Breaking Energy Research Articles

Trimetallic Alloys as an Electrocatalyst for Fuel Cells: The Case of Methyl Formate on Pt3Pd3Sn2.

The shift toward renewable energy sources plays a central role in the quest for a circular economy. In this context, methyl formate (MF) has garnered attention as a compelling hydrogen carrier and alternative fuel, because of its remarkable characteristics (energy density, ease of storage and transport, and low boiling point). In this study, DFT calculations supported by online electrochemical mass spectroscopy (OE-MS) were performed to investigate the MF electro-oxidation (MFEO) on Pt3Pd3Sn2 (111). The DFT calculations provide insight into the role of Pt, Pd, and Sn atoms in MFEO. Pt and Pd together provide a preferred active site for initiating MFEO through the O-H bond scission, and Sn plays an essential role in the mitigation of CO through oxygenation or water activation. By comparing the reaction energies and activation barriers for all possible reactions in MFEO, the suggested path necessitates a minimum energy of 0.14 eV to initiate the MFEO. This value was supported by the experimental results, showing that the oxidation wave of MF starts at 0.15 V (70 °C). Density functional theory (DFT) results, supported by OE-MS, indicate that the hydrolysis of MF prior to MFEO is not preferred on Pt3Pd3Sn2 (111) surfaces, although the formation of methanol is plausible via a CH3O intermediate. Among the three small organic molecules (SOMs) studied─MF, methanol, and formic acid─MF has the lowest activation energy for the initial bond breaking that starts the whole oxidation process (0.13 eV), compared to formic acid (0.45 eV) and methanol (0.61 eV); thus, MF is the preferred fuel on Pt3Pd3Sn2 (111).

Laboratory study of energy transformation characteristics in breaking wave groups

The spilling-breaking waves that appear in chirped wave packets are studied in a two-dimensional wave channel. These waves are produced by superposing waves with gradually decreasing frequencies. The analysis focuses on the nonlinear characteristics, energy variation, and energy transformation during the evolution and breaking of wave groups. Ensemble empirical mode decomposition is used to analyze the non-breaking and breaking energy variations of the intrinsic mode functions (IMFs). It is found that the third-order IMF component is a source of non-breaking energy dissipation and the second-order IMF, which represents a short wave group with a relatively higher energy content, is a primary source of the energy loss caused by wave breaking. Additionally, the findings reveal that among the three waves preceding the maximum crest, the wave closest to the maximum crest carried most of the energy. When wave breaking occurs, the energy dissipation caused by the wave breaking primarily originates from that wave. After wave breaking, whether it is the first breaker or subsequent breakers, the main energy dissipation occurs in a frequency range higher than the dominant frequency. This energy loss plays a significant role in increasing the energy of free waves. Moreover, a potential link between the number of carrier waves and wave breaking phenomena has been found. As the number of carrier waves increased, both the nonbreaking and breaking energy dissipation rates exhibited an overall increasing trend. The amount of nonbreaking energy dissipation was generally more than twice the breaking energy dissipation rate. For wave groups with more carrier waves, the modulation instability plays a significant role in generating larger waves. Furthermore, an analysis of the dominant frequency variations of the wave group before wave breaking suggests that wave breaking is not a sufficient condition for a frequency downshift in the wave spectra.

