Microscopic Mechanism Research Articles

Experimental and mechanistic investigation on the plastic anisotropic deformation behavior of α-phase titanium alloy Ti-2Al-2.5Zr

Ti-2Al-2.5Zr is widely used in piping and structural support applications, however, the rolling forming process results in anisotropic deformation during service. This behavior has implications for the manufacturing processes and structural safety assessments in engineering applications. In this study, the plastic anisotropic deformation behavior of a rolled Ti-2Al-2.5Zr plate was investigated using uniaxial tensile tests along the transverse, normal, and 45° directions. Acoustic emission, electron backscatter diffraction, and scanning electron microscopy methods were used to investigate dislocation slip and twinning mechanisms. The results indicated that different microscopic deformation mechanisms caused the significant macroscopic anisotropy of Ti-2Al-2.5Zr. The primary mechanisms involved were prismatic <a> slip, pyramidal <c+a> slip, and {10-12} extension twinning. The stress direction determined the influence of each of these mechanisms during the yielding and plastic deformation phases. Application of the visco-plastic self-consistent model established the relationship between the macroscopic mechanical responses and microscopic deformation mechanisms. It was revealed that Ti-2Al-2.5Zr achieved its optimum strength when the initial texture aligned most of the grain c-axis at angles ranging from 30° to 50° relative to the deformation direction. This finding provides a direction for the texture design of Ti-2Al-2.5Zr in engineering materials.

Molecular insight into the enhanced oil recovery potential of a seawater-based zwitterionic/anionic surfactant compound for heavy oil reservoirs

Zwitterionic/anionic surfactant mixtures can produce many synergistic effects that benefit heavy oil production. In this work, a seawater-based zwitterionic/anionic surfactant compound was prepared using cocoamidopropyl betaine (CAB) and alkyl polyoxyethylene ether sodium sulfate (AES), emphasizing their synergistic effects in enhancing conventional heavy oil recovery. First, the emulsification capability and the oil displacement efficiency of the surfactant compound were tested through laboratory experiments. Then the impacts of salinity, cation types, surfactant formulation and solution pH on surfactant-surfactant or surfactant-heavy oil interactions were systematically explored through molecular dynamics simulations to unveil the underlying mechanisms of enhanced oil recovery. The results showed that, (1) in a seawater-based system, when the AES/CAB concentration ratio was 1:1, a large wormlike micelle was formed due to the cation bridging of Ca2+ and Mg2+ ions, which not only strengthened the attractive interactions between the AES-SO4− and the CAB-N+ functional groups, but also screened the repulsive interactions between the AES-SO4− and the CAB-COO− functional groups. (2) Through mixed adsorption, the arrangement of AES/CAB molecules at the aqueous/heavy oil interface was more compact. (3) By incorporating the AES/CAB mixture into the associative structures of asphaltene and resins, it could effectively weaken the attraction interactions between the asphaltenes and the resins. Through these synergies, an additional oil recovery of 24.93 % was yielded by combining AES/CAB flooding and subsequent seawater flooding, compared to 19.38 % in the pure AES case. This study provides important insights into the microscopic mechanisms of zwitterionic/anionic surfactant mixtures, which can facilitate the effective development of heavy oil reservoirs and guide the complex formulation of cost-effective surfactant compounds.

Phase-Field Model of Electronic Antidoping.

Charge carrier doping usually reduces the resistance of a semiconductor or insulator, but was recently found to dramatically enhance the resistance in certain series of materials. This remarkable antidoping effect has been leveraged to realize synaptic memory trees in nanoscale hydrogenated perovskite nickelates, opening a new direction for neuromorphic computing. To understand these phenomena, we formulate a physical phase-field model of the antidoping effect based on its microscopic mechanism and simulate the voltage-driven resistance change in the prototypical system of hydrogenated perovskite nickelates. Remarkably, the simulations using this model, containing only one adjustable parameter whose magnitude is justified by first-principles calculations, quantitatively reproduce the experimentally observed treelike resistance states, which are shown unambiguously to arise from proton redistribution-induced local band gap enhancement and carrier blockage. Our work lays the foundation for modeling the antidoping phenomenon in strongly correlated materials at the mesoscale, which can provide guidance to the design of novel antidoping-physics-based devices.

