C F Bond Research Articles

A BOIMPY Dye Enables Multi-Photoinduced Electron Transfer Catalysis: Reaching Super-Reducing Properties.

An established concept to create radical intermediates is photoexcitation of a catalyst to a higher energy intermediate, subsequently leading to a photoinduced electron transfer (PET) with a reaction partner. The known concept of consecutive photoinduced electron transfer (con-PET) leads to catalytically active species even higher in energy by the uptake of two photons. Generally speaking, increased photon uptake leads to a more potent reductant. Here, we report the concept of multi-photoinduced electron transfer catalysis (>2 photons), termed multi-PET, which is enabled by photoinduced one-electron reductions of an organic dye. Further irradiation of the doubly reduced species leads to a photoexcited dianionic super-reductant, which is more potent than Li metal - one of the strongest chemical reductants known. This multi-photon process which is enabled by 390 nm LEDs allows the cleavage of strong carbon-fluorine bonds and reduction of other halides even in very electron-rich substrates. The resulting radicals are quenched by hydrogen atoms or engaged in carbon-carbon and carbon-phosphorus bond formations, highlighting the utility of multi-PET for organic chemistry. In addition, multi-PET enabled Birch-type reductions. Spectroscopic, chemical and computational investigations are presented to gain mechanistic insights.

Assessment of Cytotoxicity and Genotoxicity of Plasma-Treated Perfluorooctanesulfonate Containing Water Using In Vitro Bioassays

The contamination of ground and surface waters with per- and polyfluoroalkyl substances (PFASs) is of major concern due to their potential adverse effects on human health. The carbon–fluorine bond makes these compounds extremely stable and hardly degradable by natural processes. Therefore, methods for PFAS removal from water are desperately needed. In this context, plasma treatment of water has been proposed as an effective method with reported removal rates exceeding 90%. However, the high reactivity of plasma discharge results in the formation of many reactive species, like radicals, ozone, or even solvated electrons, which lead to a complex reaction cascade and, consequently, to the generation of a wide variety of different chemical products. The toxicological properties of these PFAS breakdown products are largely unknown. The present study focuses on a toxicological assessment of PFAS-containing plasma-treated water samples. Aqueous solutions of long-chain perfluorooctanesulfonate (PFOS) were treated with various plasma-atmospheric regimes. Subsequently, plasma-treated water samples were subjected to in vitro bioassays. Cytotoxicity and genotoxicity were assessed with the MTS assay using human liver cells (HepG2) and the Ames MPFTM assay using Salmonella Typhimurium strains. Our results demonstrate varying cyto- and genotoxic properties of water containing PFAS breakdown products depending on the atmosphere present during plasma treatment. Based on the results of this study, the atmosphere used during plasma treatment affects the toxicological properties of the treated sample. Further studies are therefore needed to uncover the toxicological implications of the different treatment parameters, including the PFAS starting compound, the atmosphere during treatment, as well as the quantity of plasma energy applied.

Biocatalytic Generation of Trifluoromethyl Radicals by Nonheme Iron Enzymes for Enantioselective Alkene Difunctionalization.

The trifluoromethyl (-CF3) group represents a highly prevalent functionality in pharmaceuticals. Over the past few decades, significant advances have been made in the development of synthetic methods for trifluoromethylation. In contrast, there are currently no metalloenzymes known to catalyze the formation of C(sp3)-CF3 bonds. In this work, we demonstrate that a nonheme iron enzyme, hydroxymandelate synthase from Amycolatopsis orientalis (AoHMS), is capable of generating CF3 radicals from hypervalent iodine(III) reagents and directing them for enantioselective alkene trifluoromethyl azidation. A high-throughput screening (HTS) platform based on Staudinger ligation was established, enabling the rapid evaluation of AoHMS variants for this abiological transformation. The final optimized variant accepts a range of alkene substrates, producing the trifluoromethyl azidation products in up to 73% yield and 96:4 enantiomeric ratio (e.r.). The biocatalytic platform can be further extended to alkene pentafluoroethyl azidation and diazidation by altering the iodine(III) reagent. In addition, anion competition experiments provide insights into the radical rebound process for this abiological transformation. This study not only expands the catalytic repertoire of metalloenzymes for radical transformations but also creates a new enzymatic space for organofluorine synthesis.