Origin of the break in the cosmic-ray electron plus positron spectrum at ∼1 TeV

Recent measurements of the cosmic-ray electron plus positron spectrum in several experiments have confirmed the presence of a break at ∼1 TeV. The origin of the break is still not clearly understood. In this work, we explored different possibilities for the origin, which include an electron source spectrum with a broken power law, a power law with an exponential or super-exponential cutoff, and the absence of potential nearby cosmic-ray sources. Based on the observed electron plus positron data from the DAMPE and the H.E.S.S experiments, and considering supernova remnants as the main sources of cosmic rays in the Galaxy, we find statistical evidence in favor of the scenario with a broken power-law source spectrum, with the best-fit source parameters obtained as Γ = 2.39 for the source spectral index, E0 ≈ 1.6 TeV for the break energy, and f = 1.59 × 1048 ergs for the amount of supernova kinetic energy injected into cosmic-ray electrons. This power-law break in the spectrum has been predicted for electrons confined inside supernova remnants after acceleration via diffusive shock acceleration process, and also indicated by the multi-wavelength study of supernova remnants. All of this evidence shows that the observed spectral break provides a strong indication of a direct link between cosmic-ray electrons and their sources. Our findings further show that electrons must undergo spectral changes while escaping the source region in order to reconcile the difference between the spectral index of electrons observed inside supernova remnants and that obtained from Galactic cosmic-ray propagation studies.

Phenyl, propyl polysiloxane modified epoxy resin II: The co-continuous phase, concurrently strengthening and toughening mechanism

The applications of epoxy resins are restricted in certain areas due to their brittleness, while improving the epoxy toughness always compromises their strength. We reported a phenyl, propyl polysiloxane modified epoxy resins with excellent tensile strength and toughness before. In this study, the mechanism of strengthening and toughening are studied and elaborated. Compared to cured EP resin (EP), cured P/E resin (P/E20) significantly improved the tensile strength, elongation at break, impact strength, and critical strain energy release rate (GIc) by 45 %, 248 %, 18 %, and 512 %, respectively. Fracture analysis of the P/E20 revealed the appearance of parabolic markings, typical and convincing evidence of ductile fracture, indicating good toughness of the resin. AFM height and Young's modulus plots reveal the complex details of the dimples and the co-continuous phases, which provide the strong evidence to explain the reinforcement and toughening mechanism.

Response of Upper Ocean to Parameterized Schemes of Wave Breaking under Typhoon Condition

The study of upper ocean mixing processes, including their dynamics and thermodynamics, has been a primary focus for oceanographers and meteorologists. Wave breaking in deep water is believed to play a significant role in these processes, affecting air–sea interactions and contributing to the energy dissipation of surface waves. This, in turn, enhances the transfer of gas, heat, and mass at the ocean surface. In this paper, we use the FVCOM-SWAVE coupled wave and current model, which is based on the MY-2.5 turbulent closure model, to examine the response of upper ocean turbulent kinetic energy (TKE) and temperature to various wave breaking parametric schemes. We propose a new parametric scheme for wave breaking energy at the sea surface, which is based on the correlation between breaking wave parameter RB and whitecap coverage. The impact of this new wave breaking parametric scheme on the upper ocean under typhoon conditions is analyzed by comparing it with the original parametric scheme that is primarily influenced by wave age. The wave field simulated by SWAVE was verified using Jason-3 satellite altimeter data, confirming the effectiveness of the simulation. The simulation results for upper ocean temperature were also validated using OISST data and Argo float observational data. Our findings indicate that, under the influence of Typhoon Nanmadol, both parametric schemes can transfer the energy of sea surface wave breaking into the seawater. The new wave breaking parameter RB scheme effectively enhances turbulent mixing at the ocean surface, leading to a decrease in sea surface temperature (SST) and an increase in mixed layer depth (MLD). This further improves upon the issue of uneven mixing of seawater at the air–sea interface in the MY-2.5 turbulent closure model. However, it is important to note that wave breaking under typhoon conditions is only one aspect of wave impact on ocean disturbances. Therefore, further research is needed to fully understand the impact of waves on upper ocean mixing, including the consideration of other wave mechanisms.

