Interfacial Hydrogen Bonds Research Articles

Extreme Environment-Adaptable and Ultralong-Life Energy Storage Enabled by Synergistic Manipulation of Interfacial Environment and Hydrogen Bonding

Extreme Environment-Adaptable and Ultralong-Life Energy Storage Enabled by Synergistic Manipulation of Interfacial Environment and Hydrogen Bonding

Rapid Assembly of Ultrafine Palladium Nanoparticle-Decorated HOF-101 Triggered by Guest Enzyme Encapsulation.

Rapid enzyme immobilization is essential for enzyme catalysis and sensing applications, yet constructing effective immobilization systems is challenging due to the need to balance enzyme activity with the properties of the surrounding framework. Herein, taking glucose oxidase (GOx) as a model, a rapid and straightforward approach was presented for synthesizing palladium nanoparticles (PdNPs)-decorated GOx encapsulated in HOF-101 nanocomposite materials (designated as PdNPs/GOx@HOF-101) through an in situ photoreduction and enzyme-triggering HOF-101 encapsulation. The enzyme's surface residues trigger the nucleation of HOF-101 around it through the hydrogen-bonded bio interface, completing the self-assembly of HOF-101 in 0.5 h. Furthermore, the biocomposites loaded with ultrafine PdNPs show satisfactory photoelectrochemical (PEC) properties. As a proof-of-concept, a PEC biosensor was constructed by utilizing PdNPs/GOx@HOF-101 as a photoactive probe, which can quickly and sensitively detect glucose and simultaneously remain stable within the circumstance of 30-60 °C and pH 4-8. These attributes pave the way for diverse applications, including improved enzyme immobilization techniques, advanced biosensors, and more efficient biocatalytic processes.

Probing atomic-scale processes at the ferrihydrite-water interface with reactive molecular dynamics

Interfacial processes involving metal (oxyhydr)oxide phases are important for the mobility and bioavailability of nutrients and contaminants in soils, sediments, and water. Consequently, these processes influence ecosystem health and functioning, and have shaped the biological and environmental co-evolution of Earth over geologic time. Here we employ reactive molecular dynamics simulations, supported by synchrotron X-ray spectroscopy to study the molecular-scale interfacial processes that influence surface complexation in ferrihydrite-water systems containing aqueous MoO42-\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${\ ext {MoO}_4}^{2-}$$\\end{document}. We validate the utility of this approach by calculating surface complexation models directly from simulations. The reactive force-field captures the realistic dynamics of surface restructuring, surface charge equilibration, and the evolution of the interfacial water hydrogen bond network in response to adsorption and proton transfer. We find that upon hydration and adsorption, ferrihydrite restructures into a more disordered phase through surface charge equilibration, as revealed by simulations and high-resolution X-ray diffraction. We observed how this restructuring leads to a different interfacial hydrogen bond network compared to bulk water by monitoring water dynamics. Using umbrella sampling, we constructed the free energy landscape of aqueous MoO42-\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${\ ext {MoO}_4}^{2-}$$\\end{document} adsorption at various concentrations and the deprotonation of the ferrihydrite surface. The results demonstrate excellent agreement with the values reported by experimental surface complexation models. These findings are important as reactive molecular dynamics opens new avenues to study mineral-water interfaces, enriching and refining surface complexation models beyond their foundational assumptions.Graphic

Hydrogen bonding network in the electrical double layer mediates fast proton skipping to Get Rid of Fenton reaction pH dependence enables highly efficient alkaline water purification