Harnessing carbon-based adsorbents for poly- and perfluorinated substance removal: A comprehensive review

Poly- and perfluoroalkyl substances (PFAS) are synthetic, highly fluorinated chemicals commonly used in products like water-resistant materials, personal care items, non-stick cookware, and cleaning agents. Due to the strength of their CF bonds, PFAS are extremely persistent in the environment, creating significant challenges for pollution control. Traditional degradation methods often prove ineffective, making adsorption a promising alternative for PFAS removal from contaminated water. Carbon-based adsorbents, valued for their sustainability and efficiency, are particularly effective for this purpose. This review provides a detailed analysis on PFAS properties and their removal using various carbon-based adsorbents, including activated carbon, biochar, graphene oxide, carbon nanotubes, and magnetic composites. Adsorption capacities of these materials were seen vary significantly, from as low as 10.7 mg/g for Fe3O4-hybrid biochar, to as high as 713.85 mg/g for functionalized graphene-based adsorbent, highlighting the superior adsorption efficiency of modified graphene adsorbents compared to traditional biochar and activated carbons. Most of these adsorbents fit the Langmuir isotherm model and pseudo-second-order kinetic model with high coefficient of determination, indicating efficient monolayer adsorption and strong interaction with PFAS. The review also explores different adsorption mechanisms, the effects of process parameters on adsorption efficiency, strategies for adsorbent regeneration, and concludes with a bibliometric analysis that highlights key research gaps. These insights are intended to guide future advancements in the development of effective, scalable PFAS remediation technologies using carbon-based adsorbents.

Photocatalytic C-F bond activation in small molecules and polyfluoroalkyl substances.

Organic halides are highly useful compounds in chemical synthesis, where the halide serves as a versatile functional group for elimination, substitution, and cross-coupling reactions with transition metals or photocatalysis1-3. However, the activation of carbon-fluorine bonds, the most commercially abundant organohalide and found in PFAS, or "forever chemicals", are much rarer. Current approaches based on photoredox chemistry for activation of small molecule carbon-fluorine (C-F) bonds are limited by the substrates and transition-metal catalysts needed4. A general method for the direct activation of organofluorines would have significant value in organic and environmental chemistry. Here, we report an organic photoredox catalyst system that can efficiently reduce C-F bonds to generate carbon-centered radicals, which can then be intercepted for hydrodefluorination (swapping F for H) and cross-coupling reactions. This system enables the general use of organofluorines as synthons under mild reaction conditions. We extend this method to the defluorination of polyfluoroalkyl substances (PFAS) and fluorinated polymers, a critical challenge in the breakdown of persistent and environmentally damaging forever chemicals.

A self-healing plastic ceramic electrolyte by an aprotic dynamic polymer network for lithium metal batteries.

Oxide ceramic electrolytes (OCEs) have great potential for solid-state lithium metal (Li0) battery applications because, in theory, their high elastic modulus provides better resistance to Li0 dendrite growth. However, in practice, OCEs can hardly survive critical current densities higher than 1 mA/cm2. Key issues that contribute to the breakdown of OCEs include Li0 penetration promoted by grain boundaries (GBs), uncontrolled side reactions at electrode-OCE interfaces, and, equally importantly, defects evolution (e.g., void growth and crack propagation) that leads to local current concentration and mechanical failure inside and on OCEs. Here, taking advantage of a dynamically crosslinked aprotic polymer with non-covalent -CH3⋯CF3 bonds, we developed a plastic ceramic electrolyte (PCE) by hybridizing the polymer framework with ionically conductive ceramics. Using in-situ synchrotron X-ray technique and Cryogenic transmission electron microscopy (Cryo-TEM), we uncover that the PCE exhibits self-healing/repairing capability through a two-step dynamic defects removal mechanism. This significantly suppresses the generation of hotspots for Li0 penetration and chemomechanical degradations, resulting in durability beyond 2000 hours in Li0-Li0 cells at 1 mA/cm2. Furthermore, by introducing a polyacrylate buffer layer between PCE and Li0-anode, long cycle life >3600 cycles was achieved when paired with a 4.2 V zero-strain cathode, all under near-zero stack pressure.

Identifying the Role of Interfacial Long-Range Order in Regulating the Solid Electrolyte Interphase in Lithium Metal Batteries.