Experimental investigation on high voltage electric pulse rock breaking under drilling mud conditions

High voltage electric pulse rock breaking technology is a novel and promising rock breaking technique that is environmentally friendly, efficient, and nearing industrial application. However, the drilling performance of electrode bits under varied drilling muds and the mechanism of high voltage electric pulse rock breaking remain unclear. This study entails real drilling experiments conducted on red sandstone using electrical pulse drilling (EPD) under different initial voltage peaks, electrode bits, and drilling muds to investigate the impact and mechanism of EPD. A laboratory experimental system for high voltage pulse rock breaking is established based on a 0–80 kV EPD pulse generator. Three types of electrode bits are devised, namely, petal-structural, four-point-structural, and circular-ring-structural electrode bits. The EPD experiments on red sandstone are executed under seven different drilling muds at initial peak voltages ranging from 13 to 17 kV. And the efficiency of EPD rock breaking is assessed using five quantitative indexes: rate of penetration, breaking volume, specific energy of rock breaking, and the proportion of electrical fragmentation and hydraulic-electric rock fragmentation. Furthermore, the physical parameters, i.e., density, conductivity, Zeta potential, PH, and apparent viscosity, of the seven drilling muds are measured, shedding light on the rock breaking mechanism of EPD under specific drilling mud conditions. Subsequently, the designed electrode bit is evaluated, and based on experimental phenomenon, structural optimizations of the electrode bit and EPD drilling recommendations under various drilling mud conditions in real drilling scenarios are proposed. This research is poised to offer valuable insights into the design of EPD electrode bits and the selection of drilling mud for enhancing drilling efficiency.

RSM-BASED STATISTICAL APPROACH TO ENHANCE THE COMPRESSIVE PERFORMANCE OF ABS P400 PARTS FABRICATED VIA FDM TECHNOLOGY

This research investigates the performance of ABS P400 parts under compressive loading. These ABS P400 parts are fabricated by fused deposition modeling (FDM) process using omnidirectional printing. The effects of three critical parameters, raster angle (A), air gap (B), and raster width (C), each at three different levels, were analyzed on three different performance measures, i.e. total deformation up to failure ([Formula: see text]) measured in %, maximum energy ([Formula: see text]) in MJ/m3 and break energy ([Formula: see text]) in MJ/m3. Results of experimentations were analyzed using analysis of variance (ANOVA), perturbation curve and 3D surface plots. The research established the anisotropic nature, durability and less brittleness of the FDM fabricated ABSP400 part, which leads to lower strength and also influence the energy absorbing behavior while deformation under compression. Complex relationships were exhibited between the chosen parameters and studied measures. It was also observed that [Formula: see text] is noticeable due to less brittleness of ABS P400 however, [Formula: see text] and [Formula: see text] vary in a contradictory fashion with changes in process parameters. The models were validated using normality plots. Multi-objective optimization was done using the desirability approach to determine the optimal combination of FDM process parameters for optimum responses. The desirability result showed that the optimized input parameter is [Formula: see text][Formula: see text]mm, and [Formula: see text][Formula: see text]mm which yield maximized optimum responses as [Formula: see text]%, [Formula: see text][Formula: see text]MJ/m3, and [Formula: see text][Formula: see text]MJ/m3. The work not only reflects the effect of three FDM parameters on the total deformation up to failure ([Formula: see text] in %) but, in addition, energy absorption behavior of FDM parts under compression is also investigated. The study on the behavior of energy at ultimate stress or ultimate load and breaking stress or breaking load were rarely investigated in earlier research which reflects the novelty of our research.

Mechanical Assessment of Denture Polymers Processing Technologies.

Removable prostheses have seen a fundamental change recently because of advances in polymer materials, allowing improved durability and performance. Despite these advancements, notable differences still occur amongst various polymer materials and processing technologies, requiring a thorough grasp of their mechanical, physical, and therapeutic implications. The compressive strength of dentures manufactured using various technologies will be investigated. Traditional, injection molding, and additive and subtractive CAD/CAM processing techniques, all utilizing Polymethyl methacrylate (PMMA) as the main material, were used to construct complete dentures. The specimens underwent a compressive mechanical test, which reveals the differences in compressive strength. All the specimens broke under the influence of a certain force, rather than yielding through flow, as is characteristic for plastic materials. For each specimen, the maximum force (N) was recorded, as well as the breaking energy. The mean force required to break the dentures for each processing technology is as follows: 4.54 kN for traditional packing-press technique, 17.92 kN for the injection molding technique, 1.51 kN for the additive CAD/CAM dentures, and 5.9 kN for the subtractive CAD/CAM dentures. The best results were obtained in the case of the thermoplastic injection system and the worst results were recorded in the case of 3D printed samples. Another important aspect depicted is the standard deviation for each group, which reveal a relatively unstable property for the thermoplastic injected dentures. Good results here in terms of absolute property and stability of the property can be conferred to CAD/CAM milled group.