A fundamental scientific quandary in environmental has always been the pH dependence in Fenton reaction, that is, the reaction kinetics decreases by approximately 1–3 orders of magnitude upon transitioning from an acidic to an alkaline state. Here, we discovered that protons significantly contribute to the Fenton reaction through an examination of the reaction's interfacial behavior characteristics. Proton transfer mediated by hydrogen bond network connectivity in the electric double layer is responsible for the pH dependence of Fenton reaction kinetics. On this basis, the surface potential of Fenton reaction catalyst was modified to optimize the distribution of H2O in the electrical double layer, enhancing the connectivity of the interfacial hydrogen bond network and providing a fast channel for rapid proton transfer. The consecutive hydrogen bond network mediates rapid proton hopping, increasing the proton concentration in the Helmholtz layer, and consequently promoting the proton conductivity from 5.38×10−7 S·cm−2 to 4.35×10−6 S·cm−2 in alkaline conditions for Fenton reaction. Meanwhile, the kinetics reaction rate was improved 20 times, and the pH dependence was reduced from 70.9 % to 12.6 %. This discovery clarifies the key role of the interfacial hydrogen bond network and proton transfer in Fenton reaction kinetics pH dependence. It provides new theories and methods for achieving alkaline high Fenton reaction kinetics.

Thermochromic behavior of pigment red 254 in nylon 6 polymer for high-chromaticity engineering plastics

Advancement in Color-Material-Finishing (CMF) plays a crucial role in enhancing the visual appeal of plastic products, particularly for the high-chroma nylon plastics that are currently in vogue. However, it is inevitable to encounter pigment-dyeing issues in polar engineering plastics during the high-temperature extrusion process, which can lead to intense fluorescence and color fading. This phenomenon, characterized by the dissolution of pigments in a polar environment, can adversely affect the color saturation and weatherability of the pigment, which ultimately cause sharp reduction of aesthetic quality and durability of the plastic. Herein, we develop a modified strategy combined with thermal annealing to realize rapid color recovery in nylon 6, and further reveal the fluorescence and discoloration mechanism of pigment red 254 in nylon 6. Through improving the mobility of nylon chain segments, the rigid heterogeneous nucleation regions centered on the interfacial hydrogen bond between nylon 6 and the pigment molecules loosens with the help of heat treatment, and then the dissolved pigment molecules reaggregate to induce fluorescence quenching. Importantly, as a consequence of the increased lubricity segments, the required thermal annealing temperature and time for color recovery and fluorescence quenching could be significantly shortened from 180 °C for 5 h to 100 °C for 0.5 h. This work provides a feasible approach for the industrial production of high-chroma polar engineering plastics.

Dual functional bio-inspired additives reconstruct metal-organic interface stability for wearable energy storage system

Aqueous zinc-ion batteries (AZIBs) hold significant promise across wearable energy storage devices due to their superior safety and cost-effectiveness. However, the instability of the electrode/electrolyte interface leads to severe hydrogen evolution reaction (HER) and dendritic growth. Herein, a bio-inspired additive, keratin (Ker), is introduced to construct a robust interfacial layer. The hydrogen bonding donors homogenize the distribution of interfacial hydrogen bond networks and increases the electron density in Zn2+-OH interaction, stabilizing bound H2O molecules and effectively inhibiting HER. Additionally, electron transfer from the highly reactive thiol (-SH) motivates the formation of Zn-S chemical linkage, enhancing interface stability. These features endow Zn||Zn symmetric cells with an impressive cycle life, reaching up to 3364 h at 1 mA cm−2/1 mAh cm−2. The Zn||α-MnO2 and Zn||VO2 full cells also exhibit a substantial capacity retention after 1000 cycles. Incorporating multi-step laser cutting technology enables the fabrication of flexible, large-area micro-batteries with prolonged cycle life. This study presents an advanced methodology for heralding a promising pathway to improve the reversibility of aqueous energy storage systems.

The Loss of Interfacial Water-Adsorbate Hydrogen Bond Connectivity Position Surface-Active Hydrogen as a Crucial Intermediate to Enhance Nitrate Reduction Reaction.