The self-assembled monolayer (SAM) technique, known for its customizable molecular segments and active end groups, is widely recognized as a powerful tool for regulating the interfacial properties of high-energy-density lithium metal batteries. However, it remains unclear how the degree of long-range order in SAMs affects the solid electrolyte interphase (SEI). In this study, we precisely controlled the hydrolysis of silanes to construct monolayers with varying degrees of long-range order and investigated their effects on the SEI nanostructure and lithium anode performance. The results indicate that the degree of long-range order in SAMs significantly influences the decomposition kinetics of the carbon-fluorine bond in lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), promoting the formation of a LiF-rich SEI and profoundly affecting the long-term stability of the highly sensitive anode during electrochemical processes. These findings provide new insights and directions for the molecular design of SAMs tailored for long-lasting lithium metal interfaces.

Photocatalytic low-temperature defluorination of PFASs.

Polyfluoroalkyl and perfluoroalkyl substances (PFASs) are found in many everyday consumer products, often because of their high thermal and chemical stabilities, as well as theirhydrophobic and oleophobic properties1. However, the inert carbon-fluorine (C-F) bonds that give PFASs their properties also provide resistance to decomposition through defluorination, leading to long-term persistence in the environment, as well as in the human body, raising substantial safety and health concerns1-5. Despite recent advances in non-incineration approaches for the destruction of functionalized PFASs, processes for the recycling of perfluorocarbons (PFCs) as well as polymeric PFASs such as polytetrafluoroethylene (PTFE) are limited to methods that use either elevated temperatures or strong reducing reagents. Here we report the defluorination of PFASs with a highly twisted carbazole-cored super-photoreductant KQGZ. A series of PFASs could be defluorinated photocatalytically at 40-60 °C. PTFE gave amorphous carbon and fluoride salts as the major products. Oligomeric PFASs such as PFCs, perfluorooctane sulfonic acid (PFOS), polyfluorooctanoic acid (PFOA) and derivatives give carbonate, formate, oxalate and trifluoroacetate as the defluorinated products. This allows for the recycling of fluorine in PFASs as inorganic fluoride salt. The mechanistic investigation reveals the difference in reaction behaviour and product components for PTFE and oligomeric PFASs. This work opens a window for the low-temperature photoreductive defluorination of the 'forever chemicals' PFASs, especially for PTFE, as well as the discovery of new super-photoreductants.

IPr*F - Highly Hindered, Fluorinated N-Heterocyclic Carbenes.

The introduction of fluorine atom has attracted considerable interest in molecular design owing to the high electronegativity and the resulting polarization of carbon-fluorine bonds. Simultaneously, sterically-hindered N-heterocyclic carbenes (NHCs) have received major interest due to high stabilization of the reactive metal centers, which has paved the way for the synthesis of stable and reactive organometallic compounds with broad applications in main group chemistry, inorganic synthesis and transition-metal-catalysis. Herein, we report the first class of sterically-hindered, fluorinated N-heterocyclic carbenes. These ligands feature variable fluorine substitution at the N-aromatic wingtip, permitting to rationally vary steric and electronic characteristics of the carbene center imparted by the fluorine atom. An efficient, one-pot synthesis of fluorinated IPr*F ligands is presented, enabling broad access of academic and industrial researchers to the fluorinated ligands. The evaluation of steric, electron-donating and π-accepting properties as well as coordination chemistry to Au(I), Rh(I) and Se is presented. Considering the unique properties of carbon-fluorine bonds, we anticipate that this novel class of fluorinated carbene ligands will find widespread application in stabilizing reactive metal centers.

Anion-driven C[sbnd]F bond cleavage of trifluoromethyl N-aryl hydrazones toward the assembly of N-heterocycles

Herein we report an efficient and convenient method for synthesizing 1H-benzo[d]imidazoles via a base-promoted reaction of readily available α-CF3 ketone-derived hydrazones with o-phenylenediamines. The key innovation is the anion-driven triple-cleavage of the CF bond in the CF3 group, which acts as a C1 synthon at the 2-position of the 1H-benzo[d]imidazole. This novel approach simplifies the synthesis and can be extended to the preparation of benzo[d]oxazoles and benzo[d]thiazoles. Our method offers a versatile and robust platform for the synthesis of important heterocyclic compounds, with potential applications in medicinal chemistry and drug discovery.

