Bond Breaking Research Articles

Combining machine learning and molecular dynamics to predict strength-toughness and energy dissipation mechanisms of hybrid double-crosslinked CNT networks

Cross-linking has a significant strengthening effect on the mechanical properties of carbon nanoparticles, but there are still great challenges in how to control their mechanical properties through precise cross-linking ratios. Therefore, we use coarse-grained molecular dynamics (CGMD) to simulate its mechanical properties as data samples and combine it with machine learning methods to predict the optimal strength and toughness of carbon nanotubes (CNTs) corresponding to optimal cross-linking conditions. We found that the cross-linking density range is 2.60 ∼ 2.75 × 10-4/nm3, and the strong and weak cross-linking ratio range is 91 % S+9% W∼95 % S+5% W, which is the optimal range to achieve the mechanical properties of CNTs. Excessively high cross-link density and strong bond ratios can reduce the total number of cross-link bond breaks, thus decreasing their toughness. Meanwhile, high cross-linking density has a greater impact on the shear and slip between CNTs, tending to make CNTs brittle. Our proposed new approach for extracting data from coarse-grained models can obtain substantial optimization results without requiring much simulation computation. Furthermore, these cross-linking strategies and machine learning algorithms proposed in this work can provide a theoretical basis for controlling the mechanical properties of CNT materials, and also open up a new way for functional network materials other than CNTs.

Effect of Electric Fields on the Decomposition of Phosphate Esters.

Phosphate esters decompose on metal surfaces and form protective polyphosphate films. For many applications, such as in lubricants for electric vehicles and wind turbines, an understanding of the effect of electric fields on molecular decomposition is urgently required. Experimental investigations have yielded contradictory results, with some suggesting that electric fields improve tribological performance, while others have reported the opposite effect. Here, we use nonequilibrium molecular dynamics (NEMD) simulations to study the decomposition of tri-n-butyl phosphate (TNBP) molecules nanoconfined between ferrous surfaces (iron and iron oxide) under electrostatic fields. The reactive force field (ReaxFF) method is used to model the effects of chemical bonding and molecular dissociation. We show that the charge transfer with the polarization current equalization (QTPIE) method gives more realistic behavior compared to the standard charge equilibration (QEq) method under applied electrostatic fields. The rate of TNBP decomposition via carbon-oxygen bond dissociation is faster in the nanoconfined systems than that in the bulk due to the catalytic action of the surfaces. In all cases, the application of an electric field accelerates TNBP decomposition. When electric fields are applied to the confined systems, the phosphate anions are pulled toward the surface with high electric potential, while the alkyl cations are pulled to the surface with lower potential, leading to asymmetric film growth. Analysis of the temperature- and electric field strength-dependent dissociation rate constants using the Arrhenius equation suggests that, on reactive iron surfaces, the increased reactivity under an applied electric field is driven mostly by an increase in the pre-exponential factor, which is linked to the number of molecule-surface collisions. Conversely, the accelerated decomposition of TNBP on iron oxide surfaces can be attributed to a reduction in the activation energy with increasing electric field strength. Single-molecule nudged-elastic band (NEB) calculations also show a linear reduction in the energy barrier for carbon-oxygen bond breaking with electric field strength, due to stabilization of the charged transition state. The simulation results are consistent with experimental observations of enhanced and asymmetric tribofilm growth under electrostatic fields.

The Role of Protein Disulfide Isomerase Inhibitors in Cancer Therapy.

Protein disulfide isomerase (PDI) is a member of the mercaptan isomerase family, primarily located in the endoplasmic reticulum (ER). At least 21 PDI family members have been identified. PDI plays a key role in protein folding, correcting misfolded proteins, and catalyzing disulfide bond formation, rearrangement, and breaking. It also acts as a molecular chaperone. Dysregulation of PDI activity is thus linked to diseases such as cancer, infections, immune disorders, thrombosis, neurodegenerative diseases, and metabolic disorders. In particular, elevated intracellular PDI levels can enhance cancer cell proliferation, metastasis, and invasion, making it a potential cancer marker. Cancer cells require extensive protein synthesis, with disulfide bond formation by PDI being a critical producer. Thus, cancer cells have higher PDI levels than normal cells. Targeting PDI can induce ER stress and activate the Unfolded Protein Response (UPR) pathway, leading to cancer cell apoptosis. This review discusses the structure and function of PDI, PDI inhibitors in cancer therapy, and the limitations of current inhibitors, proposing especially future directions for developing new PDI inhibitors.