Research Progress on Ti3C2Tx-Based Composite Materials in Antibacterial Field.

The integration of two-dimensional Ti3C2Tx nanosheets and other materials offers broader application options in the antibacterial field. Ti3C2Tx-based composites demonstrate synergistic physical, chemical, and photodynamic antibacterial activity. In this review, we aim to explore the potential of Ti3C2Tx-based composites in the fabrication of an antibiotic-free antibacterial agent with a focus on their systematic classification, manufacturing technology, and application potential. We investigate various components of Ti3C2Tx-based composites, such as metals, metal oxides, metal sulfides, organic frameworks, photosensitizers, etc. We also summarize the fabrication techniques used for preparing Ti3C2Tx-based composites, including solution mixing, chemical synthesis, layer-by-layer self-assembly, electrostatic assembly, and three-dimensional (3D) printing. The most recent developments in antibacterial application are also thoroughly discussed, with special attention to the medical, water treatment, food preservation, flexible textile, and industrial sectors. Ultimately, the future directions and opportunities are delineated, underscoring the focus of further research, such as elucidating microscopic mechanisms, achieving a balance between biocompatibility and antibacterial efficiency, and investigating effective, eco-friendly synthesis techniques combined with intelligent technology. A survey of the literature provides a comprehensive overview of the state-of-the-art developments in Ti3C2Tx-based composites and their potential applications in various fields. This comprehensive review covers the variety, preparation methods, and applications of Ti3C2Tx-based composites, drawing upon a total of 171 English-language references. Notably, 155 of these references are from the past five years, indicating significant recent progress and interest in this research area.

Reconstructing higher-order interactions in coupled dynamical systems

Higher-order interactions play a key role for the operation and function of a complex system. However, how to identify them is still an open problem. Here, we propose a method to fully reconstruct the structural connectivity of a system of coupled dynamical units, identifying both pairwise and higher-order interactions from the system time evolution. Our method works for any dynamics, and allows the reconstruction of both hypergraphs and simplicial complexes, either undirected or directed, unweighted or weighted. With two concrete applications, we show how the method can help understanding the complexity of bacterial systems, or the microscopic mechanisms of interaction underlying coupled chaotic oscillators.

Quantum Dynamics Studies of the Li + Na2 (V = 0, j = 0) → Na + NaLi Reaction on a New Neural Network Potential Energy Surface.

The ultracold reaction offers a unique opportunity to elucidate the intricate microscopic mechanism of chemical reactions, and the Na2Li system serves as a pivotal reaction system in the investigation of ultracold reactions. In this work, a high-precision potential energy surface (PES) of the Na2Li system is constructed based on high-level ab initio energy points and the neural network (NN) method, and a proper asymptotic functional form is adopted for the long-range interaction, which is suitable for the study of cold or ultracold collisions. Based on the new NN PES, the dynamics of the Li + Na2 (v = 0, j = 0) → Na + NaLi reaction are studied in the collision energy range of 10-7 to 80 cm-1. In the high collision energy range of 8 to 80 cm-1, the dynamics of the reaction is studied using the time-dependent wave packet method and the statistical quantum mechanical (SQM) method. Comparing the results of the two methods, it is found that the SQM method provides a rough description of the product ro-vibrational state distribution but overestimates the integral cross-section values. With the decrease of collision energy, the reaction differential cross section gradually changes from forward-backward symmetric scattering to predominant forward scattering. In the low collision energy range from 10-7 to 8 cm-1, the SQM method is used to study the reaction dynamics, and the rate constant in the Wigner threshold region is estimated to be 2.87 × 10-10 cm3/s.

Simulations on coal water slurry gasification by molecular dynamics method with ReaxFF.

