Polymerizable Monomers Research Articles

Fatigue Behavior of Polymer Nanocomposites under Low-Strain Cyclic Loading: Insights from Molecular Dynamics Simulation.

Understanding the structural evolution and bond-breaking behavior under cyclic loading is crucial for designing polymer nanocomposites (PNCs) with superior fatigue resistance. Coarse-grained models of PNCs filled with spherical carbon black nanoparticles (NPs) at varying filling fractions of φ were successfully constructed using molecular dynamics simulations. Structural and dynamic simulation results reveal that higher φ leads to increased aggregation of NPs and markedly restricts the relaxation behavior of the polymer matrix. Subsequently, fatigue testing of PNCs was conducted under low-strain cyclic tensile deformation, and the real-time bond-breaking behavior was tracked. The decay behavior of the bond number autocorrelation function was found to be accurately described by the KWW equation, enabling precise determination of the characteristic lifetime τf. With increasing φ, the dominant factor influencing bond-breaking behavior gradually shifts from the polymer network, including entanglements and cross-linking networks, to the filler network. This suggests the presence of a critical filling fraction φc where τf is maximized. For low-strain failure mechanisms, temperature field observations at varying cycles reveal that localized temperature rise emerges as the predominant factor. Furthermore, the mobility of both polymers and NPs increases with cycles. Specifically, the diffusion coefficient of polymer monomers shows a clear power-law relationship with the bond-breaking rate, characterized by . Finally, the stiffness of polymer chains significantly influences the fatigue behavior, evidenced by an initial increase followed by a decrease in the τf with increasing bending energy k. This behavior is attributed to the competitive relationship between high entanglement density at low k and enhanced preorientation at high k. In summary, this study provides a general paradigm for describing failure behavior under cyclic deformation and offers insights into fatigue mechanisms at the molecular level, thereby guiding the development of improved fatigue-resistant PNCs.

Heat diffusion coefficient study of polymers based on interpretable machine learning

Abstract. Polymers hold significant application value across various fields of modern society, with different application scenarios requiring specific thermal diffusivity coefficients. Finding polymer materials with targeted thermal diffusivities is crucial. However, due to the vast variety and complex structures of polymers, constructing a unified structured dataset for machine learning modeling is challenging. Although machine learning has shown great potential in materials science, it has rarely been applied to predict the heat diffusion coefficient of polymers. This paper constructs a dataset for predicting the thermal diffusion coefficient of polymers using a publicly available dataset by transforming the SMILES code of polymers into eight features with practical physical and chemical meanings. Using the Random Forest algorithm, training with 400 of these data and randomly selecting 200 of them for cross-validation, the accuracy of the test set reached 0.9. Additionally, through interpretability analysis, we found that the molecular weight of the polymer monomers, the TPSA (the polar surface area of the molecule), and the NRB (the number of rotatable bonds) are the main features affecting the polymer thermal diffusion coefficient. An increase in the TPSA and the NRB positively contributes to the thermal diffusivity, while an increase in molecular weight negatively contributes. Our study provides a new method for the prediction of polymer thermal diffusivity and creates a new paradigm for the study of polymer thermal diffusivity, promoting further development in this field.

Amplification and Attenuation of Asymmetry via Kinetically Controlled Seed-Induced Supramolecular Polymerization.

