Search Results (4,759)

Although concentrated solar power (CSP) coupled with calcium looping (CaL) offers a promising avenue for efficient thermal chemical energy storage, calcium-based sorbents suffer from accelerated structural degradation and decreased CO₂ capture capacity during multiple cycles. This study used Density Functional Theory (DFT) calculations to investigate the mechanism by which Mg and Ni doping improves the adsorption/desorption performance of CaO. The DFT results indicate that Mg and Ni doping can effectively reduce the formation energy of oxygen vacancies on the CaO surface. Mg–Ni co-doping exhibits a significant synergistic effect, with the formation energy of oxygen vacancies reduced to 5.072 eV. Meanwhile, the O²⁻ diffusion energy barrier in the co-doped system was reduced to 2.692 eV, significantly improving the ion transport efficiency. In terms of CO₂ adsorption, Mg and Ni co-doping enhances the interaction between surface O atoms and CO₂, increasing the adsorption energy to −1.703 eV and forming a more stable CO₃²⁻ structure. For the desorption process, Mg and Ni co-doping restructured the CaCO₃ surface structure, reducing the CO₂ desorption energy barrier to 3.922 eV and significantly promoting carbonate decomposition. This work reveals, at the molecular level, how Mg and Ni doping optimizes adsorption–desorption in calcium-based materials, providing theoretical guidance for designing high-performance sorbents. Full article

In this study, we propose a bidirectional chemical sensor platform based on a reconfigurable ion-sensitive field-effect transistor (R-ISFET) architecture. The device incorporates Ni-silicide Schottky barrier source/drain (S/D) contacts, enabling ambipolar conduction and bidirectional turn-on behavior for both p-type and n-type configurations. Channel polarity is dynamically controlled via the program gate (PG), while the control gate (CG) suppresses leakage current, enhancing operational stability and energy efficiency. A dual-control-gate (DCG) structure enhances capacitive coupling, enabling sensitivity beyond the Nernst limit without external amplification. The extended-gate (EG) architecture physically separates the transistor and sensing regions, improving durability and long-term reliability. Electrical characteristics were evaluated through transfer and output curves, and carrier transport mechanisms were analyzed using band diagrams. Sensor performance—including sensitivity, hysteresis, and drift—was assessed under various pH conditions and external noise up to 5 V_pp (i.e., peak-to-peak voltage). The n-type configuration exhibited high mobility and fast response, while the p-type configuration demonstrated excellent noise immunity and low drift. Both modes showed consistent sensitivity trends, confirming the feasibility of complementary sensing. These results indicate that the proposed R-ISFET sensor enables selective mode switching for high sensitivity and robust operation, offering strong potential for next-generation biosensing and chemical detection. Full article

Soil organic carbon (SOC) pool plays an extremely important role in regulating the global carbon (C) cycle and climate change. Atmospheric nitrogen (N) and phosphorus (P) deposition caused by human activities has significant impacts on soil C sequestration potential of terrestrial ecosystem. To investigate the effects of N and P deposition on soil C sequestration and C-N coupling relationship in broad-leaved evergreen forests, a 6-year field nutrient regulation experiment was implemented in subtropical Castanopsis sclerophylla forests with four different N and P additions: N addition (100 kg N·hm⁻²·year⁻¹), N + P (100 kg N·hm⁻²·year⁻¹ + 50 kg P·hm⁻²·year⁻¹), P addition (50 kg P·hm⁻²·year⁻¹), and CK (0 kg N·hm⁻²·year⁻¹). The changes in the C and N contents and stable isotope distributions (δ¹³C and δ¹⁵N) of different soil organic fractions were examined. The results showed that the SOC and total nitrogen (STN) (p > 0.05) increased with N addition, while SOC significantly decreased with P addition (p < 0.05), and N + P treatment has low effect on SOC, STN (p > 0.05). By density grouping, it was found that N addition significantly increased light fraction C and N (LFOC, LFN), significantly decreased the light fraction C to N ratio (LFOC/N) (p < 0.05), and increased heavy fraction C and N (HFOC, HFN) accumulation and light fraction to total organic C ratio (LFOC/SOC, p > 0.05). Contrary to N addition, P addition was detrimental to the accumulation of LFOC, LFN and reduced LFOC/SOC. It was found that different reactive oxidized carbon (ROC) increased under N addition but ROC/SOC did not change, while N + P and P treatments increased ROC/SOC, resulting in a decrease in SOC chemical stability. Stable isotope analysis showed that N addition promoted the accumulation of new soil organic matter, whereas P addition enhanced the transformation and utilization of C and N from pre-existing organic matter. Additionally, N addition indirectly increased LFOC by significantly decreasing pH; significantly contributed to LFOC and ROC by increasing STN accumulation promoted by NO₃⁻-N and NH₄⁺-N; and decreased light fraction δ¹³C by significantly increasing dissolved organic C (p < 0.05). P addition had directly significant negative effect on LFOC and SOC (p < 0.05). In conclusion, six-year N deposition enhances soil C and N sequestration while the P enrichment reduces the content of soil C, N fractions and stability in Castanopsis sclerophylla forests. The results provide a scientific basis for predicting the soil C sink function of evergreen broad-leaved forest ecosystem under the background of future climate change. Full article