Concurrent Particle Acceleration and Pitch-angle Anisotropy Driven by Magnetic Reconnection: Ion-electron Plasmas

Particle acceleration and pitch-angle anisotropy resulting from magnetic reconnection are investigated in highly magnetized ion-electron plasmas. By means of fully kinetic particle-in-cell simulations, we demonstrate that magnetic reconnection generates anisotropic particle distributions fs∣cosα∣,ε , characterized by broken power laws in the particle energy spectrum f s (ε) ∝ ε −p and pitch angle 〈sin2α〉∝εm . The characteristics of these distributions are determined by the relative strengths of the magnetic field’s guide and reconnecting components (B g /B 0) and the plasma magnetization (σ 0). Below the injection break energy ε 0, ion and electron energy spectra are extremely hard (p < ≲ 1) for any B g /B 0 and σ 0 ≳ 1, while above ε 0 the spectral index steepens (p > ≳ 2), displaying high sensitivity to both B g /B 0 and σ 0. The pitch angle displays power-law ranges with negative slopes (m <) below and positive slopes (m >) above εminα , steepening with increasing B g /B 0 and σ 0. The ratio B g /B 0 regulates the redistribution of magnetic energy between ions (ΔE i ) and electrons (ΔE e ), with ΔE i ≫ ΔE e for B g /B 0 ≪ 1, ΔE i ∼ ΔE e for B g /B 0 ∼ 1, and ΔE i ≪ ΔE e for B g /B 0 ≫ 1, with ΔE i /ΔE e approaching unity when σ 0 ≫ 1. The anisotropic distribution of accelerated particles results in an optically thin synchrotron power spectrum F ν (ν) ∝ ν (2−2p+m)/(4+m) and a linear polarization degree Πlin = (p + 1)/(p + 7/3 + m/3) for a uniform magnetic field. Pitch-angle anisotropy also induces temperature anisotropy and eases synchrotron cooling, along with producing beamed radiation aligned with the magnetic field, which is potentially responsible for rapid frequency-dependent variability.

Evolution of High-energy Electron Distribution in Pulsar Wind Nebulae

In this paper, we analyze the spectral energy distributions of 17 powerful (with a spin-down luminosity greater than 1035 erg s−1) young (with an age less than 15,000 yr) pulsar wind nebulae (PWNe) using a simple time-independent one-zone emission model. Our aim is to investigate correlations between model parameters and the ages of the corresponding PWNe, thereby revealing the evolution of high-energy electron distributions within PWNe. Our findings are as follows: (1) The electron distributions in PWNe can be characterized by a double power-law with a super-exponential cutoff. (2) As PWNe evolve, the high-energy end of the electron distribution spectrum becomes harder with the index decreasing from approximately 3.5 to 2.5, while the low-energy end spectrum index remains constant near 1.5. (3) There is no apparent correlation between the break energy or cutoff energy and the age of PWNe. (4) The average magnetic field within PWNe decreases with age, leading to a positive correlation between the energy loss timescale of electrons at the break energy or the high-energy cutoff, and the age of the PWN. (5) The total electron energy within PWNe remains constant near 2 × 1048 erg, while the total magnetic energy decreases with age.