High-Value Utilization of Cellulose: Intriguing and Important Effects of Hydrogen Bonding Interactions─A Mini-Review.

Cellulose has been widely used in papermaking, textile, and chemical industries due to its diverse sources, environmental friendliness, and renewability. Recently, much more attention has been paid to converting cellulose into high-value-added products. Therefore, the extraction of nanocellulose, the dissolution of cellulose, and their applications are some of the most important research topics currently. However, cellulose's dense hydrogen bond network poses challenges for efficient extraction and dissolution, limiting its potential for functional material development. This review discusses the mechanisms of hydrogen bond disruption and weak interactions during nanocellulose extraction and cellulose dissolution. Key challenges and future research directions are highlighted, emphasizing developing efficient, ecofriendly, and cost-effective methods. Additionally, this review provides theoretical insights for constructing high-performance cellulose-based materials.

Comprehensive analysis of lignin dimer dissolution microscopic mechanism in different aromatic-based deep eutectic solvent

Aromatic-based deep eutectic solvent (DES) is a novel kind of DES that can dissolve lignin efficiently. Density functional (DFT) calculation, molecular dynamics (MD) simulation and multivariate analysis were used to investigate the interaction mechanism of five aromatic-based DES on two lignin dimer models. The effects of dissolution temperature and the type of aromatic hydrogen bond donor (HBD) on the breaking bonds between β-O-4 and 5–5 substructural units or interacting with different functional groups on lignin were investigated. With the introduction of DES, the electrostatic interaction between Cl- and lignin was obvious, while the van der Waals interaction between HBD, Ch+ and lignin was obvious. Among all the aromatic-based DES, choline chloride/p-hydroxybenzoic acid (ChCl/PB) is considered to have efficient dissolution effect. In the process of lignin dissolution, γ-OH was the preferred site for PB and Cl- acting on the lignin dimer (β-O-4), and the proportion of hydrogen bonding with γ-OH is 40 %. It was distributed around the lignin dimer (β-O-4) at 0.28–0.32 nm, and the total interaction energy was −4041.1452 kJ/mol. This study provided novel insights and theoretical basis for the preparation of renewable DES using aromatic components.

DFT insight into the structural, vibrational, and electronic properties of thin [110] Ge nanowires as anodic material for Li batteries

Germanium nanowires could be used to improve as anodic materials since their charge rate is better than that of the current graphite electrodes. In this work, we present a Density Functional Theory study of the effect of interstitial Li atoms on the vibrational, electronic, and mechanical properties of ultrathin hydrogen-passivated Ge nanowires (HGeNWs) with diamond structure, grown along the [110] crystallographic direction, and with a diameter of ∼14.4 Å. The interstitial Li atoms were placed at the tetrahedral positions (Td) reported as the more favorable ones. The phonon band structure of the HGeNWs reveals the existence of high frequency vibrations due to the hydrogen atoms at the nanowire surface. The effect of one interstitial Li atom in the nanowire leads to the apparition of three flat phonon bands almost independent of the collective vibrational states of the nanowire, reflecting a weak interaction between the Li atom and the neighboring ones; and a shift of the high vibrational modes to lower frequencies that results in more dispersive states. The electronic band structure confirms a transition from semiconducting to metallic behavior by adding a single Li interstitial atom per unit cell. The formation energies indicate that the nanowires with interstitial Li atoms are stable, and the average binding energy per Li atom slightly increases as a function of the concentration of Li atoms. The insertion of Li atoms in the nanowire leads to a volumetric expansion, without fracture or broken bonds. Even more, the redistribution of the electronic charge due to the Li atoms give the Ge-Ge bonds more axial elasticity and the values of the modulus of Young are almost constant for all studied concentrations of Li atoms. These theoretical results indicate an improvement of mechanical and electronic properties of Ge nanowires through the addition of interstitial Li atoms that could be important for their use as anodes in rechargeable Li batteries.

Computational Investigation of the Ru‐Mediated Preparation of Benzothiazoles From N‐Arylthioureas: Elucidation of the Reaction Mechanism and the Origin of Differing Substrate Reactivity

ABSTRACTSynthesis of novel benzothiazoles via intramolecular CS bond formation reactions is increasingly being explored since they have been found in a wide range of natural products and pharmaceutical agents. Sharma et al. reported the ruthenium‐catalyzed preparation of novel benzothiazole derivatives from N‐arylthiourea precursors, with a range of reaction yields and selectivity being observed. We have employed a density functional theory‐based computational model to investigate the reaction mechanism leading to the benzothiazole product and help uncover the origin of the differing experimental yields and substrate specificities. We proposed a modified mechanistic scheme where the rate‐determining step to be the synchronized breaking of the peroxide bond of the oxidizing agent with the concomitant proton‐coupled electron transfer from the haloarene urea and a Ru‐bound water molecule, not electrophilic RuC bond activation. Evidence for this being the rate‐determining step is (a) the barrier is consistent with a lack of kinetic isotope effects associated with the ortho‐H atom and (b) the computed rate‐determining barriers for 10 N‐arylthiourea substrates show good correlation with the observed yield.