Deoxyfluorination: A Detailed Overview of Recent Developments

AbstractFluorine organic compounds have been a predominant force of pharmaceutical chemistry for modern drug design, with an increasing amount of fluorine-containing compounds entering the market. Methodologies for fluorine atom incorporation into organic molecules are still challenging to date and thus represent an important research area. Deoxyfluorination serves as a useful tool for the construction of carbon–fluorine bonds in biologically active molecules by converting a common hydroxyl group into the corresponding fluoride. In this review, we have summarized and categorized deoxyfluorination reaction protocols developed over the last decade (2015–2024) by the structural type of C–O bond deoxyfluorination, including substrates like alcohols, phenols, ketones, aldehydes, and carboxylic acids.1 Introduction2 Deoxyfluorination of C(sp3)–O Bonds2.1 Alcohols2.2 Alcohol Derivatives3 Deoxyfluorination of C(sp2)–O Bonds3.1 Phenols3.2 Phenol Derivatives3.3 Aldehydes and Ketones3.4 Carboxylic Acids4 Conclusions

PFAS: The Journey from Wonder Chemicals to Environmental Nightmares and the Search for Solutions

Per- and polyfluoroalkyl substances (PFAS) are diverse synthetic chemicals manufactured over seven decades. It is an aliphatic molecule with a basic hydrophobic structure of carbon and fluorine linked to a hydrophilic end group. Due to their physicochemical properties associated with the unique structure, PFAS has been used in a wide variety of applications including aqueous film-forming foams (AFFF), paper, carpets, non-stick cookware, etc. as they make products resistant to water, heat, and stains. These molecules have drawn great attention recently for their unique properties, high stability and low degradability, and so-called “Forever Chemicals”. PFAS has the strongest carbon-fluorine bond which makes them persistent in the environment. Hence it contaminates natural resources and endangers public health. This review discusses the discovery, development, and evolution of PFAS from the wonder chemical era to a nightmare chemical era, exposure and its impacts on human health and the environment, current remediation techniques, and future trends of PFAS molecules and related products. The primary objective of this review is to identify knowledge gaps on PFAS contamination, remediation methods, and possible PFAS alternatives.

Identification of transformation products from fluorinated lithium-ion battery additives TPFPB and TPFPP: forever chemicals of tomorrow?

Fluorinated organic compounds (FOCs) represent a class of synthetic chemicals distinguished by their resilient carbon-fluorine bonds, which demonstrate an ability to withstand environmental degradation over an extended period. The integration of FOCs into cutting-edge applications, including lithium-ion batteries (LiBs), presents considerable potential for environmental harm that has not yet been sufficiently addressed. This study focuses on the environmental fate of two fluorinated aromatics, tris(pentafluorophenyl)borane (TPFPB) and tris(pentafluorophenyl)phosphine (TPFPP), given their important role in improving the performance of LiBs. To achieve this, laboratory simulation methods including total oxidizable precursor assay, electrochemistry (EC), Fenton reaction, UV-C irradiation, and hydrolysis were employed. Liquid chromatography and gas chromatography coupled with high-resolution mass spectrometry were used for identification of transformation products (TPs) and prediction of their molecular formulae. Despite the structural similarity between TPFPB and TPFPP, distinct differences in electrochemical behavior and degradation pathways were observed. TPFPB readily underwent hydroxylation and hydrolysis, resulting in a wide range of 49 TPs. A total of 28 TPs were newly identified, including oligomers and highly toxic dioxins. In contrast, TPFPP degraded exclusively under harsh conditions, requiring the development of innovative conditioning protocols for EC. In total, the simulation experiments yielded nine structurally different compounds, including seven previously undescribed, partially defluorinated TPs. This study highlights the potential risks associated with the use of FOCs in LiBs and provides insight into the complex environmental behavior of FOCs.

Fugacity model covering abiotic and biotic matrices to investigate the transfer and fate of perfluoroalkyl acids in a large shallow lake of eastern China