The electrochemical nitrate reduction reaction (NO3RR) offers a promising solution for remediating nitrate-polluted wastewater while enabling the sustainable production of ammonia. The control strategy of surface-active hydrogen (*H) is extensively employed to enhance the kinetics of the NO3RR, but atomic understanding lags far behind the experimental observations. Here, we decipher the cation-water-adsorbate interactions in regulating the NO3RR kinetics at the Cu (111) electrode/electrolyte interface using AIMD simulations with a slow-growth approach. We demonstrate that the key oxygen-containing intermediates of the NO3RR (e.g., *NO, *NO2, and *NO3) will stably coordinate with the cations, impeding their integration with the hydrogen bond network and further their hydrogenation by interfacial water molecules due to steric hindrance. The *H can migrate across the interface with a low energy barrier, and its hydrogenation barrier with oxygen-containing species remains unaffected by cations, offering a potent supplement to the hydrogenation process, playing the predominant factor by which the *H facilitates NO3RR reaction kinetic. This study provides valuable insights for understanding the reaction mechanism of NO3RR by fully considering the cation-water-adsorbate interactions, which can aid in the further development of the electrolyte and electrocatalysts for efficient NO3RR.

Molecular dynamics simulation of nanocellulose and cement matrix composites

The interfacial properties of nanocellulose and cement matrix are the key factors affecting the mechanical properties of composite materials. However, it is challenging to study the interface combination through conventional experiments and microscopic characterization techniques. Molecular dynamics simulation (MD), as a nanoscale analytical method, can be used to calculate and analyze the strength, deformation, destruction and interfacial interaction of materials on the atomic scale. Since the existing methods of C-S-H modeling and fiber pull-out from the matrix in molecular dynamics simulations were not suitable for cellulose/C-S-H composite models. In this paper, a molecular dynamics simulation method for nanocellulose cement matrix composites was proposed. Based on the embedded composite model, the tensile stress-strain, interfacial interaction energy, hydrogen bond, and interface failure mode were studied when cellulose was pulled out of the matrix. The results showed that adding cellulose could improve the local ductility and tensile strength of cement matrix materials. The interfacial interaction energy between cellulose and C-S-H was approximately −1.09 J/m2, which was much higher than that between carbon nanotubes and C-S-H. Cellulose would adsorb hydrogen and oxygen atoms on H2O, OH− and silica tetrahedron in C-S-H. In the pull-out simulation of cellulose in C-S-H, C-S-H on the surface of cellulose would be destroyed and attached to the cellulose surface and moved along with it, indicating that cellulose could play a good bridging role in the matrix. The simulation results revealed the action mechanism of cellulose in cement matrix materials.

Polyelectrolyte Additive‐Modulated Interfacial Microenvironment Boosting CO2 Electrolysis in Acid

Acidic CO2 electrolysis offers a promising strategy to achieve high carbon utilization and high energy efficiency. However, challenges remain in suppressing the competitive hydrogen evolution reaction (HER) and improving product selectivity. High concentrations of potassium ions (K+) can suppress HER and accelerate CO2 reduction, but they still inevitably suffer from salt precipitation problems. In this study, we demonstrate that the sulfonate‐based polyelectrolyte, polystyrene sulfonate (PSS), enables to reconstruct the electrode‐electrolyte interface to significantly enhance the acidic CO2 electrolysis. Mechanistic studies reveal that PSS induces high local K+ concentrations through electrostatic interaction between PSS anions and K+. In situ spectroscopy reveals that PSS reshapes the interfacial hydrogen–bond (H–bond) network, which is attributed to the H–bonds between PSS anions and hydrated proton as well as the steric hindrance of the additive molecules. This greatly weakens proton transfer kinetics and leads to the suppression of undesirable HER. As a result, a Faradaic efficiency of 93.9% for CO can be achieved at 250 mA cm–2, simultaneous with a high single‐pass carbon efficiency of 72.2% on commercial Ag catalysts in acid. This study highlights the important role of the electrode‐electrolyte interface induced by polyelectrolyte additives in promoting electrocatalytic reactions.

Polyelectrolyte Additive-Modulated Interfacial Microenvironment Boosting CO2 Electrolysis in Acid.