Subsurface mass concrete infrastructure—including immersed tunnels, dams, and nuclear waste containment systems—frequently faces calcium-leaching risks from prolonged groundwater exposure. An anisotropic stress-leaching damage model incorporating microcrack propagation is developed for underground concrete’s chemo–mechanical coupling. This model investigates stress-induced anisotropy in concrete through the evolution of oriented microcrack networks. The model incorporates nonlinear anisotropic plastic strain from coupled chemical–mechanical damage. Unlike conventional concrete rheology, this model characterizes chemical creep through stress-chemical coupled damage mechanics. The numerical model is incorporated within COMSOL Multiphysics to perform coupled multiphysics simulations. A close match is observed between the numerical predictions and experimental findings. Under high stress loads, calcium leaching and mechanical stress exhibit significant coupling effects. Regarding concrete durability, chemical degradation has a more pronounced effect on concrete’s stiffness and strength reduction compared with stress-generated microcracking. Full article

The anodic behavior of zinc electrodes is important for energy storage, corrosion protection, electrochemical processing, and other practical applications. This study investigates the anodic galvanostatic polarization of zinc foil and bulk electrodes in aqueous oxalic acid solutions, revealing significant differences in their electrochemical behavior, particularly in induction period durations. The induction period’s duration depended on electrolyte concentration, current density, and temperature. Notably, the temperature dependence of the kinetics exhibited contrasting trends: the induction period for foil electrodes increased with temperature, while that of bulk electrodes decreased. Chemical analysis and polishing treatment comparisons showed no significant differences between the foil and bulk electrodes. However, Scanning Electron Microscopy (SEM) observations of samples anodized at different temperatures, combined with Inductively Coupled Plasma–Optical Emission Spectroscopy (ICP-OES) analysis of dissolved electrode material, provided insights into the distinct anodic behaviors. X-ray Diffraction (XRD) studies further confirmed these findings, revealing a crystallographic orientation dependence of the anodic behavior. These results provide detailed information about the electrochemical properties of zinc electrodes, with implications for optimizing their performance in various applications. Full article

Elevated extracellular potassium (K⁺) in the tumor microenvironment (TME) of breast and other cancers is increasingly recognized as a critical factor influencing tumor progression and immune suppression. Current methods for noninvasive mapping of the potassium distribution in tumors are limited. Here, we employed photoacoustic chemical imaging (PACI) with a solvatochromic dye-based, potassium-sensitive nanoprobe (SDKNP) to quantitatively visualize extracellular potassium levels in an orthotopic metaplastic breast cancer mouse model, Ccn6-KO. Tumors of three distinct sizes (5 mm, 10 mm, and 20 mm) were imaged using multi-wavelength photoacoustic imaging at five laser wavelengths (560, 576, 584, 605, and 625 nm). Potassium concentration maps derived from spectral unmixing of the photoacoustic images at the five laser wavelengths revealed significantly increased potassium levels in larger tumors, confirmed independently by inductively coupled plasma mass spectrometry (ICP-MS). The PACI results matched ICP-MS measurements, validating PACI as a robust, noninvasive imaging modality for potassium mapping in tumors in vivo. This work establishes PACI as a promising tool for studying the chemical properties of the TME and provides a foundation for future studies evaluating the immunotherapy response through ionic biomarker imaging. Full article