One Pot Synthesis of Thiopyrimidine Derivatives from Lignin Reproductions by Microwave-Assisted Ultrasonic Microscopy with DFT Description for Clarifying the Mass Spectrum

In this work, an efficient and sustainable procedure for the one-pot synthesis of thiopyrimidine derivatives starting 1,3-diketone cut off β-O-4 lignin precursors to create anticancer agents. Microwave-ultrasonic assisted lignin extract in accessing various heterocyclic precursors such as pyrimidine, pyridine, and thiophene moieties. The results designated the ultrasonic-assisted microwave significantly accelerated synthesis with reduced time. We have diversely prolonged to tight-binding approaches to the electron ionization mass spectrometry with quantum stimulation (DFT/EIMS) to examine electron ionization mass spectra correlated to the experiment. Moreover, DFT/EIMS provides into the mechanism of the reaction of mass spectra trials. It cabins on the fragmentation method to raise the challenging bond breaking and structural rearrangements. The quantum chemical process for effective precursors of a mass spectrum is exactness required and discussed. Foremost fragmentation designs are studied and related to experimental data of the pyrimidin-thione derivatives and their glycosides.

Facile heterolytic bond splitting of molecular chlorine upon reactions with Lewis bases: Comparison with ICl and I2

AbstractFormation of molecular complexes and subsequent heterolytic halogen‐halogen bond splitting upon reactions of molecular Cl2 with nitrogen‐containing Lewis bases (LB) are computationally studied at M06‐2X/def2‐TZVPD and for selected compounds at CCSD(T)/aug‐cc‐pvtz//CCSD/aug‐cc‐pvtz levels of theory. Obtained results are compared with data for ICl and I2 molecules. Reaction pathways indicate, that in case of Cl2∙LB complexes the activation energies for the heterolytic Cl‐Cl bond splitting are lower than the activation energies of the homolytic splitting of Cl2 molecule into chlorine radicals. The heterolytic halogen splitting of molecular complexes of X2∙Py with formation of [XPy2]+… contact ion pairs in the gas phase is slightly endothermic in case of Cl2 and I2, but slightly exothermic in the case of ICl. Formation of {[ClPy2]+…}2 dimers makes the overall process exothermic. Taking into account that polar solvents favor ionic species, generation of donor‐stabilized Cl+ in the presence of the Lewis bases is expected to be favorable. Thus, in polar solvents the oxidation pathway via donor‐stabilized Cl+ species is viable alternative to the homolytic Cl‐Cl bond breaking.

Quantum Chemical Calculation on ScCl3-NaCl-KCl Molten Salt System

Background: The study of the ionic structure of the ScCl3-NaCl-KCl molten salt system is of guiding significance for the production of metal Sc and Sc alloy by molten salt electrolysis using ScCl3-NaCl-KCl molten salt system as electrolyte. However, limited research has been conducted on the structural analysis of molten salt within this system using Raman spectroscopy. Methods: The Gaussian and GaussView programs are used to simulate Sc-Cl ionic groups that may exist in the ScCl3-NaCl-KCl molten salt system based on density functional theory (DFT) and calculate their theoretical Raman spectra. Then, the wave function analysis of these Sc-Cl ionic groups is carried out using the Multiwfn program. Results: When the ScCl3-NaCl-KCl system is used as the electrolyte, it is considered that the 8 Sc atom in ScCl74− ionic groups is most easily reduced by electrochemistry at the cathode when the concentrations of eight Sc-Cl ionic groups are the same. In Sc2Cl7− Sc2Cl82− and Sc2Cl93− ionic groups, the sites that are most likely to attract electrophiles to attack and react are 1Cl and 7Cl, respectively, and the two Sc atoms located in the "chlorine bridge" structure contribute the most to LUMO orbitals, and nucleophiles will preferentially attack the Sc atoms located in the "chlorine bridge" structure. For Sc2Cl7−、Sc2Cl82− and Sc2Cl93− ionic groups, which have two Sc atoms, the bonds formed between Sc and Cl in the "chlorine bridge" structure have the smallest bond order, so the bonds formed by Sc and Cl in the "chlorine bridge" structure break first during the reaction, and then the bond formed by Sc and Cl located at both ends of the whole structure breaks Conclusion: The key information, such as bond length, point group structure, and theoretical Raman spectral characteristic peak after optimization, are obtained by the Gaussian and GaussView programs. The net atomic charge in each ionic group, the direction of electron migration during the formation of the ionic groups, the sites where electrophilic and nucleophilic reactions are most likely to occur in each ionic group, and the order of bond breaking during chemical reactions are obtained by the Multiwfn program.