Acidic CO2 electrolysis offers a promising strategy to achieve high carbon utilization and high energy efficiency. However, challenges remain in suppressing the competitive hydrogen evolution reaction (HER) and improving product selectivity. High concentrations of potassium ions (K+) can suppress HER and accelerate CO2 reduction, but they still inevitably suffer from salt precipitation problems. In this study, we demonstrate that the sulfonate-based polyelectrolyte, polystyrene sulfonate (PSS), enables to reconstruct the electrode-electrolyte interface to significantly enhance the acidic CO2 electrolysis. Mechanistic studies reveal that PSS induces high local K+ concentrations through electrostatic interaction between PSS anions and K+. In situ spectroscopy reveals that PSS reshapes the interfacial hydrogen-bond (H-bond) network, which is attributed to the H-bonds between PSS anions and hydrated proton as well as the steric hindrance of the additive molecules. This greatly weakens proton transfer kinetics and leads to the suppression of undesirable HER. As a result, a Faradaic efficiency of 93.9% for CO can be achieved at 250 mA cm-2, simultaneous with a high single-pass carbon efficiency of 72.2% on commercial Ag catalysts in acid. This study highlights the important role of the electrode-electrolyte interface induced by polyelectrolyte additives in promoting electrocatalytic reactions.

Coordination and Hydrogen Bond Chemistry in Tungsten Oxide@Polyaniline Composite toward High-Capacity Aqueous Ammonium Storage.

Aqueous ammonium ion batteries (AAIBs) have garnered significant attention due to their unique energy storage mechanism. However, their progress is hindered by the relatively low capacities of NH4 + host materials. Herein, the study proposes an electrodeposited tungsten oxide@polyaniline (WOx@PANI) composite electrode as a NH4 + host, which achieves an ultrahigh capacity of 280.3 mAh g-1 at 1 A g-1, surpassing the vast majority of previously reported NH4 + host materials. The synergistic interaction of coordination chemistry and hydrogen bond chemistry between the WOx and PANI enhances the charge storage capacity. Experimental results indicate that the strong interfacial coordination bonding (N: →W6+) effectively modulates the chemical environment of W atoms, enhances the protonation level of PANI, and thus consequently the conductivity and stability of the composites. Spectroscopy analysis further reveals a unique NH4 +/H+ co-insertion mechanism, in which the interfacial hydrogen bond network (N-H···O) accelerates proton involvement in the energy storage process and activates the Grotthuss hopping conduction of H+ between the hydrated tungsten oxide layers. This work opens a new avenue to achieving high-capacity NH4 + storage through interfacial chemistry interactions, overcoming the capacity limitations of NH4 + host materials for aqueous energy storage.

Topological properties of interfacial hydrogen bond networks

Topological properties of interfacial hydrogen bond networks

Interfacial Hydrogen-Bond Interactions Driven Assembly toward Polychromatic Copper Nanoclusters.

Constructing versatile metal nanoclusters (NCs) assemblies through noncovalent weak interactions between inter-ligands is a long-standing challenge in interfacial chemistry, while compelling interfacial hydrogen-bond-driven metal NCs assemblies remain unexplored so far. Here, the study reports an amination-ligand o-phenylenediamine-coordinated copper NCs (CuNCs), demonstrating the impact of interfacial hydrogen-bonds (IHBs) motifs on the luminescent behaviors of metal NCs as the alteration of protic solvent. Experimental results supported by theoretical calculation unveil that the flexibility of interfacial ligand and the distance of cuprophilic CuI···CuI interaction between intra-/inter-NCs can be tailored by manipulating the cooperation between the diverse IHBs motifs reconstruction, therewith the IHBs-modulated fundamental structure-property relationships are established. Importantly, by utilizing the IHBs-mediated optical polychromatism of aminated CuNCs, portable visualization of humidity sensing test-strips with fast response is successfully manufactured. This work not only provides further insights into exploring the interfacial chemistry of NCs based on inter-ligands hydrogen-bond interactions, but also offers a new opportunity to expand the practical application for optical sensing of metal NCs.

Positive and Negative Impacts of Interfacial Hydrogen Bonds on Photocatalytic Hydrogen Evolution.