The Shenhu sea area is rich in unconsolidated hydrate reserves, but the formation mineral particles are small, the rock cementation is weak, and the coupling mechanism of hydrate phase change, fluid seepage, and formation deformation is complex, resulting in unclear productivity change law under depressurization exploitation. Therefore, a thermal–fluid–solid–chemical coupling model for natural gas hydrate depressurization exploitation in the Shenhu sea area was constructed to analyze the variation law of reservoir parameters and productivity. The results show that within 0–30 days, rapid near-well pressure drop (13.83→9.8 MPa, 36.37%) drives peak gas production (25,000 m³/d) via hydrate dissociation, with porosity (0.41→0.52) and permeability (75→100 mD) increasing. Within 30–60 days, slower pressure decline (9.8→8.6 MPa, 12.24%) and fines migration cause permeability fluctuations (120→90 mD), reducing gas production to 20,000 m³/d. Within 60–120 days, pressure stabilizes (~7.6 MPa) with residual hydrate saturation < 0.1, leading to stable low permeability (60 mD) and gas production (15,000 m³/d), with cumulative production reaching 2.2 × 10⁶ m³. This study clarifies that productivity is governed by coupled “pressure-driven dissociation–heat limitation–fines migration” mechanisms, providing key insights for optimizing depressurization strategies (e.g., timed heat supplementation, anti-clogging measures) to enhance commercial viability of unconsolidated hydrate reservoirs. Full article

The most important bauxite deposits in Türkiye are located in the Seydişehir (Konya) and Akseki (Antalya) regions, situated along the western Taurus Mountain, with a total reserve of approximately 44 million tons. Some of the bauxite deposits have been exploited for alumina since the 1970s. In this study, bauxite samples, collected from six different deposits were examined to determine their mineralogical and chemical composition, as well as their REE content, with the aim of identifying which bauxite types are enriched in REEs and assessing their economic potential. The samples included massive, oolitic, and brecciated bauxite types, which were analyzed using optical microscopy, X-ray diffraction (XRD), X-ray fluorescence (XRF) and inductive coupled plasma-mass spectrometry (ICP-MS), field emission scanning electron microscopy (FESEM-EDX), and electron probe micro-analysis (EPMA). Massive bauxites were found to be more homogeneous in both mineralogical and chemical composition, predominantly composed of diaspore, boehmite, and rare gibbsite. Hematite is the most abundant iron oxide mineral in all bauxites, while goethite, rutile, and anatase occur in smaller quantities. Quartz, feldspar, kaolinite, dolomite, and pyrite were specifically determined in brecciated bauxites. Average oxide contents were determined as 52.94% Al₂O₃, 18.21% Fe₂O₃, 7.04% TiO₂, and 2.69% SiO₂. Na₂O, K₂O, and MgO values are typically below 0.5%, while CaO averages 3.54%. The total REE content of the bauxites ranged from 161 to 4072 ppm, with an average of 723 ppm. Oolitic-massive bauxites exhibit the highest REE enrichment. Cerium (Ce) was the most abundant REE, ranging from 87 to 453 ppm (avg. 218 ppm), followed by lanthanum (La), which reached up to 2561 ppm in some of the massive bauxite samples. LREEs such as La, Ce, Pr, and Nd were notably enriched compared to HREEs. The lack of a positive correlation between REEs and major element oxides, as well as with their occurrences in distinct association with Al- and Fe-oxides-hydroxides based on FESEM-EDS and EPMA analyses, suggests that the REEs are present as discrete mineral phases. Furthermore, these findings indicate that the REEs are not incorporated into the crystal structures of other minerals through isomorphic substitution or adsorption. Full article