The amplification of asymmetry in supramolecular polymers has recently garnered significant attention. While asymmetry amplification has predominantly been explored under thermodynamic conditions, the kinetic aspect of this process unveils intriguing observations, yet is scarcely reported in the literature. Herein, drawing inspiration from macromolecular systems, we propose a novel strategy for enhancing asymmetry in supramolecular polymers through a seed-induced supramolecular polymerization approach under kinetic conditions, employing a naphthalene diimide-derived monomer (ANSG) for template-induced supramolecular polymerization, utilizing adenosine triphosphate (ATP) and pyrophosphate (PPi) as templates. A chiral seed comprising [ANSG-ATP]S effectively amplifies the overall supramolecular asymmetry when exposed to a mixture of achiral templates (PPi) and monomers (ANSG), owing to its efficient seeding characteristics under kinetic conditions. As a result of efficient co-operativity, conversely, employing an achiral seed [ANSG-PPi]S in a mixture of chiral templates (ATP) and monomers (ANSG) results in the attenuation of asymmetry, highlighting the effective modulation achievable through the seeding approach, an unprecedented observation in the field. Exploiting the efficient aggregation-induced emission enhancement (AIEE) of the resultant supramolecular polymers further extends the amplification and attenuation of circularly polarized luminescence (CPL) as a potential function.

Sequence-Defined Synthesis Enabled by Fast and Living Anionic Monoaddition of Vinyl Monomers.

The selective monoaddition of polymerizable vinyl monomers like styrenes and methacrylates in a living manner has been achieved for the flash-flow preparation of molecules in a defined sequence with high selectivity. We demonstrated the sequence-defined synthesis of multifunctional molecules using an initiator, functionalized styrenes, diarylethylenes, various methacrylates, and an electrophilic trapping reagent at the living terminus (six-component sequential connection at maximum) without any intermediate purification steps. The anionic living terminus of the vinyl monomers in the flow system described herein is active for polymerization, such that the styrene or methacrylate sequence can be expanded to afford highly dispersed oligomers without affecting other single units, which means that the unequivocal sequences were successfully inserted into the internal or terminal positions. The methodology described herein provides an adaptable method for the construction of new molecular spaces based on unimolecular sequence control and pinpoint functionalization.

Sequence‐Defined Synthesis Enabled by Fast and Living Anionic Monoaddition of Vinyl Monomers

The selective monoaddition of polymerizable vinyl monomers like styrenes and methacrylates in a living manner has been achieved for the flash‐flow preparation of molecules in a defined sequence with high selectivity. We demonstrated the sequence‐defined synthesis of multifunctional molecules using an initiator, functionalized styrenes, diarylethylenes, various methacrylates, and an electrophilic trapping reagent at the living terminus (six‐component sequential connection at maximum) without any intermediate purification steps. The anionic living terminus of the vinyl monomers in the flow system described herein is active for polymerization, such that the styrene or methacrylate sequence can be expanded to afford highly dispersed oligomers without affecting other single units, which means that the unequivocal sequences were successfully inserted into the internal or terminal positions. The methodology described herein provides an adaptable method for the construction of new molecular spaces based on unimolecular sequence control and pinpoint functionalization.

Synthesized Crosslinking Suspension Stabilizer for Spacer Fluid in High-Temperature Conditions: Synthesis, Behavior, and Mechanism Research

Summary High-temperature stability of spacer fluid is a vital prerequisite to ensure the safety of cementing operations in deep or ultradeep wells. Faced with this problem, the thermal stability of the suspension agent in the spacer fluid at high temperatures is improved from the aspects of polymerization monomer and molecular chain. A terpolymer SAD was synthesized by free radical polymerization of sodium styrene sulfonate (SSS), acrylamide (AM), and N, N’-diethylacrylamide (DEAA) in aqueous solution. The name of the terpolymer, SAD, is the initial letter composition of the three polymerization monomers. Polyethyleneimine (PEI) can improve the molecular chain structure of SAD by transamidation reaction with the amide group in SAD, so a high temperature suspension agent PSAD (polyethyleneimine + SAD) was obtained by compounding PEI with SAD. The structure and properties of PSAD were characterized by Fourier infrared spectroscopy, hydrogen nuclear magnetic resonance (NMR) spectroscopy, gel permeation chromatography, X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis, scanning electron microscopy (SEM), and viscosity test. In addition, the comprehensive properties of the spacer fluid under the action of PSAD are evaluated. The results showed that the crosslinking degree of PSAD gradually increased with the increase in temperature. After aging at 200°C, the decomposition temperature of PSAD was 305°C, which show terrific thermal stability. At the same time, the spacer fluid prepared by PSAD not only has excellent rheological properties in the range of 90 ~ 200°C but also keeps the density difference between the upper and lower parts of the slurry less than 0.02 g/cm3 and the filtration loss of the slurry less than 50 mL.

