Intrinsic Instability Research Articles

Lignin-reinforced eutectogel with environmentally stability for high-performance human multi-functional sensor

Intrinsic environmental instability of hydrogels has limited their practical applications as durable flexible sensors in human life. In this study, a bio-based eutectogel (BEG) with environmental tolerance was designed via deep eutectic solvent (DES), thioctic acid (TA) and lignin. Benefit from self-ring-opening polymerization of TA monomer in the ethanol and the lignin acting as free radicals, the BEG was fabricated through efficient cast-drying method. The dynamic interaction formation between DES and TA polymer network was revealed by using in-situ infrared spectroscopy during the ethanol evaporation process. The introduction of lignin not only improve the mechanical properties of the eutectogels, but also endow the BEG with moisture tolerance by activating self-aggregated dense hydrophobic layer on the surface while in high humidity environment. This bio-based eutectogels with non-volatility, board range operating temperature and proper self-adhesion could serve as long-term stable temperature-strain dual sensor with high sensitivity (GF = 1.17, TCR = 4.26 %/K) and rapid response behavior (373 ms). Furthermore, the biocompatible BEG was validated for recording human physiological signals over extended period with performance comparable to commercial hydrogel electrodes. This strategy could broaden the range of making durable stretchable eutectogels in human healthcare monitoring.

Effect of oxygen enrichment and NH3 pre-cracking on laminar burning velocity and intrinsic instability of NH3/bio-syngas

This paper investigates the laminar burning velocity (SL) and instability of NH3/bio-syngas under different bio-syngas contents, oxygen enrichment factors (Ω), and the cracking ratio of NH3 (ζ) using a constant-volume combustion bomb. The results show that increasing bio-syngas, Ω, and ζ effectively enhance the SL of the fuel. Around ζ = 60%, the relationship between SL and the NH3 content before cracking is reversed. Increasing the bio-syngas and ζ enhance SL through the chemical effect, while Ω primarily enhances SL through the thermal effect. When Ω = 50%, the contribution of thermal effect can reach up to 94.53%. Linear stability analysis indicates that increasing the bio-syngas content and ζ reduces the critical Peclet number (Pec), while Ω increases Pec. As the bio-syngas content and ζ increase, the growth rate of perturbation (∑) monotonically increases, indicating instability. Ω, on the other hand, decreases ∑, making it negative.

Dealuminated H–Y zeolites generate, stabilize and catalytically insert carbenes from diazocarbonyl compounds

Carbenes are among the most powerful reactants in organic synthesis, with capacity to insert into a variety of otherwise stable bonds, and generate two new bonds in a straightforward manner. However, the intrinsic instability of such carbenes makes them to be catalytically generated, in–situ, from precursors such as diazocarbonyl compounds, and the catalyst, in turn, also controls the subsequent insertion reaction. The catalyst is generally a metal complex in solution, mainly Cu, Ag or Rh, but also others, including protons in rare cases. Here we show that carbenes are generated, stabilized and inserted into C–C, C–H, O–H, N–H, Si–H and O–O bonds after reacting diazocarbonyl compounds with catalytic amounts of metal–free, commercially available dealuminated H–Y zeolites. These results open the way to design carbene–mediated organic reactions on readily available and reusable catalytic solids without involving metals.

Self-adhesive, stretchable, anti-freezing conductive organohydrogels with fast gelation from catechol-metal ion self-catalytic system for flexible strain sensors

Conductive hydrogels have attracted tremendous attention in flexible sensors due to their flexibility, durability, and multifunctionality. However, time and energy-consumption fabrication process and intrinsic instability in extreme environments severely limit their practical implementations. Herein, a universal and facile synergetic self-catalytic system based on catechol-based molecules and metal ions has been developed to the fast gelation (≈3s) of conductive organohydrogels in water–ethylene glycol (EG) binary solvent, which exhibits excellent stretchability (up to 630 % elongation), satisfactory self-adhesion (up to 16.3 kPa), and extreme environment applicability (−80 °C to 45 °C). This dual self-catalytic system consists of tannic acid (TA) and ferric ions (Fe3+), which form stable redox pairs to activate ammonium persulfate to generate free radicals, rapidly initiating the polymerization of monomers. Furthermore, the introduction of H2O/EG binary solvent not only facilitates the dispersion of components to improve the mechanical performance of organohydrogels, but also the generation of abundant hydrogen bonds between EG and water molecules endows extreme freezing drying resistance, and enhances self-adhesion for organohydrogels. The organohydrogels showing high sensitivity toward tensile deformation are assembled into flexible strain sensors to detect human motions with high sensitivity, exceptional stability, and excellent durability, which holds great promise in flexible electronics.