Light-Induced Ring-to-Chain Transformations of Elemental Sulfur: Nonadiabatic Dynamics Simulations.

The emergence of high-sulfur content polymeric materials and their diverse applications underscore the need for a comprehensive understanding of the ring-to-chain transformation of elemental sulfur. In this study, we delve into the ultrafast transformation of the elemental sulfur S8 ring upon photoexcitation employing advanced nonadiabatic dynamics simulations. Our findings reveal that the bond breaking of the S8 ring occurs within tens of femtoseconds. At the time of bond breaking, most molecules are in the lowest singlet excited state S1. S1 survives for 40-450 fs before relaxing to the quasi-degenerate manifolds formed by the T1 and S0 states of the S8 chain. This suggests that upon photoexcitation the polymerization of the S8 chains might proceed before the chains relax to their lowest energy states. The derived temporal resolution provides a detailed perspective on the dynamics of S8 rings upon photoexcitation, shedding light on the intricate processes involved in its excited-state transformations.

Revealing the Bro̷nsted Acidic Nature of Penta-Coordinated Aluminum Species in Dealuminated Zeolite Y with Solid-State NMR Spectroscopy.

The inevitable dealumination process of zeolite Y is closely related to ultrastabilization, enhanced Bro̷nsted acidity, and deactivation throughout its life cycle, producing complex aluminum and acidic hydroxyl species. Most investigations on dehydrated zeolites have focused on the Bro̷nsted acidity of tetra-coordinated Al (Al(IV)) and Lewis acidity associated with tricoordinated Al (Al(III)) sites, which has left the penta-coordinated Al (Al(V)) in dealuminated zeolites scarcely discussed. This is largely due to the oversimplified view of detectable Al(V) as an exclusively extra-framework species with Lewis acidity. Here we report the formation of Bro̷nsted acidic penta-coordinated Al species (Al(V)-BAS) in the dealumination process. Two-dimensional (2D) through-bond and multiquantum 1H-{27Al} correlation solid-state NMR experiments demonstrate the presence of a bridging Si-OH-Al(V) structure in dealuminated Y zeolites. Different from the conventional belief that water attack leads to the breaking of zeolite framework Al-O bonds in the initial stage of zeolite dealumination, the observed Al(V) as a dealumination intermediate is directly correlated with a BAS pair because of the direct dissociation of water on the framework tetrahedral aluminum (Al(IV)), thus bypassing the cleavage of Al-O bonds. 1H double-quantum solid-state NMR experiments and theoretical calculations provide further evidence for this mechanism, whereas pyridine adsorption experiments confirm stronger acidity of Al(V)-BASs than the traditional bridging hydroxyl groups associated with Al(IV). We were also able to detect the Al(V)-BAS site from dealuminated SSZ-13 zeolite with CHA topology, suggesting that its creation is not specific to the framework structure of zeolites.

The Role of Frustrated Lewis Pair in Catalytic Transfer Hydrogenation of Furfural using Nickel Single-Atom Catalysts: A Theoretical Study.

The burgeoning field of frustrated Lewis pair (FLP) heterogeneous catalysts has garnered significant interest in recent years, primarily due to their inherent ability to activate H-source molecules, such as H2, thereby facilitating hydrogenation reactions. However, the application of single metal atom catalysts incorporating FLP sites has been relatively under-explored. In this study, non-precious transition metal atoms were anchored onto a C2N framework with an intrinsic cavity and a defective N-C sheet. Theoretical calculations substantiated energy barriers as low as 0.10 eV for isopropanol activation, thereby positioning these catalysts as highly promising candidates for catalytic transfer hydrogenation of furfural. Electronic structure analyses revealed that the H-O bond breakage in isopropanol molecules was significantly facilitated by the presence of FLP sites within the catalysts. Notably, both Ni-C2N and Ni-N6-C demonstrated exceptional potential as selective catalysts for the hydrogenation of furfural into furfuryl alcohol, exhibiting remarkably low barriers of only 0.65-0.72 eV for the rate-determining steps, which are notably lower than those observed in many traditional catalysts. Theoretical investigations strongly imply that the construction of single atom catalysts with FLP sites could significantly enhance the activity and selectivity for hydrogenation reactions, thus stimulating the experimental synthesis of such catalysts.