Polymerizable deep eutectic solvent-gels synthesized in situ under molecular engineering control exhibit excellent adhesion, freeze resistance, as well as stretching and humidity sensing capabilities

Hydrogels generally do not adhere well to different substrates and freeze at sub-zero temperatures, limiting their application. In this study, the strategy of replacing water in hydrogels with deep eutectic solvents (DES) was used to address these challenges. Specifically, choline chloride (ChCl) as hydrogen bond acceptor, acrylic acid (AA) and itaconic acid (IA) as hydrogen bond donors and polymerizable monomers constitute PDES. Afterwards, PDES-gel (PG) was obtained by adding a thermal initiator to polymerize AA and IA in PDES. PG has the following characteristics, because PG is almost water-free, it has remarkable low-temperature tolerance without any phase change at −60 °C∼20 °C. Thanks to the carboxyl groups and chloride ions contained in PG, it can form non-covalent interactions such as hydrogen bonding and ionic interactions with different substrates, so PG can adhere to various substrate surfaces. Furthermore, the breaking elongation of the novelty PG was up to ca. 960 %, tensile strength ca. 1 MPa, outstanding transparency with an average light transmittance of about 95 % in the visible-light range. Ultimately, the novel PG exhibited certain capabilities for moisture detection and deformation sensing. The new PDES-gel material developed using PDES is expected to provide new ideas for the advancement of wearable devices.

Perovskite nanocrystals photo-initiated in situ encapsulation for optical tracking

Metal halide perovskite (CsPbX3, X = Cl, Br, I) nanocrystals (MHP NCs) have been widely investigated for a variety of optoelectronic applications due to their superior photophysical characteristics. However, the inherent poor stability has limited broad applications. Herein, a facile in situ photopolymerization strategy using MHP NCs as photo-initiators is designed to fabricate homogeneous perovskite-silicone composites with outstanding stability, flexibility, and scalability. The fabrication process is completed upon exposure to 30 W ultraviolet light for 5 min under ambient conditions without additional protections and additives. The composites have exceptional stability in air and can even withstand harsh conditions, such as a basic pH of 13 for six months. The mechanical properties of composites are tunable from rigid to elastic by regulating the composition, ratios of polymerization monomers, and reaction time. Their superb properties enable optical visualization tracking for magnetically driven soft robots. This convenient and effective approach opens a new pathway for future applications in optical tracking, soft displays, biological detection, and bioimaging of perovskite nanocrystals.

Allylic Epoxides Increase the Strain Energy of Cyclic Olefin Monomers for Ring-Opening Metathesis Polymerization.

Ring-opening metathesis polymerization (ROMP) is an effective method for synthesizing functional polymers, but since the technique typically relies on high ring strain cyclic olefins, the most common monomers are norbornene derivatives. The reliance on one class of monomer limits the obtainable properties of ROMP polymers. In this work, we investigate new bicyclic monomers synthesized via epoxidation of commercial dienes. DFT estimates of these monomers' ring strains suggests a significant increase in strain for cyclic olefins containing allylic epoxides. We found that the eight-membered (3,4-COO) and five-membered (CPO) cyclic olefins were particularly effective for ROMP. CPO was of especially intriguing due to its excellent polymerizability when compared to the limited reactivity of other five-membered rings. Unlike polynorbornenes, the resulting polymers of both monomers displayed glass transition temperatures well below room temperature. Interestingly, poly(3,4-COO) showed both high stereo- and regioregularity while poly(CPO) showed little regularity. Both polymers could be readily modified via post-polymerization ring-opening of the reactive allylic epoxides. With a high epoxide density in poly(CPO), CPO is an exciting new ROMP monomer that is easily synthesized, can be polymerized to high conversion at room temperature, and may be facilely modified to yield a wide range of functional materials.