Solving the challenges faced during the measurement of the cross-interface transfer of perfluoroalkyl acids (PFAAs) in lakes is crucial for clarifying environmental behaviours of these chemicals and their efficient governance. This study developed a multimedia fugacity model based on the quantitative water–air–sediment interaction (QWASI) covering abiotic/biotic matrices to investigate the cross-interface transfer and fate of PFAAs in Luoma Lake, a typical PFAA-contaminated shallow lake in eastern China. The accuracy and reliability of the established model were confirmed using Percent bias and Monte Carlo simulation, respectively. Using the QWASI model, the multimedia transfer of the PFAAs and their accumulation and persistence in different sub-compartments were described and measured, and the differences among individual PFAAs were explored. The simulation results showed that the sedimentation and resuspension of PFAAs were the most intense cross-interfacial transfers, and the sediments served as a chemical sink in the long term. A significant negative correlation of NC-F (the number of CF bonds) with the relative outflow flux (TW·out-ct) but a positive correlation with the relative net transfer across the interface between water and aquatic plants (Tp-ct) was detected, indicating that the PFAA migration capacity decreased but the bioaccumulation potential increased with the CF bond number. The persistence in water (Pw) of individual PFAAs ranged from 19.65d (PFOA) to 32.22d (PFOS), with an average of 26.15d; their persistence in sediment (Ps) ranged from 432d (PFBA) to 3216d (PFOS), with an average of 1524d, increasing linearly with an increase in NC-F. The water advection flows into and out of the lake (QW·in and QW·out), the PFAA concentration of water inflow (CW·in), and bioconcentration factor of aquatic plants (BCFp) were the primary parameters sensitive to PFAAs in all sub-compartments, which are essential indexes for exploring promising remediation pathways for lacustrine PFAA contamination based on the fugacity model simulation.

Photo-reductive decomposition of perfluorooctane sulfonate (PFOS) and its common alternatives by UV/VUV/sulfite process: Mechanism, kinetic modeling, and water matrix effects

The present study investigated the photo-reduction of perfluorooctane sulfonate (PFOS) and its alternatives, focusing on decomposition mechanisms, active species involvement, the influence of background water constituents, and kinetic model development. The decomposition and defluorination rates followed the order of PFOS > PFHxS > 6:2 FTSA > PFBS, with shorter chains and CH2 linkers enhancing the resistance of PFOS alternatives against the attack of hydrated electrons (eaq−). Two primary pathways were identified during the photodegradation of PFAS: (i) H/F exchange at CF bonds with the lowest bond dissociation energies (BDEs) and (ii) functional group cleavage followed by short-chain PFCAs formation, with OH playing a crucial role in transforming intermediates. Adding iodide and elevated temperatures demonstrated a synergistic effect on PFBS decomposition and defluorination, with high temperatures promoting functional group cleavage as the preferred defluorination pathway. The study examined the impact of background water constituents in different aqueous environments, from surface waters to wastewater streams and ion-exchange brine concentrates. Chloride exhibited a concentration-based dual impact on the UV/VUV/sulfite process: promotive effects at low dosages (1–10 mM) by acting as a secondary eaq− mediator, and adverse effects at high dosages (20–500 mM) due to the scavenging effect of generated chlorine radicals (Cl). High ionic strength adversely affected eaq− quantum efficiency. Additionally, bicarbonate and natural organic matter (NOM) had opposing effects on PFOS photo-reduction, primarily through eaq− scavenging and pH alteration. Kinetic modeling revealed reaction rate constants of the studied PFAS with eaq− ranging from 1.8 × 106 to 1.3 × 109 M−1 s−1, corroborating the concentration profiles of active species and highlighting the reductive nature of sulfite-mediated processes.

Halogen Atom Transfer-Induced Homolysis of C-F Bonds by the Excited-State Boryl Radical.

A novel reactivity toward C-F bond functionalization has been developed, which could be designated as fluorine atom transfer (FAT). A photoexcited state of an N-heterocyclic carbene-ligated boryl radical exhibits a transcendent reactivity, capable of activating chemically inert carbon-fluorine bonds through homolysis. Combined experimental and computational studies suggest that the ligated boryl radical species directly abstracts a fluorine atom from the organofluoride substrates to provide valuable carbon-centered radicals.

Solubility Change Behavior of Fluoroalkyl Ether-Tagged Dendritic Hexaphenol under Extreme UV Exposure.

This study focuses on the discovery of a single-component molecular resist for extreme ultraviolet (EUV) lithography by employing the ionizing radiation-induced decomposition of carbon-fluorine chemical bonds. The target material, DHP-L6, was synthesized by bonding perfluoroalkyl ether moieties to amorphous dendritic hexaphenol (DHP) with a high glass transition temperature. Upon exposure to EUV and electron beam irradiation, DHP-L6 films exhibited a decreasing solubility in fluorous developer media, resulting in negative-tone images. The underlying chemical mechanisms were elucidated by Fourier transform-infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy, and nanoindentation experiments. These analyses highlighted the possible electron-induced decomposition of C-F bonds in DHP-L6, leading to molecular network formation via recombination of the resulting C-centered radicals. Subsequent high-resolution lithographic patterning under EUV irradiation showed that DHP-L6 could create stencil patterns with a line width of 26 nm at an exposure dose of 110 mJ cm-2. These results confirm that single-component small molecular compounds with fluoroalkyl moieties can be employed as patterning materials under ionizing radiation. Nonetheless, additional research is required to reduce the relatively high exposure energy for high-resolution patterning and to enhance the line-edge roughness of the produced stencil.