Combination of nanoparticles with single-metal sites synergistically boosts co-catalyzed formic acid dehydrogenation

The development of hydrogen technologies is at the heart of a green economy. As prerequisite for implementation of hydrogen storage, active and stable catalysts for (de)hydrogenation reactions are needed. So far, the use of precious metals associated with expensive costs dominates in this area. Herein, we present a new class of lower-cost Co-based catalysts (Co-SAs/NPs@NC) in which highly distributed single-metal sites are synergistically combined with small defined nanoparticles allowing efficient formic acid dehydrogenation. The optimal material with atomically dispersed CoN2C2 units and encapsulated 7-8 nm nanoparticles achieves an excellent gas yield of 1403.8 mL·g−1·h−1 using propylene carbonate as solvent, with no activity loss after 5 cycles, which is 15 times higher than that of the commercial Pd/C. In situ analytic experiments show that Co-SAs/NPs@NC enhances the adsorption and activation of the key intermediate monodentate HCOO*, thereby facilitating the following C-H bond breaking, compared to related single metal atom and nanoparticle catalysts. Theoretical calculations show that the integration of cobalt nanoparticles elevates the d-band center of the Co single atoms as the active center, which consequently enhances the coupling of the carbonyl O of the HCOO* intermediate to the Co centers, thereby lowering the energy barrier.

Molecular Dynamics Simulation Model of Alkali Metal Reduction of Gaseous Halides and Reaction Mechanism Analysis.

The reaction of gaseous hydrogen halides with alkali metals provides a new pathway for producing hydrogen. The structure and reactivity of alkali metals are crucial for the reduction of gaseous halides. However, traditional gas-phase reaction models fail to provide insights into the dynamic processes occurring during alkali metal reactions. In this paper, based on the reaction between Hydrogen fluoride (HF) and alkali metal sodium (Na), we have established a metallic Na slab. HF molecules were randomly inserted above the surface of the Na slab, creating a reaction model for the reduction of HF by metallic Na. The reaction of HF on the Na surface was calculated using first-principles molecular dynamics. The configuration and reaction of the Na surface and HF molecules at different times were judged by analyzing the radial distribution function and mean squared displacement. Na atoms reacted with HF to produce intermediate NaFH, and then the F-H bond broke to form NaF and H. The F-H bond breaking of intermediate NaFH was the key step, and the kinetic parameters of this key step were calculated.

Back-Side Stress to Ease p-MOSFET Degradation on e-MRAM Chips

Abstract Magnetoresistive random access memory process makes great contribution to threshold voltage deterioration of metal-oxide-silicon field-effect transistors, especially on p-type devices. Herein, a method was proposed to reduce threshold voltage degradation by utilizing back-side stress. Through the deposition of tensile material on the back side, positive charges generated by silicon-hydrogen bond breakage were inhibited, resulting in a potential reduction of threshold voltage shift by up to 20%. In addition, it was found that the method could only relieve silicon-hydrogen bond breakage physically, failing to provide a complete cure. However, it holds significant potential for applications where additional thermal budget is undesired. Furthermore, it was also concluded that the method used in this work was irreversible, with its effect sustained to the chip package phase, and it ensures competitive reliability of the resulting magnetic tunnel junction devices.

Assembly of Dye Molecules in Covalent Organic Frameworks for Enhanced Colorimetric Biosensing.

Colorimetric assays have been extensively investigated for biosensing applications due to their advantages of visual recognizability, ease of use, and low cost. However, advancing their development is a great challenge due to the inherent limitations of colorimetric dyes. Herein, we report a strategy to assemble dyes in covalent organic frameworks (COFs) to effectively reinforce the applicability of pH-responsive dyes in colorimetric bioassays. Experimental results reveal that three-dimensional COFs can promote the assembly of dyes through hydrogen bonding, resulting in the formation of a dye-supermolecule@COF assembly. Consequently, when sensitized at increased pH levels (e.g., hydroxyl ions), disruption of hydrogen bonds may trigger a rapid transition from their insoluble fixed state within the COFs into soluble, visibly detectable dye anions. This process can also be facilitated by increased hydrophilicity and elevated electrostatic repulsion between the dye anions and COFs, leading to the substantial release of chromogenic dye anions from the COF pores into the solution, thereby amplifying the colorimetric signal output. Therefore, by employing various synthesized dye-supermolecule@COFs as signal tags, we developed a colorimetric bioassay capable of accurately identifying breast cancer cell subtypes. This study not only highlights the effectiveness of dye-supermolecule@COFs in enhancing colorimetric biosensing but also underscores the potential of employing the COF-mediated dye assembly strategy for colorimetric assays.