Antimicrobial properties and biocompatibility of semi-synthetic carbohydrate-based ionic hydrogels.

Hydrogels have gained significant interest in the last decades, especially in the medical sector, due to their versatile properties. While hydrogels from naturally occurring polysaccharides (e.g. cellulose) are well-known, those produced from polymerizable carbohydrate-based monomers remain underexplored. However, these semi-synthetic hydrogels offer the great advantage of having adjustable properties for customization depending on their application. The objective of this study was to characterize semi-synthetic carbohydrate-based ionic hydrogels produced from GVIM-I (glucosyl vinyl imidazolium iodide). The antimicrobial activity was evaluated using the disk diffusion method, which demonstrated that all samples exhibit inhibitory effects on the growth of Candida auris. In vitro biocompatibility was determined by cell viability studies with L929 mouse fibroblasts, and a correlation was observed between eluate concentration and cell viability. In particular, the type of initiator system employed for polymerization was found to affect cell viability. The direct contact assessments showed that specific pre-treatments of the hydrogels resulted in higher cell viability than non-treated hydrogels. The results also revealed the impact of crosslinker concentration and type and identified poly(ethylene glycol)diacrylate (PEGDA) 575 as a promising crosslinker for future medical applications. LC-MS analysis of the wash medium identified unreacted GVIM-I as the leached material, which is presumed to be the cause of the observed cytotoxicity. Overall, the study provides valuable insights into the characteristics of GVIM-I based hydrogels and sheds light on the factors that influence their cytotoxicity and potential for medical application.

Photo-induced time-dependent controllable wettability of dual-responsive multi-functional electrospun MXene/polymer fibers

Switchable wettability potential in smart fibers is of paramount importance in various applications. Light-induced controllable changes in surface wettability have a significant role in this area. Herein, smart waterborne homopolymer, functional copolymer with different polarity and flexibility, and multi-functional terpolymer particles containing a time-dependent dual-responsive acrylated spiropyran, as a polymerizable monomer, were successfully synthesized through eco-friendly single-step emulsifier-free emulsion polymerization. Presence of 10 wt% of butyl acrylate and dimethylaminoethyl methacrylate relative to methylmethacrylate as functional comonomers decreased the Tg of the samples almost 20 ℃ and increased their polarity. The optical properties of the particles were investigated, and the UV–vis and fluorescence spectroscopy results showed that not only polarity and flexibility of the polymer chains may have a positive effect on improving the optical properties, but also the simultaneous presence of functional groups has a synergistic effect. The smart polymer particles with flexibility and polarity features exhibited higher absorption and emission compared to other samples. Inspired by these findings, multi-functional smart polymer fibers were prepared using the electrospinning method. The smart multi-functional electrospun fibers containing few-layer Ti3C2 MXenes were synthesized to improve the fibers’ properties and change the surface wettability due to the hydrophilic functional groups of MXene. Field-emission scanning electron microscopy images displayed the successful preparation of few-layer MXenes. Smooth and bead-free fibers with bright red fluorescence emission under UV irradiation were shown using fluorescence microscopy. The study on the surface wettability of fibers revealed that UV and visible light irradiation induced reversible time-dependent changes in the wettability of the smart multi-functional MXene/polymer electrospun fibers from hydrophobic to hydrophilic, reaching a water contact angle of 10° from an initial water contact angle of 100° under UV light and also changing to superhydrophilic state with passing time. Upon visible light exposure, the fibers returned to their original state. Furthermore, the fibers demonstrated a high stability over five alternating cycles of UV and visible light irradiation. This study shows that the fabrication of time-dependent smart fibers, utilizing the flexibility and polarity in the presence of MXenes, significantly improves and controls surface wettability changes. The outstanding dynamically photo-switchable wettability of these fibers may offer exciting opportunities in various applications, especially in the separation of oil from water contaminants.