Coal water slurry (CWS) is a new type of liquid coal product with low pollution, which is mainly used in the chemical industry to produce syngas (CO + H2). It is of great significance to study the microscopic mechanism of CWS gasification reaction for improving the efficiency of coal gasification. In this paper, the method of molecular dynamics based on reaction force fields (ReaxFF-MD) is used to study the gasification process of CWS/O2 system at different temperatures. The results show that, in the range of 1600-2400 K, the macromolecular network structure of lignite is decomposed into a large number of small molecular structures and a small number of light tar free radical fragments, and the types and quantities of reaction products increased rapidly. At 2400-4000 K, the free radical fragments of light tar are further decomposed and reacted with gasification agents, but the types and quantities of reaction products have little change. At 3600 K, a full gasification reaction occurred in the system, and the content of syngas is the highest. The model was established and optimized by Materials Studio (MS) software. Based on ReaxFF-MD method, Lammps software was used to simulate the gasification process of CWS/O2 system, and the reaction force field files containing C, H, O, N, and S element were used. By calculating the activation energy of gasification reaction, the rationality of the model and calculation method was illustrated. The post-processing of the results was implemented using OVITO, ChemDraw software, and self-programmed Python scripts.

Microscopic Mechanism and Road Performance Analysis of MgO Carbonation–Solidification of Dredged Sediment

MgO carbonization is a green and low-carbon soil improvement technology. The use of MgO carbonization to solidify dredged sediment and transform it into road-building materials has significant environmental sustainability advantages. A series of microscopic characterization tests, including X-ray Diffraction (XRD), Scanning Electron Microscope–Energy Dispersive Spectrometer (SEM-EDS), and Mercury-in-Pressure (MIP) tests, were conducted to elucidate the evolution characteristics of mineral composition, microscopic morphology, and pore structure of sediment under carbonation. Based on the results, the mechanism of MgO carbonation–solidification of dredged sediment was explored. In order to verify the improvement of carbonation on the road performance of sediment, comparative tests were carried out on sediment, non-carbonated sediment, and carbonated sediment. The results indicate a significant improvement in the solidification of MgO-treated sediment through carbonation, with enhanced macroscopic strength and densified microscopic structure. This can be attributed to the encapsulation, cementation, and pore-filling effects of the hydration products and carbonation products of MgO on soil particles. The rebound modulus and splitting strength of carbonated sediment were 3.53 times and 2.16 times that of non-carbonated sediment, respectively. Additionally, the carbonated sediment showed improved saturated stability, resistance to salt solution wet–dry cycles, and resistance to freeze–thaw cycles.

Experimental study on the engineering properties and failure mechanism of moraine in Southeast Tibet under freeze–thaw cycles conditions

The effect of freeze–thaw cycles (FTCs) is a prevalent hydrothermal phenomenon in seasonal permafrost regions, significantly affecting the micro and engineering properties of moraine. This study investigates the engineering properties and failure mechanisms of moraine induced by FTCs, using samples with varying dry densities subjected to 0–20 FTCs. The permeability characteristics, particle breakage characteristics, elastic modulus, stress–strain curve, excess pore water pressure, peak friction angle, and critical state line characteristics of the moraine were analyzed before and after the FTCs, and the microscopic failure mechanism of moraine induced by FTCs was revealed. The test results show a degradation in the engineering properties of moraine induced by FTCs, exhibiting the greater the dry density the more obvious the damage to the engineering properties of the moraine. In addition, the particle fragmentation and fine particle aggregation caused by the FTCs changed the distribution, shape, arrangement, and particle intercontact patterns, which revealed the failure mechanism of moraine induced by FTCs. The correlation analysis between the shear strength index and microstructural parameters demonstrated that the particle arrangement has the greatest effect on the peak friction angle and particle shape has the greatest effect on the critical state line of moraine under the FTCs conditions. The findings offer experimental evidence and theoretical support for preventing and resolving geological risks and engineering project problems resulting from the deterioration of moraine shear strength during FTCs in the alpine mountain region.

