yet achieving high-performance in the NIR region remains difficult remains challenging due to intrinsic trade-offs at both the material and device levels, due to the inherent balance required among bandgap narrowing, exciton dissociation, charge transport, and dark-current suppression. This review provides a concise overview of OPD operating mechanisms and the performance metrics governing sensitivity and noise. We highlight recent molecular-engineering strategies—core fluorination, asymmetric π-bridge design, fused-ring rigidification, and polymer backbone/side-chain tuning—that effectively enhance intermolecular ordering, reduce energetic disorder, and extend NIR absorption. Progress in all-polymer detectors and ambipolar phototransistors further demonstrates improved stability and broadened detection capability. Additionally, emerging applications, including NIR communication, biosignal monitoring, flexible imaging, and biometric recognition, showcase the expanding utility of NIR-OPDs. Remaining challenges include pushing detection beyond 1200 nm, simplifying synthesis, and improving long-term stability. Overall, advances in low-bandgap molecular design and device engineering continue to accelerate the practical adoption of NIR-OPDs. Full article