LCxSFC Valve Technologies: Guidelines toward a Successful Online Modulation.

Online two-dimensional liquid chromatography can be used under various separation modes but is sometimes limited in terms of orthogonality, especially for the analysis of neutral compounds. The use of SFC in the second dimension offers a wide choice of mobile and stationary phases, suggesting retention properties complementary to those of the first dimension. Initial works on online LCxSFC coupling published in the literature highlighted the first difficulties of solvent compatibility or potential problems with bubbles created by CO2 in loops. The present work highlights the impact of the interface between the LC and SFC dimensions on the performance of the 2D separation. Six different configurations have been evaluated, differing by the addition of a makeup flow in the first dimension, a division, or a separation of flow paths in the second dimension. Their performances with empty loops eliminated the need for complex trapping columns, regardless of the LC mobile phase nature. Injection in partial fill mode was possible without any problems of CO2 bubble formation, solvent miscibility, pressure, or modulation repeatability in each of the studied configurations. Selected configurations even allowed for the use of a mobile phase split upstream of the valve, so that the online LCxSFC configuration could be as flexible as LCxLC instrumentation in terms of the first dimension flow rate or second dimension injected volume. The obtained results allowed for building guidelines presenting the best interfaces to set up depending on the nature of the mobile phases in both dimensions. Two applications on monomers of lignin and industrial polymers confirmed preliminary results on configuration testing and illustrated that online LCxSFC could now be easily implemented. Precision tests on retention time were conclusive and are promising for the future use of this technique in industrial routines.

Direct Synthesis of Perovskite Quantum Dot Photoresist for Direct Photolithography.

Perovskite quantum dots (PQDs) photoresists are promising building blocks for photolithographically patterned devices. However, their complex synthesis and combination processes limit their optical properties and potential patterning applications. Here, we present an exceptionally simple strategy for the synthesis of PQDs photoresist. Unlike traditional approaches that involve centrifugation, separation, and combination processes, our direct synthesis technique using polymerizable acrylic monomer as solvent to fabricate PQDs photoresists without complex post-synthesis process. We demonstrate that the change in solubility of the precursors is the main reason for the formation of PQDs in the polymerizable monomer. By direct photolithography, colorful PQD patterns with high photoluminescence quantum yields and excellent fluorescence uniformity are successfully demonstrated. This work opens a new avenue for the direct synthesis of PQDs photoresist, expanding their applications in various integrated applications, such as photonic, energy harvesting, and optoelectronic devices.

Direct Synthesis of Perovskite Quantum Dot Photoresist for Direct Photolithography

Perovskite quantum dots (PQDs) photoresists are promising building blocks for photolithographically patterned devices. However, their complex synthesis and combination processes limit their optical properties and potential patterning applications. Here, we present an exceptionally simple strategy for the synthesis of PQDs photoresist. Unlike traditional approaches that involve centrifugation, separation, and combination processes, our direct synthesis technique using polymerizable acrylic monomer as solvent to fabricate PQDs photoresists without complex post‐synthesis process. We demonstrate that the change in solubility of the precursors is the main reason for the formation of PQDs in the polymerizable monomer. By direct photolithography, colorful PQD patterns with high photoluminescence quantum yields and excellent fluorescence uniformity are successfully demonstrated. This work opens a new avenue for the direct synthesis of PQDs photoresist, expanding their applications in various integrated applications, such as photonic, energy harvesting, and optoelectronic devices.