Synergistic effect of reducing volume expansion and improving electrochemical performance through a LiF-based SEI formation on SiOx/C electrodes

SiOx/C electrodes are widely used due to their high lithium storage capacities and cycling stabilities. However, the SiOx/C electrode exhibits large volume expansion and unstable SEI layer formation during cycling. In this work, a carbon tetrafluoride (CF4) plasma was used to introduce C-F bonds onto the electrode surface to form a LiF-based SEI layer on a SiOx/C electrode (SGE) to improve its mechanical and electrochemical properties. The fluorinated SiOx/C electrode (FSGE) subjected to the CF4 plasma treatment for 10 min mitigated 2.5 times the volume expansion compared to the SGE by forming a LiF-based SEI layer to increase the mechanical properties. This mitigation of FSGE volume expansion resulted in excellent long-term cycling stability of 83 % for 100 cycles (1C). In addition, the LiF-based SEI layer formed on the FSGE increased the mobility of Li ions, resulting in 1.2 times better cycle stability than that of SGE at a high rate (10C). Thus, the improvement in the electrochemical performance achieved by reducing the volume expansion of SiOx in the electrode and enhancing the Li-ion conductivity was attributed to the stable LiF SEI layer formed with semi-ionic CF bonds introduced by the CF4 plasma.

On the Existence and Relevance of Copper(III) Fluorides in Oxidative Trifluoromethylation

AbstractNumerous reports invoke CuIII–F intermediates engaging in oxidative cross-couplings mediated by low/mid-valent copper and formal sources of ‘F+’ oxidants. These elusive and typically instable CuIII fluorides have been rarely characterized or spectroscopically identified, making their existence and participation within catalytic cycles somehow questionable. We have authenticated a stable organocopper(III) fluoride that undergoes Csp–CF3 bond formation upon addition of silyl-capped alkynes following a 2 e– CuIII/CuI redox shuttle. This finding strongly supports the intermediacy of CuIII fluorides in C–C coupling. We review herein the state of the art about well-defined CuIII fluorides enabling cross-coupling reactions.1 Introduction2 Brief History of Coupling-Competent CuIII Fluorides3 Design of an Isolable – yet Reactive – Organocopper(III) Fluoride4 Alkyne Trifluoromethylation: Scope and Mechanism5 Extension to Aryl–CF3 and C–Heteroatom Couplings6 Summary and Outlook

Super hydrophobic self-stratified coating based on epoxy terminated polyurethane/siloxane nano-composite

ABSTRACT Recently, the application of superhydrophobic coatings on insulators has emerged as an effective strategy for mitigating risks and damages. In the current investigation, a superhydrophobic coating formulated with polyurethane (PU) prepolymer and polydimethylsiloxane (PDMS) has been developed, featuring a surface layer of SiO2 nanoparticles (NPs) modified with fluoroalkyl silane (FAS). The identification of peaks within the ranges of 567, 650, 747, and 898 cm− 1, corresponding to CF, CF₂, and CF₃ bonds, along with the reduction of the peak associated with the hydroxyl group around 3433 cm− 1, substantiates the interaction between FAS13 and SiO2 nanoparticles. The resultant coating exhibited a 39% increase in hydrophobicity compared to the coating without nanoparticles. The surface modification of nanoparticles resulted in an escalated degradation rate for the USMN sample, reaching a temperature range of 300 to 400°C. This phenomenon is attributed to the interaction between the hydroxyl groups on the nanoparticle’s surface and the Si-O bonds present in the FAS13 composition, leading to increased thermal resistance of the nanoparticle. This study successfully produced a PDMS/PU coating utilizing modified SiO2 particles through a self-stratified approach. This coating acts as an adhesive layer for high-voltage insulation surfaces, effectively protecting against water intrusion and dust accumulation.