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20 pages, 3077 KiB  
Article
Influence of Carboxylic Acids (CAs) on the Structure–Properties Relationship in PLA/Pecan Nutshell (PN) Composites
by Giordano Pierozan Bernardes, Matheus de Prá Andrade and Matheus Poletto
J. Compos. Sci. 2025, 9(8), 422; https://doi.org/10.3390/jcs9080422 - 6 Aug 2025
Abstract
Reinforcing PLA composites with natural fibres is a prominent strategy for improving PLA’s properties while benefiting from its intrinsic biodegradation. However, these composites may be susceptible to an inefficient stress-transferring process due to the weak intermolecular interactions between PLA and natural fibres. A [...] Read more.
Reinforcing PLA composites with natural fibres is a prominent strategy for improving PLA’s properties while benefiting from its intrinsic biodegradation. However, these composites may be susceptible to an inefficient stress-transferring process due to the weak intermolecular interactions between PLA and natural fibres. A well-known practice is to incorporate coupling agents to improve polymer–fibre adhesion, such as carboxylic acids (CAs) and grafted copolymers. CAs are a more affordable and biodegradable option for improving PLA/natural fibre interface strength, resulting in a material with superior mechanical and thermal properties. In this context, this research discusses the potential use of mono (C6 and C8) and di (CC6 and CC8) carboxylic acids as coupling agents in PLA/pecan nutshells (PN) composites. PLA/PN composites with four different CAs were processed in a twin-screw extruder and subsequently injection moulded. The results indicated an increase in the flexural strength of the PLA due to the presence of PN in the neat composite. The use of CAs increased the storage modulus of PLA/PN composites, while C6 and CC8 reduced the PLA composite tan δ peak height. The PLA’s Tg in PLA/PN composite shifted to lower temperatures after the incorporation of CAs while increasing the PLA crystallinity degree. These results strongly suggested that besides acting as efficient coupling agents, these acids also exerted roles as nucleating agents and plasticisers. Full article
(This article belongs to the Section Polymer Composites)
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19 pages, 13584 KiB  
Article
Enhanced Diffraction and Spectroscopic Insight into Layer-Structured Bi6Fe2Ti3O18 Ceramics
by Zbigniew Pędzich, Agata Lisińska-Czekaj, Dionizy Czekaj, Agnieszka Wojteczko and Barbara Garbarz-Glos
Materials 2025, 18(15), 3690; https://doi.org/10.3390/ma18153690 - 6 Aug 2025
Abstract
Bi6Fe2Ti3O18 (BFTO) ceramics were synthesized via a solid-state reaction route using stoichiometric amounts of Bi2O3, TiO2, and Fe2O3 powders. A thermal analysis of the powder mixture was [...] Read more.
Bi6Fe2Ti3O18 (BFTO) ceramics were synthesized via a solid-state reaction route using stoichiometric amounts of Bi2O3, TiO2, and Fe2O3 powders. A thermal analysis of the powder mixture was conducted to optimize the heat treatment parameters. Energy-dispersive X-ray spectroscopy (EDS) confirmed the conservation of the chemical composition following calcination. Final densification was achieved through hot pressing. The crystal structure of the sintered samples, examined via X-ray diffraction at room temperature, revealed a tetragonal symmetry for BFTO ceramics sintered at 850 °C. Electron backscatter diffraction (EBSD) provided detailed insight into the crystallographic orientation and microstructure. Broadband dielectric spectroscopy (BBDS) was employed to investigate the dielectric response of BFTO ceramics over a frequency range of 10 mHz to 10 MHz and a temperature range of −30 °C to +200 °C. The temperature dependence of the relative permittivity (εr) and dielectric loss tangent (tan δ) were measured within a frequency range of 100 kHz to 900 kHz and a temperature range of 25 °C to 570 °C. The impedance data obtained from the BBDS measurements were validated using the Kramers–Kronig test and modeled using the Kohlrausch–Williams–Watts (KWW) function. The stretching parameter (β) ranged from ~0.72 to 0.82 in the impedance formalism within the temperature range from 200 °C to 20 °C. Full article
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14 pages, 3150 KiB  
Article
Research on the Influence Mechanism of Thermal Load on the Au-Sn Sealing Weld State on Three-Dimensional DPC Substrates
by Heran Zhao, Lihua Cao, ShiZhao Wang, He Zhang and Mingxiang Chen
Materials 2025, 18(15), 3678; https://doi.org/10.3390/ma18153678 - 5 Aug 2025
Abstract
Direct copper-plated ceramic (DPC) substrates have emerged as a favored solution for power device packaging due to their unique technical advantages. AuSn, characterized by its high hermeticity and environmental adaptability, represents the optimal sealing technology for DPC substrates. Through the application of vacuum [...] Read more.