Stereospecific supramolecular polymerization of nanoclusters into ultra-long helical chains and enantiomer separation

During the construction of supramolecular polymers of smaller nanoparticles/nanoclusters bearing hierarchy and homochirality, the mechanism understanding via intuitive visualization and precise cross-scale chirality modulation is still challenging. For this goal, a cooperative self-assembly strategy is here proposed by using ionic complexes with uniform chemical composition comprising polyanionic nanocluster cores and surrounded chiral cationic organic components as monomers for supramolecular polymerization. The single helical polymer chains bearing a core-shell structure at utmost length over 20 μm are demonstrated showing comparable flexibility resembling covalent polymers. A nucleation-elongation growth mechanism that is not dealt with in nanoparticle systems is confirmed to be accompanied by strict chiral self-sorting. A permeable membrane prepared by simple suction of such supramolecular polymers displays high enantioselectivity (e.e. 98% after four runs) for separating histidine derivatives, which discloses a benefiting helical chain structure-induced functionalization for macroscopic supramolecular materials in highly efficient racemate separation.

Synergistic preparation of organic solvent nanofiltration membranes from polydopamine/polyethyleneimine interlayers with aminated attapulgite

This study utilized polydopamine (PDA)/polyethyleneimine(PEI) as the hydrophilic interlayer and added aminated attapulgite (ATP-NH2) to the aqueous phase monomer for interfacial polymerization (IP) to synergistically create nanofiltration membranes resistant to organic solvents. The hydrophilic nature of the PDA/PEI interlayer facilitates the rapid passage of polar solvents and results in excellent adhesion, ensuring tight bonding between the ultrafiltration support membranes and the active layer. Furthermore, the incorporation of the ATP-NH2 nanoparticles played a pivotal role in regulating the IP process. The resulting nanofiltration membranes, produced through the combined efforts of these components, achieved an optimal methanol permeation flux of 14.05 L m−2h−1 bar−1, with a rejection rate of Evans blue dye maintained at 99.42 %. Despite being exposed to N, N-dimethylformamide (DMF) at 80 ℃ for a period of 5 days, the nanofiltration membranes maintained both their exceptional separation effectiveness and stability. These findings suggest promising application prospects for the developed nanofiltration membranes.

Reverse Mode Polymer Stabilized Cholesteric Liquid Crystal Flexible Films with Excellent Bending Resistance.

The reverse-mode smart windows, which usually fabricated by polymer stabilized liquid crystal (PSLC), are more practical for scenarios where high transparency is a priority for most of the time. However, the polymer stabilized cholesteric liquid crystal (PSCLC) film exhibits poor spacing stability due to the mobility of CLC molecules during the bending deformation. In this work, a reverse-mode PSCLC flexible film with excellent bending resistance was fabricated by the construction of polymer spacer columns. The effect of the concentration of the polymerizable monomer C6M and chiral dopant R811 on the electro-optical properties and polymer microstructure of the film were studied. The sample B2 containing 3 wt% of C6M and 3 wt% R811 presented the best electro-optical performance. The electrical switch between transparent and opaque state of the flexible PSCLC film after bending not only indicated the excellent electro-optical switching performance, but also demonstrated the outstanding bending resistance of the sample with polymer spacer columns, which makes the PSCLC film containing polymer spacer columns have a great potential to be applied in the field of flexible devices.

Large Molecular Rotation in Crystal Changes the Course of a Topochemical Diels-Alder Reaction from a Predicted Polymerization to an Unexpected Intramolecular Cyclization.

A designed anthracene-based monomer for topochemical Diels-Alder cycloaddition polymerization crystallized with head-to-tail arrangement of molecules, as revealed by single-crystal X-ray diffraction (SCXRD) analysis. The diene and dienophile units of adjacent monomer molecules are aligned at an average distance of 4.6 Å, suggesting a favorable crystalline arrangement for their intermolecular Diels-Alder cycloaddition reaction to form a linear polymer. Surprisingly, heating the monomer crystals at a temperature above 125 °C resulted in the formation of intramolecular Diels-Alder cycloadduct, which could be characterized by various spectroscopy and SCXRD analysis. Various time-dependent studies such as NMR, PXRD, and DSC, studies established that the reaction followed topochemical pathway. Schmidt's topochemical postulates are generally used to predict the topochemical reactivity and product, by analyzing the crystal structure of the reactant. Though the crystal arrangement predicted polymerization, upon heating, the molecule avoided this pathway by undergoing a large rotation to form an intramolecular cycloadduct. Theoretical calculations supported the feasibility of the rotation, exploiting the flexibility of the molecule and voids present. These findings caution that the reliance on Schmidt's criteria for topochemical reactions may sometimes be misleading, especially in heat-induced reactions.