A self-assembled surfactant for efficient flotation of cassiterite: Experimental study and DFT calculation

Surfactants of different kinds are important in the flotation of metal oxide ores. In this paper, a combined organic surfactant was formed through self-assembly of salicylhydroxamic acid (SHA) and isopropanolamine dodecylbenzenesulfonate (DBIA). The effects of SHA and DBIA on the flotation behavior of cassiterite were investigated. Density functional theory (DFT) calculations were used to clarify the microscopic adsorption mechanism of SHA and DBIA on the cassiterite surface. The flotation performance of the combined surfactant was investigated to determine the optimum ratio. Subsequently, the self-assembly behavior of the surfactants in aqueous solutions was examined using surface tension tests and molecular dynamics simulations. Flotation experiments and zeta potential, X-ray photoelectron spectroscopy (XPS), atomic force microscope (AFM), contact angle, and adsorption capacity analyses were used to explore the flotation behavior and adsorption mechanism at the solid–liquid–gas boundary. The maximum flotation recovery of cassiterite were 45.73 % and 71.25 % when SHA and DBIA were used alone. By contrast, with the developed combined surfactant, the flotation recovery at the same reagent concentration was 84.92 %. The SHA/DBIA surfactant co-adsorbed at the aqueous solution interface, which decreased the surface tension of the solution to 4.943 × 10−4 mol/L and resulted in formation of a stable foam layer. These effects altered the surface properties of cassiterite and enhanced its surface hydrophobicity. Overall, this study provides valuable mechanistic insights into the enhanced chelation complexation of self-assembled surface collectors with metal oxides.

Effect of nanosilica on the hydrological properties of loess and the microscopic mechanism

Loess areas, such as the Loess Plateau, are characterized by a fragile ecological environment, high soil erosion, and frequent geological disasters due to the unique hydrological properties of loess (e.g., collapsibility and permeability). Therefore, the loess must be stabilized for use in engineering construction. Traditional stabilizers (lime, cement, and fly ash) cause environmental problems, such as soil salinization and greenhouse gas emissions. Therefore, this study investigated the effect of nanosilica on the hydrological properties of loess and the microscopic mechanism. Different nanosilica contents (0.2%, 0.4%, 0.8%, 1%, and 3%) were added to loess sample, and the particle size distribution, Atterberg limits, collapsibility, and soil water characteristics were analyzed. The results revealed the following. The addition of nanosilica changed the particle size distribution, liquid limit, plastic limit, and plasticity index of loess. After the addition of nanosilica with different contents, the loess collapsibility coefficient curve shifted downward, the soil water retention curve shifted upward, and the unsaturated permeability coefficient curve shifted downward. The pores between particles were filled, and the number of large and medium pores and the pore connectivity were lower after the nanosilica addition. The surface of the coarse particles adsorbed more fine particles, and a large number of micro-aggregates or clay aggregates were present in the pores between particles. In conclusion, the environmentally friendly material nanosilica can be used to improve the hydrological properties of loess, which is applicable to alleviating soil erosion and preventing geological disasters on the Loess Plateau.

The influence of blast furnace slag on the mechanical properties and mesoscopic damage mechanisms of recycled aggregate concrete compared to natural aggregate concrete at different ages