Potentiation of Catalase-Mediated Plant Thermotolerance by N-Terminal Attachment of Solubilizing/Thermostabilizing Fusion Partners.

Catalase (CAT) plays a crucial role in plant responses to environmental stresses and maintaining redox homeostasis. However, its putative heat lability might compromise its activity and function, thus restricting plant thermotolerance. Herein, we verified Arabidopsis CAT3 was of poor thermostability that was then engineered by fusion expression in Escherichia coli. We found that our selected fusion partners, three hyperacidic mini-peptides and the short rubredoxin from hyperthermophile Pyrococcus furiosus, were commonly effectual to enhance the solubility and thermostability of CAT3 and enlarge its improvement on heat tolerance in E. coli and yeast. Most importantly, this finding was also achievable in plants. Fusion expression could magnify CAT3-mediated thermotolerance in tobacco. Under heat stress, transgenic lines expressing CAT3 fusions generally outperformed native CAT3 which in turn surpassed wild-type tobacco, in terms of seed germination, seedling survival, plant recovery growth, protection of chlorophyll and membrane lipids, elimination of H2O2, as well as mitigation of cell damage in leaves and roots. Moreover, we revealed that the introduced CAT3 or its fusions seemed solely responsible for the enhanced thermotolerance in tobacco. Prospectively, this fusion expression strategy would be applicable to other crucial plant proteins of intrinsic heat instability and thus provide an alternative biotechnological route for ameliorating plant heat tolerance.

Adaptive variable gain linear active disturbance rejection control parameter optimization in magnetic levitation

The magnetic levitation ball system is characterized by strong nonlinearity, multiple disturbances, and intrinsic instability, which has long been a thorny problem in the field of control engineering. The magnetic levitation system can be continuously and stably levitated, even in a complex environment. In this thesis, the model of the magnetic levitation ball system is firstly constructed according to the kinetic theory and simplified according to the actual situation. After that, a linear active disturbance rejection control (LADRC) controller for the magnetic levitation ball system is designed. Considering that there are many parameters in the LADRC controller and it is difficult to obtain the optimal control effect by manual tuning, an adaptive variable gain LADRC algorithm is proposed to optimize the control strategy of LADRC parameters. An adaptive iterative algorithm is used to adaptively adjust the bandwidth of the linear extended state observer (LESO) in LADRC, and the convergence of the algorithm is demonstrated by using the Lyapunov function. To solve the problem that the proportional and differential gains of the LADRC controller can only be adjusted unidirectionally and simultaneously, this paper proposes an error variable gain algorithm. The aim is to realize the non-unidirectional and more detailed adjustment of the controller parameters, and it is rigorously analyzed and demonstrated through simulation and experiment. The results show that the proposed algorithm is better than proportional–integral–derivative (PID), sliding mode control (SMC), and LADRC in terms of dynamic performance, steady-state performance, and anti-interference.

Scales and self-sustained mechanism of reattachment unsteadiness in separated shock wave/boundary layer interaction

The spatio-temporal scales, as well as a comprehensive self-sustained mechanism of the reattachment unsteadiness in shock wave/boundary layer interaction, are investigated in this study. Direct numerical simulations reveal that the reattachment unsteadiness of a Mach 7.7 laminar inflow causes over $26\,\%$ variation in wall friction and up to $20\,\%$ fluctuation in heat flux at the reattachment of the separation bubble. A statistical approach, based on the local reattachment upstream movement, is proposed to identify the spanwise and temporal scales of reattachment unsteadiness. It is found that two different types, i.e. self-induced and random processes, dominate different regions of reattachment. A self-sustained mechanism is proposed to comprehend the reattachment unsteadiness in the self-induced region. The intrinsic instability of the separation bubble transports vorticity downstream, resulting in an inhomogeneous reattachment line, which gives rise to baroclinic production of quasi-streamwise vortices. The pairing of these vortices initiates high-speed streaks and shifts the reattachment line upstream. Ultimately, viscosity dissipates the vortices, triggering instability and a new cycle of reattachment unsteadiness. The temporal scale and maximum vorticity are estimated with the self-sustained mechanism via order-of-magnitude analysis of the enstrophy. The advection speed of friction, derived from the assumption of coherent structures advecting with a Blasius-type boundary layer, aligns with the numerical findings.

