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At least 757 records · Page 42

Novel catalysts with multivalence copper for organic pollutants removal from wastewater with excellent selectivity and stability in Fenton‐like process under neutral pH conditions

Abstract Fenton‐like reaction has been widely used for organics degradation. However, most Fenton‐like reaction works at low pH range (pH < 4) with uncontrollable selectivity of hydroxyl radicals from H 2 O 2 activation, and unsatisfied catalyst stability, which is compromised advanced oxidation performance for water/wastewater treatments. In this work, to solve the drawbacks, novel copper catalysts were fabricated via hydrogen reduction/calcination of Cu 2+ ‐supported Al/MCM‐41 with precisely controllable copper valence state. Compared with catalysts with monovalence copper (i.e., CuO, Cu, and Cu 2+ ), the obtained catalysts with multivalence copper present higher selectivity, excellent stability towards •OH radical pathways, and outperformance in p CBA degradation efficiency at neutral state. In addition, the fabricated catalysts also exhibited excellent phenol removal efficiency (75.5%) and H 2 O 2 utilization efficiency (47.9%) within neutral environment. Moreover, the degradation efficiency of phenol approaches to 100% within only 2 h. The catalyst also shows good stability for organic pollutants removal, which shows good potential in catalytic oxidation for phenolic compounds‐containing wastewater in Fenton‐like reaction, especially under neutral pH conditions. Practitioner Points Multivalence copper presents great potentials for organic compounds removal at neutral condition. Multivalence copper shows higher selectivity toward •OH and good stability at neutral condition. Multivalence copper exhibiters outperformed phenol removal efficiency at neutral condition.

Li, Haitao↗

Vacuum stability in inert higgs doublet model with right-handed neutrinos

We analyze the vacuum stability in the inert Higgs doublet extension of the Standard Model (SM), augmented by right-handed neutrinos (RHNs) to explain neutrino masses at tree level by the seesaw mechanism. We make a comparative study of the high- and low-scale seesaw scenarios and the effect of the Dirac neutrino Yukawa couplings on the stability of the Higgs potential. Bounds on the scalar quartic couplings and Dirac Yukawa couplings are obtained from vacuum stability and perturbativity considerations. These bounds are found to be relevant only for low-scale seesaw scenarios with relatively large Yukawa couplings. The regions corresponding to stability, metastability and instability of the electroweak vacuum are identified. These theoretical constraints give a very predictive parameter space for the couplings and masses of the new scalars and RHNs which can be tested at the LHC and future colliders. The lightest non-SM neutral CP-even/odd scalar can be a good dark matter candidate and the corresponding collider signatures are also predicted for the model.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Comparative study of three yttrium organometallic compounds for the stabilization of the cubic phase in YSZ deposited by PE-CVD

In this work, the efficiencies of three organometallic yttrium precursors used to produce YSZ coatings by plasma-enhanced chemical vapor deposition were studied. Yttrium (III) acetylacetonate, Y (acac) 3 , yttrium (III) hexafluoroacetylacetonate, Y (acacF 6 ) 3 , and yttrium (III) tris(2,2,6,6-tetramethyl-3,5-heptanedionate), Y (tmhd) 3 , were used to stabilize the cubic phase in zirconia deposited at temperatures from 500 to 800 °C. Our results showed that at temperatures between 500 and 600 °C, Y (tmhd) 3 appeared to be the most efficient dopant as it introduced the highest concentration of yttria (1–2.7 mol%) with only 6.4–5.6 at.% carbon. However, at 700 and 800 °C, Y (acac) 3 introduced twice as much yttria (8–15 mol%) as Y (tmhd) 3 with almost the same amount of carbon (5.4–3 at.%). Conversely, Y (acacF6)3 was the least efficient as it maintained a low concentration of yttria of around 0.7–1.8 mol% with 3.6–8.2 at.% carbon for all the deposition temperatures. Among these precursors, only Y (acac) 3 surpassed 8 mol% yttria and achieved a fully stabilized cubic phase at 800 °C, with the remaining samples stabilizing only the tetragonal phase. The tetragonal phase was stabilized due to the formation of crystallites of around 10 nm. The observed difference in the efficiency of the three precursors was correlated to important differences in their decomposition behavior as observed by mass spectrometry and thermogravimetry/differential scanning calorimetry.