Solar Eruptive Phenomena Associated with Solar Energetic Electron Spectral Types

The energy spectral shape of solar energetic electron events carries important information on the energetic electron source/acceleration at the Sun. We investigate the association of six newly identified solar energetic electron spectral types with solar eruptive phenomena, including the downward double-power-law (DDPL) spectrum with break energy E B above 20 keV (DDPL EB≥20keV ), DDPL with E B below 20 keV (DDPL EB<20keV ), upward double-power law (UDPL), single-power-law (SPL), Ellision–Ramaty–like (ER), and logarithmic-parabola (LP). We find that the SPL type shows (the other five types show) an association with hard X-ray flares of ∼38% (∼55%–82%) and an association with west-limb coronal mass ejections (CMEs) of ∼76% (∼85%–93%). Among the other five types, the DDPL EB<20keV and ER (LP and DDPL EB≥20keV ) types only have an association with type II radio bursts of ∼7%–8% (∼16%–20%) and an association with halo CMEs of ∼5%–9% (∼11%–21%); however, the UDPL type exhibits a significant (∼47% and ∼50%) association with type II bursts and halo CMEs, with a significantly faster median CME speed of 1000−120+550 km s−1. For DDPL EB≥20keV (DDPL EB<20keV ) with a positive (no) correlation between spectral indexes and no (a positive) correlation between the spectral index and break energy, the spectrum appears to be flatter as the associated CME (flare) becomes faster (stronger). These results suggest that the SPL type can result from the initial acceleration process that likely occurs high in the corona, and then provide seed populations for further acceleration processes to form the other five types: the DDPL EB<20keV and ER types via flare-related processes, the LP and DDPL EB≥20keV types via CME-related processes, and the UDPL type via CME-driven shocks.

Examples of dynamic test procedures for steel fibre reinforced concrete

Abstract The aim of this work is to present some examples of experimental tests, which can be usefull for characterizing the resistance to failure of special steel fibre reinforced concrete – SFRC, intended especially for security use in the framework of ballistic and explosion protection. The first type of the tests was the strain gauge - based characterization of the dynamic response of the SFRC concrete block under ballistic loading. The tests were aimed at measuring the deformation response of a concrete specimen of 500 x 500 x 105 mm in dimensions upon the impact of a projectile. The tests were used to support the development and verification of numerical simulation models. For numerical simulations 3D models of individual projectiles were developed. Four T-type strain gauges were glued according to the geometric scheme on the opposite side of a specimen, i.e. on the side behind the impact of the projectile, and they measured the deflection of the plate after the impact of the projectile. The strain response records obtained from the strain gauges were subsequently used for numerical analyses by the use of the LS-DYNA software. The average maximum deflection of the plate at the impact of the projectile was characterized by the strain 400 µm/m. The second type of the tests was concerned with the method of measuring the quasi-dynamic tensile strength of special concrete specimens using an instrumented Charpy tester. The results compare both the breaking energy and the maximum force achieved for hobby concrete (HB) and hobby concrete with wires (HBD) specimens. These were pilot tests to develop the most suitable testing method. For the HB and HBD specimens the maximum force in the tests was found to be 55 N vs. 600 N, and the breaking energy to be 0.4 J vs. 1.3 J.

The Frequency Characteristics of Vibration Events in an Underground Coal Mine and Their Implications on Rock Burst Monitoring and Prevention

The main frequency of microseismic signals has recently been identified as a dominant indicator for characterizing vibration events because it reflects the energy level of these events. Frequency information directly determines whether effective signals can be collected, which has a significant impact on the accuracy of predicting rock burst disasters. In this study, we adopted a characterizing method and developed a monitoring system for capturing rock failure events at various strata in an underground coal mine. Based on the rock break mechanism and energy release level, three types of rock failure events, namely, high roof breaking, low roof breaking, and coal fracture events, were evaluated separately using specific sensors and monitoring systems to optimize the monitoring accuracy and reduce the general cost. The captured vibration signals were processed and statistically analyzed to characterize the main frequency features for different rock failure events. It was found that the main frequency distribution ranges of low roof breaking, high roof breaking, and coal fracture events are 20–400 Hz, 1–180 Hz, and 1–800 Hz, respectively. Therefore, these frequency ranges are proposed to monitor different vibration events to improve detection accuracy and reduce the test and analysis times. The failure mechanism in a high roof is quite different from that of low roof failure and coal fracturing, with the main frequency and amplitude clustering in a limited zone close to the origin. Coal fracturing and lower roof failure show a synergistic effect both in the maximum amplitude and main frequency, which could be an indicator to distinguish failure locations in the vertical direction. This result can support the selection and optimization of the measurement range and main frequency parameters of microseismic monitoring systems. This study also discussed the distribution law of the maximum amplitude and main frequency of different events and the variation in test values with the measurement distance, which are of great significance in expanding the application of optimized microseismic monitoring systems for rock burst monitoring and prevention.