Synergistically regulating the structural tolerance of Co-free Ni-rich cathode materials at high-rate through multi-heteroatoms substitution

Cobalt-free, nickel-rich layered oxides are attracting extensive interest as cathodes to construct high-energy and sustainable lithium-ion batteries, but the intrinsic structure instability and weakened reaction kinetics deteriorate their application. Nowadays, doping engineering, especially multielement doping, has become an effective modification method for obtaining high-performance Ni-rich materials. Herein, the designed doping strategy with high oxidation states element (Zr4+, Mo6+) substituting transition metal element and Mg2+ replacing Li+ in LiNi0.9Mn0.1O2 (NM-ZMM) has been designed to enhance its electrochemical properties. The introduced doping elements with high oxidation states can generate the strong metal-O bond, which contributes to suppress the structural collapse induced by internal stress, and then maintain unblock ion channels for NM-ZMM. Meanwhile, the presence of Mg2+ can also be employed as the pillar ions to reinforce the structure stability, and occupy the Li-sites to inhibit lattice distortion during charging/discharging process. Thus, benefitting from the synergistic reinforcement of co-doping strategy, as-prepared NM-ZMM materials exhibit the prominent capacity retention (87.5 %, 210 cycles, 1C; 85.5 %, 2C, 150 cycles). Thereof, this creative strategy is crucial in strengthening the electrochemical performance of Ni-rich Co-free materials, which contributes to promote the development of high-performance and cost-effective Li-ion storage technology.

The effects of NH3 pre-cracking and initial temperature on the intrinsic instability and NOx emissions of NH3/bio-syngas/air premixed flames

The study of the combustion characteristics of NH₃/bio-syngas/air under NH₃ partial cracking and elevated initial temperatures can enhance its feasibility as a practical fuel. The effects of NH₃ cracking rates (ζ) and initial temperature (T0) on the laminar burning velocity (SL), instability, and NO emissions of NH₃/bio-syngas/air premixed flames under different equivalence ratios are investigated. The results indicate that increasing ζ and T0 enhances the SL of the premixed flame, with ζ having a more pronounced effect on combustion enhancement. Virtual gas analysis reveals that pre-cracking primarily strengthens combustion through chemical effect. An increase in ζ significantly shifts the peak SL towards the fuel-rich region, while at any T0, the peak SL consistently occurs around Φ = 1.1. Increasing ζ and T0 reduces the critical radius (rc) and the critical Peclet number (Pec) of the premixed fuel, with rc decreasing more rapidly when ζ is below 30 %. The dimensionless growth rate (∑) increases with the rise in ζ and T0, consistently remaining positive, indicating an unstable state. Additionally, ∑ varies more significantly with T0 when T0 is below 450 K. When ζ is below 60 %, the NO mole fraction increases with the increase in ζ. However, at ζ = 80 %, the NO mole fraction is lower than at ζ = 40 %. Increasing T0 continually increases the NO mole fraction. Analysis of the NH3 reaction pathways indicates that NHi (i = 0, 1, 2) is closely related to the NO → N2 reduction reactions.

Dynamically Stabilizing Oxygen Atoms in Silver Catalyst for Highly Selective and Durable CO2 Reduction Reaction

AbstractOxide derived catalyst displays outstanding catalytic activity and selectivity in electrochemical carbon dioxide reduction reaction (CO2RR), in which, it is found that residue oxygen atoms play a pivotal role in regulating the catalyst's electronic structure and thus the CO2RR process. Unfortunately, the intrinsic thermodynamic instability of oxygen atoms in oxide derived catalyst under cathodic CO2RR potentials makes it unstable during continuous electrolysis, greatly hindering its practical industrial applications. In this work, we develop a pulsed‐bias technique that is able to dynamically stabilize the residue oxygen atoms in oxide derived catalyst during electrochemical CO2RR. As a result, the oxide derived catalyst under pulsed bias exhibits super catalytic stability in catalyzing electrochemical CO2RR, while keeping excellent catalytic activity and selectivity.