36 MATERIALS SCIENCE↗

Continuous stabilization of polyacrylonitrile (PAN) - carbon nanotube (CNT) fibers by Joule heating

We report stabilization is one of the important processes used to convert polyacrylonitrile (PAN) fibers into carbon fiber and is usually driven by energy-intensive and time-consuming convective heating. A continuous and energy-efficient alternative is desirable. Here, a continuous Joule heating process has been used for the first time to stabilize PAN fibers containing carbon nanotubes (CNT). Single-component PAN/CNT fibers and bi-component fibers with core-sheath geometry were fabricated through the gel spinning method. Joule heating was conducted continuously on a 200 filament bundle for single-component fibers and on bundles with up to 6000 filaments for the bi-component fibers. A model of heat transfer and thermodynamics occurring during Joule heating is developed and utilized to understand the reductions in stabilization time and energy consumed when compared to convective heating. The minimum energy needed for stabilization through Joule heating is estimated to be less than 1% of the energy used through convective heating.

42 ENGINEERING↗

Mixed lipid bilayers enable enhanced stability and activity retention of Lipase A in low-pH environments

Lipase A (LipA) from Bacillus subtilis is a versatile and industrially relevant enzyme, but its activity is compromised under acidic conditions due to aggregation and deactivation. In this study, we investigated the use of mixed lipid bilayers to stabilize and improve activity retention of LipA at low pH. Attachment to lipid bilayers, particularly those containing cationic lipids, greatly enhanced the long-term stability of LipA in acidic conditions while also leading to improvements in activity. Tethering to cationic bilayers not only shifted the apparent pH activity profile toward more acidic conditions, but also significantly enhanced activity retention upon incubation at pH 6. Notably, this protective effect persisted even without direct tethering, indicating that reversible, non-covalent interactions with the bilayer surface are sufficient for long-term stability. Circular dichroism further revealed that the secondary structure of LipA was retained, while dynamic light scattering suggested that activity loss in solution was primarily due to aggregation of the native state. Together, these findings support a model in which lipid bilayers mitigate aggregation and stabilize LipA through transient interactions and electrostatic modulation of the local surface environment. Furthermore, this approach exemplifies a simple, tether-free strategy for enhancing enzyme performance in acidic or destabilizing conditions, with implications for biocatalysis, biosensing, and therapeutic delivery.

Biocatalysis↗

Tuning bandgap and energy stability of Organic-Inorganic halide perovskites through surface engineering

Organohalide perovskite with a variety of surface structures and morphologies have shown promising potential owing to the choice of the type of heterostructure dependent stability. We systematically investigate and discuss the impact of 2-dimensional molybdenum-disulphide (MoS 2 ), molybdenum-diselenide (MoSe 2 ), tungsten-disulphide (WS 2 ), tungsten-diselenide (WSe 2 ), boron-nitiride (BN) and graphene monolayers on bandgap and energy stability of organic–inorganic halide perovskites. We found that MAPbI 3 deposited on BN-ML shows room temperature stability (-25 meV ~ 300 K) with an optimal bandgap of ~ 1.68 eV. The calculated absorption coefficient also lies in the visible-light range with a maximum of 4.9 × 10 4 cm –1 achieved at 2.8 eV photon energy. Furthermore, on the basis of our calculations, we suggest that the encapsulation of an organic–inorganic halide perovskite monolayers by semiconducting monolayers potentially provides greater flexibility for tuning the energy stability and the bandgap.