DC circuit breaker: A topology with regenerative current breaking capability for DC microgrid applications

The modern DC grid is predominantly inductive due to several factors, including line inductance, and the use of current-limiting inductors to control fault current rising rates. These network inductances store a significant amount of energy during regular operation, which is either dissipated or freewheeled to ensure safe current breaking. This research article proposed a highly efficient bidirectional DC circuit breaker topology that not only provides safe current breaking but also effectively recovers the post-current breaking energy from the network’s inductance instead of dissipation. An extensive simulation investigation is performed in PSIM software to test the breaker capability for a 400V/400A DC system and the laboratory-scale 48V/1A experimental setup has been developed and employed for further validation purposes.

Optimizing cutter wear in TBM operations through numerical analysis of enhanced rock-cutting interaction

The inevitable wear and degradation of disc cutters during the rock-crushing process significantly impacts the efficacy, timeline, and cost-effectiveness of tunnel construction. Optimizing cutter arrangements and adjusting suitable excavation parameters are crucial to reducing cutter wear in Tunnel Boring Machine (TBM) operations. This study probes the interaction between disc cutters and rock, employing an enhanced Bonding model to more accurately depict the failure behavior of rock specimens. Numerical simulations of the rock-breaking process using two disc cutters were conducted, focusing on highly influential excavation parameters—penetration depth (3, 5, 7, 9 mm) and cutter arrangements—tip width (14, 17, 20, 23 mm) and cutter spacing (50, 65, 80, 95, 110 mm). These simulations analyzed the impact of various factors on cutter force, wear, specific energy of rock breaking, and crushing unit rock cutter wear. The results show that increased penetration depth leads to higher cutter force and wear, with specific energy and unit wear remaining low when penetration is less than 5 mm. A larger cutter tip width incurs higher forces and wear of the first cutter, but when the tip width exceeds 20 mm, the force and wear of the second cutter will be reduced. Optimal specific energy for rock breaking and unit wear of rock volume were identified within a cutter spacing range of 80 to 95 mm. These findings can facilitate the analysis of how excavation parameters and cutter arrangements affect wear behavior, offering superior construction recommendations.

Damage prediction and improvement method based on cutting mode of circular empty hole

Based on the theory of empty hole effect of cutting blasting, the Hopkinson effect and Saint–Venant principle are integrated to establish a two-dimensional calculation model of dynamic stress evolution of the holes wall, and then the dynamic fracture mechanism and damage distribution mode of the rock mass in the cutting area under the action of longitudinal waves are predicted. The results of the calculation and numerical simulation are verified by experiments, and the results show that: The time-varying stress function of the circular cavity wall conforms to the periodic dynamic evolution of the trigonometric function, and the theoretical calculation is consistent with the simulation results. Through the calculation of the round holes cut model and the square empty hole cut model, the change of the shape of the holes in the cut area changes the failure form of the surrounding rock mass. The circular empty hole wall is affected by the stress wave to produce "interval ring" destruction, and the effect of the reflected stretch wave is inhibited. The large range of rock mass in the square empty hole wall produces tensile and shear failure, and the rock mass collapses inward under the influence of the second stage stress. Among them, the empty space utilization rate of the square empty hole model is about 8.5 times that of the circular holes model. Vibration monitoring in the center of the cutting area shows that the vibration effect of the circular empty hole is larger than that of the square empty hole, and the proportion of rock breaking energy is lower.