Dynamically Stabilizing Oxygen Atoms in Silver Catalyst for Highly Selective and Durable CO2 Reduction Reaction.

Oxide derived catalyst displays outstanding catalytic activity and selectivity in electrochemical carbon dioxide reduction reaction (CO2RR), in which, it is found that residue oxygen atoms play a pivotal role in regulating the catalyst's electronic structure and thus the CO2RR process. Unfortunately, the intrinsic thermodynamic instability of oxygen atoms in oxide derived catalyst under cathodic CO2RR potentials makes it unstable during continuous electrolysis, greatly hindering its practical industrial applications. In this work, we develop a pulsed-bias technique that is able to dynamically stabilize the residue oxygen atoms in oxide derived catalyst during electrochemical CO2RR. As a result, the oxide derived catalyst under pulsed bias exhibits super catalytic stability in catalyzing electrochemical CO2RR, while keeping excellent catalytic activity and selectivity.

Improved Charge‐Transfer Doping in Crystalline Polymer for Efficient and Stable Perovskite Solar Cells

AbstractPerovskite solar cells (PSCs) have significant potential for next‐generation photovoltaic technology applications. However, the instability of hole transport layers (HTLs) becomes the major obstacle to long‐term operational devices, which are affected by the intrinsic thermal instability and loose structure of hole transport materials, as well as the hygroscopicity and migration of dopants. Here, poly(3‐hexylthiophene‐2,5‐diyl) (P3HT) is used as a model crystalline polymer to thoroughly investigate effective p‐type doping strategies and the underlying mechanism. According to Hard–Soft‐Acid–Base theory, the soft base P3HT is more likely to form a stable Lewis acid–base adduct with the reactive soft acid radical, resulting in a strong charge‐transfer interaction, thereby enhancing conductivity and regulating the energy band of the HTL. Meanwhile, the radical cation salt can promote pre‐nucleation to optimize the crystallization orientation of P3HT. The resulting PSCs exhibited the efficiency of 25.16%, which is the highest efficiency reported so far based on doped P3HT. In addition, the resulting devices demonstrated excellent stability, maintaining 96.5%, 96%, and 91% of their initial efficiency after aging under continuous illumination for 2028 h, at 85 °C for 1080 h, and at maximum power point (MPP) tracking under continuous 1 Sun illumination at 85 °C for 528 h, respectively.

Three-dimensional dynamics of unstable lean premixed hydrogen-air flames: Intrinsic instabilities and morphological characteristics

The 3D swinging laser sheet technique was employed to study the development and morphological characteristics of premixed hydrogen-air unstable flames in a spherical explosion vessel. Pressure dependencies for laminar flame propagation were sought to exploit the role of the Darrieus-Landau (DL) and Thermal-diffusive (TD) instabilities in the unstable self-accelerating flame regime. A sufficiently low Markstein number, as a consequence of the increased pressure, leads to more cracking and smaller cells over the flame surface. The degree of wrinkling on the flame surface is proportional to the increase in flame burning velocity, a relationship that holds true for low pressures but is not applicable under high pressures. External turbulence can significantly alter the extent of flame surface wrinkling even at low root mean square velocities, producing a more wrinkled flame surface compared to intrinsic cellularity, and distinctly affecting flame dynamics. The increased wrinkling and flame speed due to external turbulence can be attributed to the synergistic effects between thermo-diffusive instabilities and turbulence, resulting in higher fuel consumption rates per flame surface area and the formation of finger-like structures that enhance flame displacement speed in curved segments. The parameters, ϵ, deviation of the Lewis number from a critical value, and ω2, obtained through classical linear stability analysis, display a clear linear relationship with the ratio of the wrinkled surface area observed in planar flames. This study enhances the understanding of hydrogen flame instabilities, which is crucial for preventing explosions in hydrogen storage and utilization, and provides valuable insights into flame dynamics, supporting the design of safer and more efficient hydrogen-fueled engines and turbines.