36 MATERIALS SCIENCE↗

Active electrochemical interfaces stabilized through self-organized potential oscillations

Some electrochemical systems are known to have higher average efficiency when operated under an oscillatory regime. Given the compromise between activity and stability, the stability of electrochemical interfaces in a self-organized, oscillatory state must be taken into account. Here we evaluate the electro-oxidation of methanol and formic acid on platinum under regular and oscillatory conditions, and study the stability by following the Pt dissolution rates in situ with a stationary probe rotating disk electrode (SPRDE) coupled to an inductively coupled plasma mass spectrometer (ICP-MS). Generally speaking, as the electro-oxidation reaction proceeds, the platinum dissolution rate increases considerably. To guarantee Pt stability, the potential must be kept below 1.0 V vs. RHE. Interestingly, no dissolution is detectable when the electrode potential undergoes temporary self-organization, ensuring a stable and active interface.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Synergistic foam stabilization and transport improvement in simulated fractures with polyelectrolyte complex nanoparticles: Microscale observation using laser etched glass micromodels

Inaccessibility to direct pore scale observation in hydrocarbon recovery of tight shale formations poses a great challenge to water-energy nexus initiatives and necessitates the use of high throughput technologies to emulate environmentally friendly processes. Herein, we employ a precise glass micromodel fabrication and visualization method to isolate the supercritical CO 2 bubbles surrounded by CO 2 -water lamella prepared in saline produced water stabilized with molecular complexation of zwitterionic surfactants (ZS) and polyelectrolyte complex nanoparticles (PECNP). The Selective Laser Enhanced Etching (SLE) technique was selected for micromodel simulation of high-pressure flow. Two representative designs, (1) fracture/micro-crack network 28 and (2) fracture/matrix were etched on fused silica glass with a laser printing machine and scCO 2 foam was injected to study the foamability, propagation, stability, and fluid loss properties. The highly monodispersed and uniformly distributed array of scCO 2 bubbles were detected in flow of scCO 2 foam in highly saline brine containing ionic complexes of positively charged PECNPs and ZS, whereas foam flow with the lamella containing ZS in fractures offered a noticeably large and polydisperse array of scCO 2 bubbles. scCO 2 bubble motion and deformation were traced, and local description of foam flow was visually examined. The confined array of scCO 2 bubbles stabilized by ZS in microcracks was affected by bubble growth and coalescence, whereas the super-populated array of monodispersed scC O2 bubbles with lamella containing complexes of PECNP and ZS were able to fill the channels with stable configurations within the timeframe of comparative stability measurements. The ability of complex fluid to prevent the formation damage was evaluated through fluid loss visualization in micromodels. Probing scCO 2 foam transport in homogenous porous media revealed smaller volume leak-off for scCO 2 foam containing PECNP-ZS ionic complexes.

04 OIL SHALES AND TAR SANDS↗

Effect of nickel on the kinematic stability of retained austenite in carburized bearing steels – In-situ neutron diffraction and crystal plasticity modeling of uniaxial tension tests in AISI 8620, 4320 and 3310 steels

The presence of kinematically metastable retained austenite in the microstructure of bearing components can significantly affect the macro and micro-mechanical material response. In the present work, the influence of Ni on the stability of the retained austenite within three different grades of high carbon bearing steel using in-situ neutron diffraction is investigated. For the first time, the results show that presence of Ni increases the stability of the austenite in the elastic regime whereas the transformation rate remains unaffected. Crystal plasticity finite element (CPFE) modeling was used to study the deformation in these three steels and shows that the predominant factor causing the difference in mechanical behavior of these steels is the austenite stability. Finally, the elastic and plastic response of the matrix martensite was found to be identical among all specimens while the austenite demonstrates similar elastic behavior but remarkably different stabilities under monotonic loading.