Understanding the behavior of water molecules at solid-liquid interfaces is crucial for various applications such as photocatalytic water splitting, a key technology for sustainable fuel production and chemical transformations. Despite extensive studies conducted in the past, the impact of the microscopic structure of interfacial water molecules on photocatalytic reactivity has not been directly examined. In this study, using real-time mass spectrometry and Fourier-transform infrared spectroscopy, we demonstrated the crucial role of hydrogen bond (H-bond) networks on the photocatalytic hydrogen evolution in thickness-controlled water adsorption layers on various TiO2 photocatalysts. Under controlled water vapor environments with relative humidity (RH) below 70%, we observed a monotonic increase in the H2 formation rate with increasing RH, indicating that reactive water molecules were present not only in the first adsorbed layer but also in several overlying layers. In contrast, at RH > 70%, when more than three water layers covered the catalyst surface, the H2 formation rate turned to decrease dramatically because of the structural rearrangement and hardening of the interfacial H-bond network induced during further water adsorption. This unique many-body effect of interfacial water was consistently observed for various TiO2 particles with different crystalline structures, including brookite, anatase, and a mixture of anatase and rutile. Our results demonstrated that depositing several water layers in a water vapor environment with RH ∼ 70% is optimal for photocatalytic hydrogen evolution rather than liquid-phase reaction conditions in aqueous solutions. This study provides molecular-level insights into designing interfacial water conditions to enhance photocatalytic performance.

Study of Interfacial Properties of Anionic–Nonionic Surfactants Based on Succinic Acid Derivatives via Molecular Dynamics Simulations and the IGMH Method

Surfactants are widely used in fields such as oil recovery and flotation. The properties and mechanisms of surfactants can be effectively studied using molecular dynamics (MD) simulations. Herein, the aggregation behavior of surfactants was studied at the oil–water interface by MD simulation, and the micro-morphology of surfactants was analyzed under a low concentration and saturated state at the oil–water interface, respectively. The visualization results of the MD simulation showed that DTOA was saturated at the oil–water interface at 120 surfactant molecules, whereas 160 surfactant molecules were required for BEMA. In addition, the effect of surfactant concentration on the interfacial thickness and hydrogen bond distribution was studied, with the inflection point of hydrogen bond distribution identified as a characteristic parameter for surfactant saturation at the oil–water interface. The aggregation behavior of their hydrophobic and hydrophilic chains at the oil–water interface was qualitatively assessed using order parameters. Finally, the aggregation state of surfactants in salt-containing systems was studied, and it was found that the surfactants could effectively adsorb magnesium ions and calcium ions at the oil–water interface. However, the curve of the number of hydrogen bonds varies greatly, with a possible reason being that BEMA has a different coordination manner with diverse metal ions. This study provides some original insights into both the theoretical study and practical application of anionic and nonionic surfactants.

Modulating Interfacial Hydrogen-Bond Environment by Electrolyte Engineering Promotes Acidic CO2 Electrolysis

Modulating Interfacial Hydrogen-Bond Environment by Electrolyte Engineering Promotes Acidic CO₂ Electrolysis

Study on mechanical properties and molecular simulation of nano‐SiO2‐modified hybrid fiber reinforced polymer bar under the dry and alkaline environment

AbstractFiber reinforced polymer (FRP) bars have received extensive promotion and application in the structural engineering. However, due to the limitations inherent in using single material, FRP reinforced concrete structures often encounter issues, such as brittle failure and inadequate energy dissipation, particularly in complex natural environments and under various loading conditions. In this study, the preparation of nano‐SiO2‐modified carbon/basalt hybrid FRP bars was carried out using the pultrusion‐winding process and ultrasonic treatment. The objective was to investigate the influence of the fiber volume ratio and mass fraction of nano‐SiO2 on the mechanical properties of FRP bars under drying and alkaline conditions. Molecular dynamics simulations were performed to construct interface models between fibers and epoxy resin in order to elucidate the toughening mechanism of nano‐SiO2 and the degradation mechanism in alkaline conditions. The research results show that elevating the substitution rate of carbon fibers and incorporating nano‐SiO2 doping bring about alterations in the brittle fracture characteristics of BFRP bars and enhance the post‐yield performance and interlaminar shear properties of hybrid FRP bars, concurrently mitigating the degradation of mechanical properties induced by exposure to alkaline solutions. MD simulations indicate that the addition of nano‐SiO2 improves the binding rate of hydrogen bonds between BF and epoxy resin, resulting in a higher interfacial energy between BF/epoxy resin compared to CF/epoxy resin. Moreover, nano‐SiO2 effectively mitigates the impact of alkaline solutions on the formation of interfacial hydrogen bonds. The findings of this study serve as a valuable reference for the design and application of FRP reinforced concrete structures.Highlights Nano‐SiO2 modified B/CFRP bars made via extrusion‐winding & ultrasonic treatment. Improved mechanical properties and plastic deformation in Nano‐SiO2 modified B/C FRP bars. Nano‐SiO2 inhibits B/CFRP bars degradation in alkaline solution. Nano‐SiO2 bind more at BF/epoxy than CF/epoxy interface. Nano‐SiO2 reduces alkaline solution effect on interfacial H‐bonding.