To improve the mechanical property defects caused by recycled aggregate (RCA) in recycled aggregate concrete (RAC) as well as the effect of blast furnace slag (BFS) addition on the mechanical properties and microscopic damage mechanisms of natural aggregate concrete (NAC) and RAC at long ages. In this paper, the effects of different curing ages (T = 7d, 14d, 28d, 56d, 90d, and 150d) and blast furnace slag contents on the mechanical properties and microscopic damage mechanisms under uniaxial compression of NAC and RAC were investigated, where the cement substitution rate of BFS was 0 % and 35 % (water-cement ratio of 0.46, water-reducing agent dosage of 0.25 %), respectively. Nuclear magnetic resonance (NMR) and scanning electron microscopy (SEM) were used to study the internal pore changes and the generation of hydration products in the specimens, and acoustic emission (AE) showed the microcrack development process. The results showed that the peak stress and modulus of elasticity of the specimens gradually increased with increasing age, the peak strain gradually decreased, and the internal porosity gradually decreased. It is worth noting that the addition of BFS caused the mechanical properties of RAC to decrease at 28 days but enhanced the mechanical properties of RAC at 56–120 days. This was attributed to the fact that the properties of BFS were not yet activated in the early stage, whereas it was activated in the later stage under an alkaline environment and reacted with CH to generate more C–S–H hydration products, which enhanced the interfacial transition zone and reduced the porosity. This highlights the potential of BFS to improve the performance of RCA over long periods of time. In contrast, BFS improved the mechanical properties of NAC throughout the age period and more significantly after 56 days. AE results showed that the peak ring counts lagged behind the peak stresses. Finally, combined with the statistical damage principal model, the fitting was performed by Matlab to analyze the microscopic damage mechanism of the specimen during uniaxial compression. It was found that the changes in the four characteristic parameters (εa, εb, εh and H) followed a certain regularity, reflecting the regular changes in fracture damage and yield damage. This revealed the intrinsic linkage between mesoscopic damage mechanisms and macroscopic mechanical properties. It was demonstrated that it was feasible to speculate on the law of the stress-strain curve at the macroscopic level by using the law of change of the four parameters (εa, εb, εh and H) at the microscopic level.

New pairing mechanism via chiral electron–hole condensation for non-BCS superconductivity

A novel chiral electron–hole (CEH) pairing mechanism is proposed to account for non-BCS superconductivity. In contrast to BCS Cooper pairs, CEH pairs exhibit a pronounced affinity to antiferromagnetism for superconductivity. The gap equations derived from this new microscopic mechanism are analyzed for both s- and d-wave superconductivity, revealing marked departures from the BCS theory. Unsurprisingly, CEH naturally describes superconductivity in strongly-correlated systems, necessitating an exceedingly large coupling parameter (λ>1 for s-wave and λ>π/2 for d-wave) to be efficacious. The new mechanism provides a better understanding of various non-BCS features, especially in cuprate and iron-based superconductors. In particular, CEH, through quantitative comparison with experimental data, shows promise in solving long-standing puzzles such as the unexpectedly large gap-to-critical-temperature ratio Δ0/Tc, the lack of gap closure at Tc, superconducting phase diagrams, and a non-zero heat-capacity-to-temperature ratio C/T at T=0 (i.e., the “anomalous linear term”), along with its quadratic behavior near T=0 for d-wave cuprates.

Effect of Surface Reinforcer on Compressive Strength and Microscopic Mechanism of Freeze–Thaw-Deteriorated Concrete

Due to the deterioration caused by repeated freeze–thaw cycles, concrete materials in cold regions often develop cracks, which have serious effects and challenge the durability of concrete-based structures. Therefore, it is worthwhile to repair and strengthen freeze–thaw-damaged concrete to extend the service duration of the structure. In the present study, to investigate the restorative effect of surface reinforcer on freeze–thaw-deteriorated concrete specimens, the effects of the surface reinforcer type, its action duration, and the number of applications on the strength and deformation parameters of repaired specimens were systematically studied. Moreover, pore size distribution, pore structure at different depths, and the micromorphology characteristics were investigated by nuclear magnetic resonance (NMR), pore structure, and scanning electron microscope (SEM) tests to reveal the repair mechanism of different surface reinforcer types. The results indicated that the compressive strength of freeze–thaw-deteriorated concrete could be increased by up to 15.67% after the application of the surface reinforcer. Both the values of compressive strength and deformation modulus E50 increased with the increase in the action duration. In addition, the surface reinforcer could efficiently penetrate the interior of the deteriorated specimen and was able to decrease the total proportion of multi-harmful pores and harmful pores. Furthermore, the pore structure parameters could be significantly improved at a depth of 10 mm; however, the reparative effect of the surface reinforcer gradually decreased with the increase in the action depth. The surface reinforcer could efficiently promote the second hydration of cement and generate more cementitious materials to fill the microvoids, thereby improving the compactness and mechanical properties of the repaired specimens.