36 MATERIALS SCIENCE↗

Transition state stabilization depends on solvent identity, pore size, and hydrophilicity for epoxidations in zeolites

Ti-silicates activate H 2 O 2 to form Ti-hydroperoxo and Ti-peroxo intermediates that can react with alkenes to form epoxide products. Comparisons of kinetics for 1-octene epoxidation with H 2 O 2 on Ti-BEA and Ti-MFI catalysts with different hydrophilicities in methanol (CH 3 OH) or acetonitrile (CH 3 CN) solvents show the significance of the solvent for stabilizing catalytically-relevant species and the complex interdependencies between solvent, catalyst topology, and hydrophilicity. Epoxidation turnover rates are higher in CH 3 CN than CH 3 OH for Ti-BEA, but the opposite trend is observed for Ti-MFI. Ti-silicates with greater silanol densities, however, give greater epoxidation turnover rates than their hydrophobic counterparts in both solvents. Kinetic, spectroscopic, and thermodynamic analyses show that differences in turnover rates mainly arise from changes in the stabilization of reactive surface species by solvent mediated interactions, because the mechanism of the reaction and stability of the fluid-phase reactants remain similar in CH 3 CN and CH 3 OH. Specifically, apparent activation free energy values ($ΔG^{‡}_{App}$) indicate that surface intermediates responsible for alkene epoxidation are stabilized to a greater extent in CH 3 CN on Ti-BEA and in CH 3 OH on Ti-MFI. Hydrophilic Ti-silicates present lower ($ΔG^{‡}_{App}$) values regardless of solvent identity, which suggests that these differences correspond to the number of hydrogen-bonding solvent molecules found near reactive species bound to Ti active sites. Finally, taken together, these findings demonstrate the role of solvent molecules in allowing reactive intermediates to recognize the properties of active sites beyond the length-scale of covalent bonds, which carry implications for epoxidation but also other reactions within solvent-filled pores of microporous materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Application of lipid-stabilized liquid-liquid interfaces in 3D printing of biomaterials

Developing strategies to stabilize liquid-liquid interfaces is essential for advancing applications in various biomedical systems. This study introduces a novel biocompatible in situ-forming material in which lipid self-assembly stabilizes water–oil interfaces, enabling controlled structuring of liquids through liquid-in-liquid 3D printing. The stabilization process, driven by the formation of nanostructures at the interface, is thoroughly analyzed through small-angle X-ray scattering (SAXS), rheometry, and microscopy techniques. This material system enables the fabrication of complex 3D constructs, including fibers, substrates, and microneedle patches, which exhibit outstanding mechanical properties and biocompatibility, as confirmed by tensile testing and cell viability tests. Here, by leveraging the unique properties of lipid-stabilized interfaces, this work demonstrates the potential of this approach for diverse biomedical applications such as drug delivery and tissue engineering while establishing a foundation for future advancements in liquid-in-liquid 3D printing technology.

36 MATERIALS SCIENCE↗

Bayesian optimization of entropy-stabilized metal fluoride conversion cathodes and their synthesis

Fluoride-based conversion cathodes are promising for next-generation Li ion batteries because of their high voltage and energy densities. High entropy earth abundant fluoride cathodes are attractive for sustainable battery because of the potentially higher cycling stability. While Ni and Co containing equimolar alloys stabilized by high entropy were considered previously, Ni and Co free non-equimolar metal alloy compositions might offer new opportunities to increase materials stability and average voltage. This opportunity was pursued using Bayesian optimization of average voltage for the computational prediction of (Fe x1 Cu x2 Zn x3 Mn x4 Mg x5 )F 2 cathode chemistries. Theoretical voltage, room temperature free energy, and electronic structure of potentially high voltage compositions were computed using density functional theory calculations. Here, the experimental realization of non-equimolar quinary Co and Ni free fluorides with stable rutile single phase and improved conversion reaction voltage by up to 28 % compared to the equimolar alloy demonstrated the power of Bayesian optimization methods for the computationally guided experimental synthesis of fluoride cathodes. Finally, non-equimolar cathode chemistries were found with cycling stability superior to known multi-element fluorides.