Density functional theory guide for copolymerization mechanism between allyl radical with radicalophile: photo-driven radical mediated [3 + 2] cyclization.

The challenge of activating inert allyl monomers for polymerization has persisted, prompting our proposal of the photo-driven radical mediated [3 + 2] cyclization reaction (PRMC). This innovative approach significantly expedites the homopolymerization of multi-allyl monomers, enabling the synthesis of embolic microspheres for hepatocellular carcinoma interventions. PRMC involves allyl monomers to form allylic radicals and then radicals participating in a cycloaddition reaction with unsaturated olefins as radicalophiles to form cyclopentane-based radical products. While extensively studied in the theoretical and experimental homopolymerization, PRMC's application in copolymerization remains unexplored. To address this knowledge gap, we explored the elementary reaction, selecting allyl methyl ether radicals (AMER) and α,β-unsaturated ketones as radicalophiles for copolymerization investigations by density functional theory (DFT) analysis. We quantified energy differences between ground and excited states of reactants, elucidated frontier molecular orbitals, and assessed thermodynamic data for copolymerization feasibility. We also evaluated the electronic properties of reactants, predicting the reactivity of radicalophiles and the interactions of intermolecular reactions. Additionally, we applied transition state theory and interaction/deformation models and conducted a local orbital analysis to comprehensively study excess electron distribution and gyration radius of cyclic radical product. Our findings offer vital insights into PRMC's potential in copolymerization. This research provides a robust theoretical foundation for practical application, enhancing the polymerization field. Based on density functional theory (DFT), the calculations were performed at the M06-2X/6-311 + + G(d,p) level in/by Gaussian 16 package. Subsequently, our analytical results apply time-dependent density-functional theory (TD-DFT) and solvent modeling (SMD). Single-point energy calculations determine the driving force behind the radicals' reaction with radicalophiles. Furthermore, we assessed the electrostatic potential (ESP) of the reactants. The results of the calculations were visualized by the Multiwfn 3.6 and VMD 1.9 programs.

Enhancing Electrocatalytic Semihydrogenation of Alkynes via Weakening Alkene Adsorption over Electron-Depleted Cu Nanowires.

Electrochemical semihydrogenation (ESH) of alkynes to alkenes is an appealing technique for producing pharmaceutical precursors and polymer monomers, while also preventing catalyst poisoning by alkyne impurities. Cu is recognized as a cost-effective and highly selective catalyst for ESH, whereas its activity is somewhat limited. Here, from a mechanistic standpoint, we hypothesize that electron-deficient Cu can enhance ESH activity by promoting the rate-determining step of alkene desorption. We test this hypothesis by utilizing Cu-Ag hybrids as electrocatalysts, developed through a welding process of Ag nanoparticles with Cu nanowires. Our findings reveal that these rationally engineered Cu-Ag hybrids exhibit a notable enhancement (2-4 times greater) in alkyne conversion rates compared to isolated Ag NPs or Cu NWs, while maintaining over 99% selectivity for alkene products. Through a combination of operando and computational studies, we verify that the electron-depleted Cu sites, resulting from electron transfer between Ag nanoparticles and Cu nanowires, effectively weaken the adsorption of alkenes, thereby substantially boosting ESH activity. This work not only provides mechanistic insights into ESH but also stimulates compelling strategies involving hybridizing distinct metals to optimize ESH activity.