Experimental and molecular dynamics simulation study on the mechanism of β-lactoglobulin self-aggregation induced by ultra-high temperature

Ultra-high temperature (UHT) treatment effectively prevents milk spoilage, yet it can cause protein aggregation, thereby impacting milk stability. β-Lactoglobulin (β-Lg) is a thermally unstable whey protein, but the mechanism of its self-aggregation induced by UHT treatment remains unclear. Herein, experimental approaches and molecular dynamics simulations were performed to elucidate β-Lg aggregation under UHT. The physicochemical properties of the aggregates were initially characterized after different UHT treatments. Size exclusion chromatography and multi-angle static light scattering showed β-Lg aggregates with molecular weights from 20 to 900 kDa and particle sizes from 100 to 350 nm, with bead string and irregular morphologies. Multispectroscopy showed that UHT treatment caused the unfolding of the β-Lg. Molecular dynamics simulations further observed hydrogen bond disruption and β-barrel opening, enhancing the electrostatic interactions and hydrophobicity of β-Lg surfaces, leading to non-covalent aggregation. Furthermore, SDS-PAGE confirmed the involvement of disulfide bonds in aggregate formation, and mass spectrometry identified the disruption of original disulfide bonds under UHT, promoting intermolecular disulfide bonding involving residues Cys119, Cys121, and Cys160. These findings provide a comprehensive understanding of β-Lg aggregation under UHT conditions, which is essential for improving the stability and quality of UHT-treated milk products.

A chemo-mechanical model for growth and mechanosensing of focal adhesion

Focal adhesion (FA), the complex molecular assembly across the lipid membrane, serves as a hub for physical and chemical information exchange between cells and their microenvironment. Interestingly, studies have shown that FAs can grow along the direction of contractile forces generated by actomyosin stress fibers and achieve larger sizes on stiffer substrates. In addition, the cellular traction transmitted to the substrate was observed to reach the maximum near the FA center. However, the biomechanical mechanisms behind these intriguing findings remain unclear. To answer this important question, here we first developed a one-dimensional (1D) chemo-mechanical model of FA where key features like adhesion plaque deformation, active contraction by stress fibers, force-dependent association/dissociation of integrin bonds connecting two surfaces, and substrate compliance have all been considered. Within this formulation, we showed that the rigidity-sensing capability of FAs originates from the deformability of stress fibers while the force-dependent breakage of integrin bonds leads to the appearance of the traction peak at the FA center. Furthermore, by extending the model into three-dimensional as well as incorporating assembly/dis-assembly kinetics of adhesion proteins, we also demonstrated how anisotropic stress/strain field within the adhesion plaque will be induced by the presence of contractile forces which leads to the directional growth of the FA.

The preparation technology and catalytic mechanism of PVDF/PVP/a-MoSx porous membrane for water flow driven piezoelectric PMS activation

Piezoelectric catalysis couples with peroxymonosulfate (PMS) activation technology can efficiently increase the yield of reactive oxygen species (ROS). Herein, a novel flexible polyvinylidene difluoride/polyvinyl pyrrolidone/amorphous molybdenum sulfide (PVDF/PVP/a-MoSx) membrane with finger-like pore structure was prepared by non-solvent induced phase separation (NIPS) method. As a result, a-MoSx nanosheets can be exposed out of the pores to provide multiple active sites. The PVDF/PVP/a-MoSx with large dipole moment can form enhanced polarization field under water flow to accelerate the charges separation and transfer, thereby promoting the breakage of the OO bond of PMS. The mechanism of piezo-photocatalytic activated PMS was confirmed by COMSOL multiphysics simulations, electrochemical experiments, contribution of active species and DFT calculations. Moreover, a self-cycling degradation reactor was proved more effective in generating piezoelectric potential and improving the degradation efficiency, supporting the practical potential of this strategy. This study provides a new platform to develop piezoelectric porous membrane for enhanced PMS activation under low density flow water energy.