25 ENERGY STORAGE↗

Polystyrene sulfonate (PSS) stabilized polyethylenimine (PEI) membranes fabricated by spray coating for highly effective CO 2 /N 2 separation

Greenhouse effect, largely caused by CO 2 emission, has become a major concern for global climate change. Post-combustion CO 2 capture is one of the critical strategies to mitigate this issue. Membrane technology for carbon capture has drawn significant attention because of the cost and energy efficiency and scalability. Many membranes for CO 2 capture are limited by the trade-off between CO 2 permeability and CO 2 /N 2 selectivity and the long-term stability under practical operating conditions. Facilitated transport membranes with efficient CO 2 carriers have demonstrated potential to surpass the permeability-selectivity trade-off, but these carriers are often lost under operational conditions. In this work, we designed and fabricated a polystyrene sulfonate (PSS) stabilized polyethylenimine (PEI) membrane by a facile and scalable spray-coating method. The deposited defect-free selective layer, in which the amine carriers in PEI can be stabilized electrostatically by PSS, exhibited superior CO 2 separation performance with good long-term stability under practical operating conditions. The separation performance was optimized by spray-coating cycles, CNT network loading, and PSS loading. Our membrane showed CO 2 permeance ranging from 820 to 1,770 GPU and CO 2 /N 2 selectivity varying from 395 to 460 under vacuum operation mode in the temperature range between 80 and 90 °C. Furthermore, the membrane was successfully scaled up to 200 cm 2 with good uniformity. These results might suggest a novel membrane structure and a scalable approach for fabrication of highly efficient CO 2 separation membranes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Evaluation of automated stability testing in machining through closed-loop control and Bayesian machine learning

Here, this paper describes a system for automated identification of the optimal stable cutting parameters in milling through Bayesian machine learning and closed-loop control. The closed-loop control system consists of a process monitoring architecture, an analysis framework, and a feedback mechanism. The analysis framework consists of a Bayesian machine learning algorithm that learns a stability map given test results. The learned stability map is used to select parameters for stability testing using an expected improvement in the material removal rate criterion. The test parameters are communicated to the machine controller to complete the test cut through a feedback mechanism. The test cuts were monitored using an audio signal; the stability of the test cut was determined by analyzing the frequency content of the audio signal. The test result was fed back to the Bayesian learning algorithm to complete the loop. Experimental results demonstrate that the system can identify the optimal stable parameters without information about the cutting force model or the structural dynamics. The system provides a low-cost method for optimal stable parameter identification in an industrial environment.

Chatter↗

Pointing stabilization of a 1 Hz high-power laser via machine learning

Abstract High-power lasers are vital for particle acceleration, imaging, fusion and materials processing, requiring precise control and high-energy delivery. Laser plasma accelerators (LPAs) demand laser positional stability at focus to ensure consistent electron beams in applications such as X-ray free-electron lasers and high-energy colliders. Achieving this stability is especially challenging for the low-repetition-rate lasers in current LPAs. We present a machine learning method that predicts and corrects laser pointing instabilities in real-time using a high-frequency pilot beam. By preemptively adjusting a correction mirror, this approach overcomes traditional feedback limits. Demonstrated on the BELLA petawatt laser operating at the terawatt level (30 mJ amplification), our method achieved root mean square pointing stabilization of 0.34 and 0.59 $\unicode{x3bc} \mathrm{rad}$ in the x and y directions, reducing jitter by 65% and 47%, respectively. This is the first successful application of predictive control for shot-to-shot stabilization in low-repetition-rate laser systems, paving the way for full-energy petawatt lasers and transformative advances across science, industry and security.

Amodio, Alessio↗

Kinetic versus Thermodynamic Stability of LLZO in Contact with Lithium Metal

Li 7 La 3 Zr 2 O 12 (LLZO) garnet-based oxides are a promising class of solid electrolytes used as the separator in all-solid-state batteries (ASSBs). While LLZO is considered to have a wide electrochemical stability window, its intrinsic stability in contact with lithium metal is not sufficiently well understood, and there is still a debate on the key question of whether LLZO does or does not form passivation layers before and during cycling. Utilizing both in situ and operando X-ray photoelectron spectroscopy techniques, in this work we reveal the presence of a kinetic barrier to the reduction of LLZO by Li metal, with the extent of oxygen-deficient interphase (ODI) formation depending sensitively on the energetics of Li metal arriving at the Li vertical bar LLZO interface. Despite the clear presence of a kinetic barrier to reduction, the electrochemical response of the Li vertical bar LLZO interface is unchanged by the presence of the ODI, indicating that ODI formation during electrochemical cycling does not hinder charge transfer across the Li vertical bar LLZO interface. Overall, these results reveal that the reactivity of LLZO with Li metal depends not only on the material properties of the adjoining phases (i.e., surface purity and active contact) and their resulting thermodynamic stability but also on the energy input at the interface and the resulting reaction kinetics. Furthermore, the presence of a kinetic barrier to reduction highlights the additional complexities governing the reactivity of solid-state interfaces in ASSBs and underscores the importance of operando characterization of interfacial stability to design more robust, high-performance protection strategies for solid electrolytes in contact with reactive electrodes.