Deep learning-based acoustic emission data clustering for crack evaluation of welded joints in field bridges

To advance the intelligent operation and maintenance of bridges, a deep learning-based acoustic emission (AE) data clustering framework was developed for evaluating fatigue cracks in welded joints under conditions of operational noise interference and complex damage mechanisms. Specifically, a convolutional autoencoder (CAE) model was implemented to extract damage-sensitive features from AE wavelet images. Additionally, a physics-guided single-and-cross-case strategy using Gaussian mixture models (GMMs) was presented to diagnose overlapping microscopic noise and damage mechanisms across different cases with various crack lengths. Field tests demonstrated the efficiency of the proposed framework to distinguish AE data induced by noise, crack propagation, surface fretting, and impact, enabling accurate identification of no-damage, minor-damage, and serious-damage cases according to their characteristic mechanisms. Future work will incorporate long-term monitoring data from additional cases to further refine the damage quantification and enhance the overall robustness.

Enhanced solar-driven photoelectrochemical water splitting of H/N co-doped TiO2: Role of defect states in a band gap reduction and promotion of charge transfer

Photoelectrodes based on reduced TiO2 are being extensively studied in the search for photocatalytic materials that can perform solar-driven water splitting and renewable hydrogen production. To date, substantial efforts have been devoted to understanding the microscopic mechanisms that underlie their photoelectrochemical (PEC) behavior, but this is a critical missing input to the Ti 3d carriers that govern the PEC activity. In this study the single and co-doping (N, H) in anatase TiO2 are prepared for PEC hydrogen production. The codoped photocathode delivers much better PEC performance from the enhanced solar light response and a fast electron pathway. Soft x-ray spectroscopy including x-ray absorption (XAS) and photoelectron spectroscopy (XPS) has been used to investigate the location and occupation of the defect levels from doping, through which the relevant engineered electronic properties in doped TiO2 are determined. It is shown that co-doping effectively produce the substitutional nitrogen in comparison with single doping. The Ti3+ defect states promoted by doping introduces localized Ti 3d-derived states below Fermi level (EF), resulting in a large reduction (approximately 1 eV) in the band gap of co-doped TiO2. The progressive production of oxygen vacancies eventually causes a surface band upward-bending induced electron transfer mechanism critical for charge separation. The present insights into defect chemistry and its determination to the electronic structure of co-doped TiO2 provide important guidance for using TiO2 in electrocatalysis and optoelectronics.

Dynamic mode decomposition of nonequilibrium electron-phonon dynamics: accelerating the first-principles real-time Boltzmann equation

Nonequilibrium dynamics governed by electron–phonon (e-ph) interactions plays a key role in electronic devices and spectroscopies and is central to understanding electronic excitations in materials. The real-time Boltzmann transport equation (rt-BTE) with collision processes computed from first principles can describe the coupled dynamics of electrons and atomic vibrations (phonons). Yet, a bottleneck of these simulations is the calculation of e–ph scattering integrals on dense momentum grids at each time step. Here we show a data-driven approach based on dynamic mode decomposition (DMD) that can accelerate the time propagation of the rt-BTE and identify dominant electronic processes. We apply this approach to two case studies, high-field charge transport and ultrafast excited electron relaxation. In both cases, simulating only a short time window of ~10% of the dynamics suffices to predict the dynamics from initial excitation to steady state using DMD extrapolation. Analysis of the momentum-space modes extracted from DMD sheds light on the microscopic mechanisms governing electron relaxation to a steady state or equilibrium. The combination of accuracy and efficiency makes our DMD-based method a valuable tool for investigating ultrafast dynamics in a wide range of materials.