Substantial oxygen loss and chemical expansion in lithium-rich layered oxides at moderate delithiation.

Delithiation of layered oxide electrodes triggers irreversible oxygen loss, one of the primary degradation modes in lithium-ion batteries. However, the delithiation-dependent mechanisms of oxygen loss remain poorly understood. Here we investigate the oxygen non-stoichiometry in Li1.18-xNi0.21Mn0.53Co0.08O2-δ electrodes as a function of Li content by using cycling protocols with long open-circuit voltage steps at varying states of charge. Surprisingly, we observe substantial oxygen loss even at moderate delithiation, corresponding to 2.5, 4.0 and 7.6 ml O2 per gram of Li1.18-xNi0.21Mn0.53Co0.08O2-δ after resting at upper capacity cut-offs of 135, 200 and 265 mAh g-1 for 100 h. Our observations suggest an intrinsic oxygen instability consistent with predictions of high oxygen activity at intermediate potentials versus Li/Li+. In addition, we observe a large chemical expansion coefficient with respect to oxygen non-stoichiometry, which is about three times greater than those of classical oxygen-deficient materials such as fluorite and perovskite oxides. Our work challenges the conventional wisdom that deep delithiation is a necessary condition for oxygen loss in layered oxide electrodes and highlights the importance of calendar ageing for investigating oxygen stability.

Realization of a 2D Lieb Lattice in a Metal-Inorganic Framework with Partial Flat Bands and Topological Edge States.

Flat bands and Dirac cones in materials are the source of the exotic electronic and topological properties. The Lieb lattice is expected to host these electronic structures, arising from quantum destructive interference. Nevertheless, the experimental realization of a 2D Lieb lattice remained challenging to date due to its intrinsic structural instability. After computationally designing a Platinum-Phosphorus (Pt-P) Lieb lattice, it has successfully overcome its structural instability and synthesized on a gold substrate via molecular beam epitaxy. Low-temperature scanning tunneling microscopy and spectroscopy verify the Lieb lattice's morphology and electronic flat bands. Furthermore, topological Dirac edge states stemming from pronounced spin-orbit coupling induced by heavy Pt atoms are predicted. These findings convincingly open perspectives for creating metal-inorganic framework-based atomic lattices, offering prospects for strongly correlated phases interplayed with topology.

The topological characteristics of the bifurcation and chaos in the motion of combustion fronts in solids.

We investigate the geometric features in the bifurcation and chaos of a partial differential equation describing the unsteady combustion of solid propellants. Driven by the interaction of the unsteady combustion at the surface and the diffusion inside solids, the motion of the combustion fronts can be steady, harmonically oscillatory, and become more complicated to chaos through a series of bifurcations. We examined the dynamics in both free and forced oscillations. In the free oscillation, by varying a parameter related to the solid property, the intrinsic instability of the combustion is discovered. We find the typical period-doubling to chaos route and verify it via both qualitative and quantitative universalities. In the forced oscillation case, the system is perturbed by an external pressure excitation, leading to a more complicated bifurcation diagram with richer dynamics. Concentrating on the topological characteristics of the periodic orbits, we discover two new types of bifurcation other than the period-doubling bifurcation. In present work, we extract a series subtle topological structures from an infinite-dimensional dynamical systems governed by a partial differential equation with free boundary. We find the results provide an explanation for the period-3 orbits in the experimental data of a full-scale motor.

Lead-Free Cs2AgBiBr6/TiO2 S-Scheme Heterojunction for Efficient Photocatalytic Antibiotic Rifampicin Degradation.