25 ENERGY STORAGE↗

Interplay between Intrinsic Thermal Stability and Expansion Properties of Functionalized UiO-67 Metal–Organic Frameworks

The UiO family of metal-organic frameworks (MOFs) has been extensively studied for several applications owing to their high stability rendered by their robust secondary building units. The efficient design and use of these materials require a fundamental understanding of their thermal stability and its impact on chemical and structural functionality. In this work, we provide a detailed characterization of the intrinsic thermal behavior of the UiO-67 and functional analogues, UiO-67-NH 2 and UiO-67-CH 3 . Using in situ temperature-programmed X-ray diffraction, we find that distortion of the carboxylate group on the organic linker leads to negative thermal expansion (NTE) of the UiO-67 MOFs during heating. This NTE behavior is correlated with rich and reversible thermal changes observed in the MOF infrared spectral signature as samples are heated to the sample activation temperature (473 K). We find that in the absence of oxygen, activated UiO-67 samples show higher thermal stability compared to ambient or inert environments, with temperature-programmed desorption revealing an overall stability trend: UiO-67 > UiO-67- CH 3 > UiO-67-NH 2 . Two stages of change are observed during thermal treatment above 473 K, which are directly related to deformation of the inorganic node and the isotropic NTE behavior of these materials. Ultimately, these results provide a real-time interpretation of the fundamental thermoresponsive behavior of UiO-67 MOFs and offer a foundation for accurate interpretation of MOF interactions with guest molecules and their temperature dependence.

36 MATERIALS SCIENCE↗

Evaluating Autoxidation Radical Scavengers and Additives to Enhance Aminopolymer Sorbent Stability

Solid amine sorbents have shown promise in the removal of ultradilute CO 2 from the atmosphere. Despite being a promising candidate material type for this application, these sorbents are prone to degradation during long-term exposure to environmental components such as CO 2 , O 2 , and H 2 O, with amine oxidation being a particularly challenging problem. In this study, we investigate the potency of different radical scavengers and additives in mitigating the degradation of a model poly- (ethylenimine) (PEI)/Al 2 O 3 sorbent under direct air capture (DAC)-relevant conditions. The results reveal that a 4,4′-bis(α,α- dimethylbenzyl)diphenylamine (BDDPA)-incorporated PEI/Al 2 O 3 sorbent showed the most resistance toward oxidative degradation at varying exposure times and BDDPA loadings under CO 2 -free air (21% O 2 /balance N 2 ) at 120 °C. Interestingly, under humid (∼43% relative humidity (RH) at 26 °C) and dry 0.04% CO 2 -air, the BDDPA/PEI/Al 2 O 3 sorbent showed enhanced sorbent stability both at 70 and 120 °C after 4.5 h of exposure. Under humid CO 2 -free air, at 120 °C, the antioxidant performance slightly declined (in comparison to the dry CO 2 -free air condition) but displayed a much higher stability than the pristine sorbent. Overall, the ability of BDDPA to inhibit sorbent degradation under dry and humid, CO 2 -free and CO 2 -containing (0.04%) air at intermediate (70 °C) and elevated (120 °C) temperatures is promising in prolonging sorbent stability and underscores the importance of performing accelerated oxidation studies in the presence of all species that are expected to be present in DAC processes to identify suitable stabilization treatments for sorbent materials.

36 MATERIALS SCIENCE↗