Emergent normal fluid in the superconducting ground state of overdoped cuprates

The microscopic mechanism for the disappearance of superconductivity in overdoped cuprates is still under heated debate. Here we use scanning tunneling spectroscopy to investigate the evolution of quasiparticle interference phenomenon in Bi2Sr2CuO6+δ over a wide range of hole densities. We find that when the system enters the overdoped regime, a peculiar quasiparticle interference wavevector with arc-like pattern starts to emerge even at zero bias, and its intensity grows with increasing doping level. Its energy dispersion is incompatible with the octet model for d-wave superconductivity, but is highly consistent with the scattering interference of gapless normal carriers. The gapless quasiparticles are mainly located near the antinodes and are independent of temperature, consistent with the disorder scattering mechanism. We propose that a branch of normal fluid emerges from the pair-breaking scattering between flat antinodal bands in the quantum ground state, which is the primary cause for the reduction of superfluid density and suppression of superconductivity in overdoped cuprates.

The photodissociation dynamics and ultrafast electron diffraction image of cyclobutanone from the surface hopping dynamics simulation

The comprehension of nonadiabatic dynamics in polyatomic systems relies heavily on the simultaneous advancements in theoretical and experimental domains. The gas-phase ultrafast electron diffraction (UED) technique has attracted significant attention as a unique tool for monitoring photochemical and photophysical processes at the all-atomic level with high temporal and spatial resolutions. In this work, we simulate the UED spectra of cyclobutanone using the trajectory surface hopping method at the extended multi-state complete active space second order perturbation theory (XMS-CASPT2) level and thereby predict the results of the upcoming UED experiments in the Stanford Linear Accelerator Laboratory. The simulated results demonstrate that a few pathways, including the C2 and C3 dissociation channels, as well as the ring opening channel, play important roles in the nonadiabatic reactions of cyclobutanone. We demonstrate that the simulated UED signal can be directly interpreted in terms of atomic motions, which provides a unique way of monitoring the evolution of the molecular structure in real time. Our work not only provides numerical data that help to determine the accuracy of the well-known surface hopping dynamics at the high XMS-CASPT2 electronic-structure level but also facilitates the understanding of the microscopic mechanisms of the photoinduced reactions in cyclobutanone.

Mechanistic investigation of ammonia adsorption and reforming over Ni, Ru loaded catalysts toward green H2 production of marine engines: DFT calculation and experimental evaluation

Highly active catalysts suitable for ammonia reforming reactions have been comprehensively investigated by density functional theory (DFT) calculations and experimental tests. Non-precious metal Ni, precious metal Ru and Ru-Ni composite metal are selected as catalytic activity surfaces, and a series of three-dimensional metal-packed catalyst models are constructed parallelly. Then, to elucidate the rate-determining step of reforming reaction, in-depth analysis of microscopic reaction mechanisms for amino groups (including H and NHx, x=0–3) adsorption, dissociation, recombination and desorption are carried out by simulation parameters and experimental data. The results indicate that NH3 exhibits highly stable adsorption configurations (Bridge site) on both Ni, Ru-based catalyst surfaces, with the adsorption position having a relatively minor effect on adsorption energy. It is worth noting that Ni-based catalyst exhibits better adsorption behaviors towards NH3 compared to Ru. Whereas, during stepwise dehydrogenation of NH3 and subsequent N2 and H2 recombination and desorption processes, the reaction energy barriers confirm experimental observations of higher activity displayed by Ru-based catalyst in low-temperature range of 400–500 °C. Interestingly, N2 synthesis behavior of innovative Ru-Ni bimetallic tandem catalyst surface possesses the lowest reaction energy barrier than other models, which is attributed to the adsorption capability of Ni layers and the catalytic activity of Ru atoms. The experimental results also demonstrate that under typical engine exhaust conditions, the H2 production efficiency of 1 %Ru-3 %Ni/Al2O3 surpasses that of 1 %Ru/Al2O3 by 6.2 %, showcasing exceptional stability.