Exploring efficient and stable halide perovskite-based photocatalysts is a great challenge due to the balance between the photocatalytic performance, toxicity, and intrinsic chemical instability of the materials. Here, the environmentally friendly lead-free perovskite Cs2AgBiBr6 confined in the mesoporous TiO2 crystal matrix has been designed to enhance the charge carrier extraction and utilization for efficient photocatalytic rifampicin degradation. The as-prepared Cs2AgBiBr6/TiO2 catalyst was stable in air for over 500 days. An S-scheme heterojunction was formed between the (004) plane of Cs2AgBiBr6 and the (101) plane of TiO2 through the Bi-O-Br bonds. The built-in electric field at the interface efficiently promoted the photoinduced charge separation and carrier extraction. The Cs2AgBiBr6/TiO2-200 showed a 92.83% degradation efficiency of rifampicin within 80 min under simulated sunlight illumination (AM 1.5G 100 mW cm-2). This work offers an effective way for the construction of halide perovskite-based photocatalysts with high photocatalytic performance, good stability, and low toxicity simultaneously.

Recent Advances in Structure Design and Application of Metal Halide Perovskite-Based Gas Sensor.

Metal halide perovskites (MHPs) are emerging gas-sensing materials and have attracted considerable attention in gas sensors due to their unique bandgap structure and tunable optoelectronic properties. The past decade has witnessed significant developments in the gas-sensing field; however, their intrinsic structural instability and ambiguous gas-sensing mechanisms hamper their practical applications. Herein, we summarize the recent advances in MHP-based gas sensors. The physicochemical properties of MHPs are discussed at first. The structure design, including dimension design and engineering design, is overviewed as well as their fabrication methods, and we put forward our insights into the gas-sensing mechanism of MHPs. It is believed that enhanced understanding of gas-sensing mechanisms of MHPs are helpful for their application as gas-sensing materials, and structure design can enhance their stability, sensing sensitivity, and selectivity to target gases as gas sensors. Subsequently, the latest developments in MHP-based gas sensors are summarized according to their different application scenarios. Finally, we conclude with the current status and challenges in this field and propose future perspectives.

Interlayer substitution enables air-stable and long-life O3-type cathode for sodium-ion batteries

The O3-type oxides (NaNi0.4Fe0.2Mn0.4O2 (NFM)) have been considered as the most commercially cathode material for high-energy-density sodium-ion batteries owing to their low price, good safety performance, and high energy density. However, their further development is seriously limited due to the complex phase transition, sluggish kinetics of Na+, and intrinsic air instability. Herein, an interlayer substituted NFM (IS-NFM) is constructed by a simple solid-state method with the introduction of alkaline-earth metal. The interlayer substitution will lead to the increase of oxygen content in the internal lattice, which will effectively suppress the irreversible phase transition during cycling and exposure to the air. In addition, the interlayer substitution effectively activated the charge compensation, leading to the mobilized cationic redox process and boosted de-/sodiated kinetic. Consequently, IS-NFM exhibits excellent capacity retention of 83.44 % at 1 C after 200 cycles and remarkable stability even at high voltage. After 15 days of exposure to the air, IS-NFM also delivers superior capacity retention (86.53 %, compared with 0.1 C) and cycling performance (82.70 % at 1 C after 200 cycles). Undoubtedly, the interlayer substitution strategy will expand a novel avenue for constructing air-stable and long-life O3-type oxides for commercial application.

Enhanced Oxidation-Resistant and Conductivity in MXene Films with Seamless Heterostructure.

MXene-based films have garnered significant attention for their remarkable electrical and mechanical properties. Nevertheless, the practical application of MXene is impeded by its intrinsic instability caused by spontaneous oxidation. The traditional anti-oxidative strategies frequently lead to a compromise in stability, electrical conductivity, and mechanical properties. In this study, a novel approach is proposed involving metal nano-armoring, wherein a copper layer with nano thickness is deposited onto MXene film surfaces to establish a uniform and seamless heterogeneous interface (MXene@Cu). The precise tunability and uniformity of this heterostructure are consistently demonstrated through both theoretical calculations and experimental results. The MXene@Cu films exhibit exceptional electrical conductivity of 1.17 × 106 S m-1, electromagnetic interference shielding effectiveness of 77.1dB, and tensile strength of 43.4MPa. More importantly, this heterostructure significantly improves MXene's stability against oxidation. After exposure to air for 30 days, the resultant MXene@Cu films exhibit a remarkable conductivity retention of 72.0%, significantly exceeding that of pristine MXene films (44.3%). This scalable synthesis approach holds significant promise for electronic device applications, particularly in electromagnetic shielding and thermal management.