The contamination of drinking water sources with selenium (Se) oxyanions, including selenite (Se(IV)) and selenate (Se(VI)), contains serious health hazards with an oral intake exceeding 400 µg/day and therefore requires urgent attention. Various natural and anthropogenic sources are responsible for high Se concentrations in aquatic environments. In addition, the chemical behavior and speciation of selenium can vary noticeably depending on the origin of the source water. The Se(VI) oxyanion is more soluble and therefore more abundant in surface water. Se levels in contaminated waters often exceed 50 µg/L and may reach several hundred µg/L, well above drinking water limits set by the World Health Organization (40 µg/L) and Germany (10 µg/L), as well as typical industrial discharge limits (5–10 µg/L). Overall, Se is difficult to remove using conventionally available physical, chemical, and biological treatment technologies. The recent literature has therefore highlighted promising advancements in Se removal using emerging technologies. These include advanced physical separation methods such as membrane-based treatment systems and engineered nanomaterials for selective Se decontamination. Additionally, other integrated approaches incorporating photocatalysis coupled adsorption processes, and bio-electrochemical systems have also demonstrated high efficiency in redox transformation and capturing of Se from contaminated water bodies. These innovative strategies may offer enhanced selectivity, removal, and recovery potential for Se-containing species. Here, a current review outlines the sources, distribution, and chemical behavior of Se in natural waters, along with its toxicity and associated health risks. It also provides a broad and multi-perspective assessment of conventional as well as emerging physical, chemical, and biological approaches for Se removal and/or recovery with further prospects for integrated and sustainable strategies. Full article

With the rising performance demands in road engineering, traditional experiments often fail to reveal the microscopic mechanisms behind asphalt behavior. Molecular dynamics (MD) simulation has emerged as a valuable complement, enabling molecular-level insights into asphalt’s composition, structure, and aging mechanisms. This review summarizes the recent advances in applying MD to asphalt research. It first outlines molecular model construction approaches, including average models, three- and four-component systems, and modified models incorporating SBS, SBR, PU, PE, and asphalt–aggregate interfaces. It then analyzes how MD reveals the key performance aspects—such as high-temperature stability, low-temperature flexibility, self-healing behavior, aging processes, and interfacial adhesion—by capturing the molecular interactions. While MD offers significant advantages, challenges remain: idealized modeling, high computational demands, limited chemical reaction simulation, and difficulties in multi-scale coupling. This paper aims to provide theoretical insights and methodological support for future studies on asphalt performance and highlights MD simulation as a promising tool in pavement material science. Full article

We present a thermodynamically consistent energetic variational model for active nematics driven by ATP hydrolysis. Extending the classical Toner–Tu framework, we introduce a chemo-mechanical coupling mechanism in which the self-advection and polarization dynamics are modulated by the ATP hydrolysis rate. The model is derived using an energetic variational approach that integrates both chemical free energy and mechanical energy into a unified energy dissipation law. The reaction rate equation explicitly incorporates mechanical feedback, revealing how active transport and alignment interactions influence chemical fluxes and vice versa. This formulation not only preserves consistency with non-equilibrium thermodynamics but also provides a transparent pathway for modeling energy transduction in active systems. We also present numerical simulations demonstrating the positive energy transduction under a specific choice of model parameters. The new modeling framework offers new insights into energy transduction and regulation mechanisms in biologically related active systems. Full article

Some chemical reactors exhibit coupled dynamics with multiple equilibrium points and strong nonlinearities. The accurate modeling of these dynamics is crucial to optimal control and increasing the reactor’s economic performance. While neural networks can effectively handle complex nonlinearities, they sacrifice interpretability. Alternatively, block-oriented Hammerstein–Wiener models and Koopman operator-based linear predictors combine nonlinear representation with linear dynamics, offering a gray-box identification approach. This paper comprehensively reviews recent advancements in both the Hammerstein–Wiener and Koopman operator methods and benchmarks their accuracy against neural network-based approaches to modeling a large-scale industrial Fluid Catalytic Cracking fractionator. Furthermore, Monte Carlo simulations are employed to validate performance under varying signal-to-noise ratios. The results demonstrate that the Koopman bilinear model significantly outperforms the other methods in terms of accuracy and robustness. Full article