Enhanced Solar-to-Hydrogen Conversion and Hydrogen Isotope Separation through Interfacial Hydrogen-Bond Engineering and Homolytic O–H Cleavage on Multianionic Sulfides in Large-Scale Floating Nanocomposites

Enhanced Solar-to-Hydrogen Conversion and Hydrogen Isotope Separation through Interfacial Hydrogen-Bond Engineering and Homolytic O–H Cleavage on Multianionic Sulfides in Large-Scale Floating Nanocomposites

Performance-enhanced cellulose ternary composite in removing toxic lead ion pollutants: Atom-level interfacial structures and pseudo-dynamic trapping process

It is appealing but challenging to modulate interfacial structures and reactivity of biomass composites at the atomic level, due to its importance in guiding experimental synthesis and developing application. In this work, the ternary composite, carbon dots-Mg(OH)2-cellulose (CMCel), was examined by experimental characterizations (XRD, FT-IR, SEM, TEM, and XPS) and theoretical computations, along with its immobilization of heavy metal ion (HMI) Pb(II) from wastewater. Using a facile hydrothermal method, the composite material was prepared. It gives a high removal capacity up to 1623.0 mg g–1 towards Pb(II). Moreover, the removal rate maintains almost 99.5 % even after 10-cycle operation. The outstanding performance is attributed to synergetic effects of chemically coupled components in the composite. Specifically, interfacial hydrogen bonds are unraveled by density functional theory calculations and experimental characterizations. The HMI removal is well delineated via a pseudo-dynamic process. The in-depth understanding of interfacial behaviors of CMCel is anticipated to advance the design of novel water treatment agents and improve their removal performance towards HMIs.

Interfacial hydrogen bond effect between CeO2 and g-C3N4 boosts conversion to adipic acid from aerobic oxidation of cyclohexane

The selective oxidation reaction of cyclohexane is one of the typical activated sp3 C-H reactions, and its product adipic acid (AA) is the indispensable raw material used to produce nylon. However, subjecting to the inertness of C-H bond and the great reactivity of AA, the targeted transformation of cyclohexane remains a challenge. Here, the interfacial hydrogen bond (IHD) was developed by anchoring CeO2 on graphite carbon nitride (g-C3N4) surface, which could boost targeted acquisition adipic acid from aerobic oxidation of cyclohexane. The results indicated that the IHD effect can be flexibly regulated by changing the ratio of Ce3+/Ce4+, further optimizing the properties of surface OH species and Lewis acid sites. Under the synergistic effect of Ce3+/Ce4+ and Lewis acid sites on reaction interface, the glorious performance (32.2% conversion of cyclohexane with 66.4% selectivity) was obtained over the as-prepared CeO2/g-C3N4 IHD system. In addition, the interfacial adsorption properties of cyclohexane were explored by the virtue of in situ infrared spectroscopy, revealing the IHD effect could tune the adsorption behavior of cyclohexanone and further improve the selectivity of AA. This work disclosed that engineering the interface hydrogen bond effect between CeO2 and g-C3N4 provided feasible strategies to obtain excellent catalyst for cyclohexane oxidation.