Stabilized Nickel-Rich oxide cathode by the confining effect of Nb lattice anchoring and epitaxial shielding layer

Ni-rich LiNixCoyMn1−x−yO2 cathodes attract growing attention for high energy density but still face great challenges in terms of cyclic lifespan and thermal stability issues. The structural degradation is primarily caused by the increased oxygen vacancy and lattice oxygen loss, especially at high temperatures. Here, we develop an anchoring-confining strategy to rivet lattice oxygen and inhibit the formation and migration of oxygen vacancy by constructing LiNbO3 & LiF epitaxial layer and Nb5+ lattice doping within LiNi0.92Co0.055Mn0.025O2 (NCM92) cathode. The optimized NCM-FN material exhibits excellent stability with retenion of 93 % after 200 cycles at 1C supassing the pristine one (68.7 %), conspicuous high-temperature capacity retention rate (81.6 % vs. 49.5 %) and superior reversible capacity of 165 mAh/g at 5C. In particular, it even possessed superior thermal safety pushing thermal runaway temperature to 223.65 °C. In-situ X-ray diffraction (XRD) result indicates that Nb5+ lattice substitution coupled with LiNbO3 & LiF epitaxial layer alleviates the irreversibility of H2-H3 phase transition, thus stabilizing the layered structure. Furthermore, the LiNbO3 & LiF epitaxial layer, as both a physical shielding layer and ionic conductive layer, protects interface structural integrity and simultaneously promotes Li+ diffusion. X-ray photoelectron spectroscopy (XPS) and electron paramagnetic resonance (EPR) results demonstrate that the formation and propagation of oxygen vacancy within NCM-FN material is significantly inhibited. DFT calculation results reveal that Nb5+ introduction can increase the formation energy of oxygen vacancies and inhibit outward migration of active oxygen Oα- (α < 2) to stabilize layer structure by tuning the breaking energy barrier of nearby metal-O bonds. This work not only demonstrates the design of advanced Ni-rich layered cathodes but also underscores the importance of stabilized lattice oxygen for advanced Ni-rich cathodes.

Dimension-Confined Growth of a Crack-Free PbS Microplate Array for Infrared Image Sensing.

Epitaxy of semiconductors is a necessary step toward the development of electronic devices such as lasers, detectors, transistors, and solar cells. However, the lattice ordering of semiconductor functional films is inevitably disrupted by excessive concentrated stress due to the mismatch of the thermal expansion coefficient. Herein, combined with the first-principles calculation, we find that a rigid film/substrate bilayer heterostructure with a large thermal expansion mismatch upon cooling to room temperature from growth is free of surface cracks when the rigid film exhibits a dimension smaller than the critical condition for the breaking energy. The principle has been verified in a PbS/SrTiO3 bilayer system that is crack free on PbS single-crystalline microplate arrays through the designing of a dimension-confined growth (DCG) method. Interestingly, this crack-free, large-scale PbS microplate array exhibits exceptional uniformity in morphology, dimensions, thickness, and photodetection properties, enabling a broad-band infrared image sensing. This work provides a new perspective to design materials and arrays that demand smooth and continuous surfaces, which are not limited only to semiconductor electronics but also include mechanical structures, optical materials, biomedical materials, and others.

Towards highly-selective H2O2 photosynthesis: In-plane highly ordered carbon nitride nanorods with Ba atoms implantation