The valence-shell electronic state spectroscopy of β-butyrolactone (CH₃CHCH₂CO₂) is comprehensively investigated by employing experimental and theoretical methods. We report a novel vacuum ultraviolet (VUV) absorption spectrum in the photon wavelength range from 115 to 320 nm (3.9–10.8 eV), together with ab initio quantum chemical calculations at the time-dependent density functional (TD-DFT) level of theory. The dominant electronic excitations are assigned to mixed valence-Rydberg and Rydberg transitions. The fine structure in the CH₃CHCH₂CO₂ photoabsorption spectrum has been assigned to C=O stretching, $v_7^{\prime }\left(a\right)$, CH₂ wagging, $v_{14}^{\prime }\left(a\right)$, C–O stretching, $v_{22}^{\prime }\left(a\right)$, and C=O bending, $v_{26}^{\prime }\left(a\right)$ modes. Photolysis lifetimes in the Earth’s atmosphere from 0 km up to 50 km altitude have been estimated, showing to be a non-relevant sink mechanism compared to reactions with the ^•OH radical. The nuclear dynamics along the C=O and C–C–C coordinates have been investigated at the TD-DFT level of theory, where, upon electronic excitation, the potential energy curves show important carbonyl bond breaking and ring opening, respectively. Within such an intricate molecular landscape, the higher-lying excited electronic states may keep their original Rydberg character or may undergo Rydberg-to-valence conversion, with vibronic coupling as an important mechanism contributing to the spectrum. Full article

Titanium dioxide (TiO₂), a widely used semiconductor in photocatalysis owing to its adequate potential for water hydrolysis, chemical stability, low toxicity, and low cost. However, its efficiency is limited by fast charge-carrier recombination and poor visible light absorption. Coupling TiO₂ with a p-type semiconductor, such as nickel oxide (NiO), forming a p-n heterojunction, decreases the recombination of charge carriers and increases photocatalytic activity. In this work, the surface of TiO₂ modified with NiO nanoparticles (NPs) induced by radiolysis for photocatalytic hydrogen production was studied. The photocatalytic activity of NiO/TiO₂ was evaluated using methanol as a hole scavenger under UV–visible light. All modified samples presented superior photocatalytic activity compared to bare TiO₂. The dynamics of the charge carriers, a key electronic phenomenon in photocatalysis, was investigated by time-resolved microwave conductivity (TRMC). The results highlight the crucial role of Ni-based NPs modification in enhancing the separation of the charge carrier and activity under UV–visible irradiation. Furthermore, the results revealed that under visible irradiation, NiO-NPs inject electrons into the conduction band of titanium dioxide. Full article

In this study, we perform density functional theory (DFT) simulations to investigate the Raman spectra of the bulk and surface phases of β-Li₃PS₄ (LPS) and Li₂S, as well as their interfaces at varying compositional ratios. This analysis is relevant given the widespread application of these materials in Li–S solid-state batteries, where Li₂S functions not only as a cathode material but also as a protective layer for the lithium anode. Understanding the interfacial structure and how compositional variations influence its chemical and mechanical stability is therefore crucial. Our results demonstrate that the LPS/Li₂S interface remains stable regardless of the compositional ratio. However, when the content of both materials is low, the Raman-active vibrational mode associated with the [PS₄]³⁻ tetrahedral cluster dominates the interface spectrum, effectively obscuring the characteristic peaks of Li₂S and other interfacial features. Only when sufficient amounts of both LPS and Li₂S are present does the coupling between their vibrational modes become sufficiently pronounced to alter the Raman profile and reveal distinct interfacial fingerprints. Full article