Graphitic carbon nitride (g-C3N4) shows great potential in photocatalytic H2O2 production. However, challenges arise from its low in-plane crystallinity and selectivity in two-electron oxygen reduction reaction (2e−-ORR), greatly limiting its H2O2 photosynthesis efficiency. Herein, we develop an ingenious strategy to simultaneously increase the in-plane crystallinity and induce the highly-selective 2e−-ORR by rationally designing barium (Ba) atom-implanted in-plane highly ordered g-C3N4 nanorods. The approach involves controllable synthesis of in-plane high crystallinity g-C3N4 nanorods with Ba implantation (BI-CN) using a BaCl2-mediated in-plane polymerization strategy. The unique Ba-N interaction induces the oriented polymerization of 3-s-triazine units to form well-arranged in-plane structures. Experimental and theoretical calculations clarify that the implanted Ba atoms function as positive charge centers, resulting in a Pauling-type O2 adsorption configuration. This minimizes O–O bond breaking energy, thus suppressing the four-electron oxygen reduction reaction (4e−-ORR) and facilitating a highly-selective 2e−-ORR pathway for efficient photocatalytic H2O2 production. Consequently, the optimized BI-CN3 photocatalyst exhibits an outstanding H2O2 production rate of as high as 353 μmol L−1 h−1, surpassing the pristine g-C3N4 by 6.1 times. This study concurrently optimizes the in-plane crystallinity and O2 adsorption sites of g-C3N4 photocatalysts for highly-selective H2O2 production, providing innovative insights for designing efficient photocatalysts with diverse applications.

Randomly cross-linked amphiphilic copolymer networks of n-butyl acrylate and N,N-dimethylacrylamide: synthesis and characterization

Abstract Five randomly cross-linked amphiphilic copolymer networks (ACPN) were prepared via the free radical cross-linking copolymerization of the hydrophobic n-butyl acrylate (BuA) and the hydrophilic N,N-dimethylacrylamide (DMAAm), in the presence of a small amount (5 mol% with respect to the sum of BuA plus DMAAm monomers) of the hydrophobic 1,6-hexanediol diacrylate (HexDA) cross-linker, initiated by 4,4ʹ-azobis(4-cyanovaleric acid) in 1,4-dioxane at a 10 % w/v total monomer concentration. The five ACPNs differed in their BuA content, fixed at 10, 30, 50, 70 and 90 mol%. The two homopolymer networks, BuA and DMAAm, were also prepared using the same polymerization method. Thus, this study involved a total of seven polymer networks, forming a homologous series with BuA contents ranging from 0 to 100 mol%. These networks were characterized in terms of their degrees of swelling in tetrahydrofuran (THF) and water, their mechanical properties in water, and their adhesion to human skin. The degrees of swelling (DS) of the networks in THF were higher than those in water because THF is a non-selective solvent, whereas water is selective for the hydrophilic DMAAm units. The DSs in THF increased with the network content in the less polar BuA units, while the opposite was true for the DSs in water which decreased with the content in the hydrophobic BuA units from 11 (0 mol% BuA) down to 1.1 (100 mol% BuA). A maximum in the elastic modulus was observed for the hydrogel with 50 mol% BuA, reflecting the opposing effects of polymer composition in soft polymer (polyBuA) content and hydrogel water content. In contrast, the tensile strain at break increased monotonically with the hydrogel BuA content, reaching a remarkable ∼900 % for the hydrogel with 90 mol% BuA. Finally, the adhesion of the ACPNs, both in their dried and hydrated states, onto human skin was explored. The adhesion of the hydrated samples onto skin was stronger than that of the dried ones. The hydrated ACPN with 30 mol% BuA exhibited the strongest adhesion onto skin, attributable to the best combination of a rather high content in polar DMAAm units (70 mol%), and a rather low aqueous DS (∼2.5), with the low DS value causing only a small dilution in the DMAAm units participating in the polar interactions with skin. The present work demonstrates that, even in this synthetically simple ACPN system, the multiple effects of ACPN composition on a certain property, in some cases opposing and in some other cooperating, lead to a rather complicated behavior. In particular, as the BuA content increases, some properties display maxima (elastic modulus, stress at break and fracture energy of hydrated ACPNs, and adhesion of hydrated ACPNs onto skin) while some other properties exhibit monotonic increases (strain at break of hydrated ACPNs, and adhesion of dried ACPNs onto skin). Thus, the optimal ACPN for a particular application will highly depend on the property best-serving the particular application, e.g., the ACPNs with 30, 50 and 90 mol% BuA for strongest wet adhesion to skin, stiffest hydrogel response, and highest hydrogel extensibility and toughness, respectively.