Direct copper-plated ceramic (DPC) substrates have emerged as a favored solution for power device packaging due to their unique technical advantages. AuSn, characterized by its high hermeticity and environmental adaptability, represents the optimal sealing technology for DPC substrates. Through the application of vacuum sintering techniques and adjustment of peak temperatures (325 °C, 340 °C, and 355 °C), the morphology and composition of interfacial compounds were systematically investigated, along with an analysis of their formation mechanisms. A gradient aging experiment was designed (125 °C/150 °C/175 °C × oxygen/argon dual atmosphere × 600 h) to elucidate the synergistic effects of environmental temperature and atmosphere on the growth of intermetallic compounds (IMCs). The results indicate that the primary reaction in the sealing weld seam involves Ni interacting with Au-Sn to form (Ni, Au)3Sn2 and Au5Sn. However, upon completion of the sealing process, this reaction remains incomplete, leading to a coexistence state of (Ni, Au)3Sn2, Au5Sn, and AuSn. Additionally, Ni diffuses into the weld seam center via dendritic fracture and locally forms secondary phases such as δ(Ni) and ζ’(Ni). These findings suggest that the weld seam interface exhibits a complex, irregular, and asymmetric microstructure comprising multiple coexisting compounds. It was determined that Tpeak = 325 °C to 340 °C represents the ideal welding temperature range, where the weld seam morphology, width, and Ni diffusion degree achieve optimal states, ensuring excellent device hermeticity. Aging studies further demonstrate that IMC growth remains within controllable limits. These findings address critical gaps in the understanding of the microstructural evolution and interface characteristics of asymmetric welded joints formed by multi-material systems. Full article
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17 pages, 545 KiB  
Article
Concordance Index-Based Comparison of Inflammatory and Classical Prognostic Markers in Untreated Hepatocellular Carcinoma
by Natalia Afonso-Luis, Irene Monescillo-Martín, Joaquín Marchena-Gómez, Pau Plá-Sánchez, Francisco Cruz-Benavides and Carmen Rosa Hernández-Socorro
J. Clin. Med. 2025, 14(15), 5514; https://doi.org/10.3390/jcm14155514 - 5 Aug 2025
Abstract
Background/Objectives: Inflammation-based markers have emerged as potential prognostic tools in hepatocellular carcinoma (HCC), but comparative data with classical prognostic factors in untreated HCC are limited. This study aimed to evaluate and compare the prognostic performance of inflammatory and conventional markers using Harrell’s [...] Read more.
Background/Objectives: Inflammation-based markers have emerged as potential prognostic tools in hepatocellular carcinoma (HCC), but comparative data with classical prognostic factors in untreated HCC are limited. This study aimed to evaluate and compare the prognostic performance of inflammatory and conventional markers using Harrell’s concordance index (C-index). Methods: This retrospective study included 250 patients with untreated HCC. Prognostic variables included age, BCLC stage, Child–Pugh classification, Milan criteria, MELD score, AFP, albumin, Charlson comorbidity index, and the inflammation-based markers neutrophil-to-lymphocyte ratio (NLR), platelet-to-lymphocyte ratio (PLR), monocyte-to-lymphocyte ratio (MLR), Systemic Inflammation Response Index (SIRI), and Systemic Immune-inflammation Index (SIII). Survival was analyzed using Cox regression. Predictive performance was assessed using the C-index, Akaike Information Criterion (AIC), and likelihood ratio tests. Results: Among the classical markers, BCLC showed the highest predictive performance (C-index: 0.717), while NLR ranked highest among the inflammatory markers (C-index: 0.640), above the MELD score and Milan criteria. In multivariate analysis, NLR ≥ 2.3 remained an independent predictor of overall survival (HR: 1.787; 95% CI: 1.264–2.527; p < 0.001), along with BCLC stage, albumin, Charlson index, and Milan criteria. Including NLR in the model modestly improved the C-index (from 0.781 to 0.794) but significantly improved model fit (Δ–2LL = 10.75; p = 0.001; lower AIC). Conclusions: NLR is an accessible, cost-effective, and independent prognostic marker for overall survival in untreated HCC. It shows discriminative power comparable to or greater than most conventional predictors and may complement classical stratification tools for HCC. Full article
(This article belongs to the Section General Surgery)
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23 pages, 2750 KiB  
Article
Seasonal Sea Surface Temperatures from Mercenaria spp. During the Plio-Pleistocene: Oxygen Isotope Versus Clumped Isotope Paleothermometers
by Garrett F. N. Braniecki, Donna Surge and Ethan G. Hyland
Geosciences 2025, 15(8), 295; https://doi.org/10.3390/geosciences15080295 - 2 Aug 2025
Viewed by 199
Abstract
The Mid-Piacenzian Warm Interval (MPWI) is marked by warmer temperatures and higher atmospheric CO2 levels than today, making it an analogue for late-21st-century-warming, whereas the early Pleistocene cooling is more like today. We compare seasonal growth temperatures derived from oxygen isotope ratios [...] Read more.
The Mid-Piacenzian Warm Interval (MPWI) is marked by warmer temperatures and higher atmospheric CO2 levels than today, making it an analogue for late-21st-century-warming, whereas the early Pleistocene cooling is more like today. We compare seasonal growth temperatures derived from oxygen isotope ratios (δ18O) and clumped isotopes (∆47) in Mercenaria. Modern shells were previously collected from coastal NC. The fossil shells are from the Duplin (MPWI) and Waccamaw Formations (early Pleistocene), NC. Oxygen isotope ratios range from −2.2‰ to 2.3‰ (modern), −0.9‰ to 2.4‰ (MPWI), and −0.9‰ to 2.9‰ (early Pleistocene). The values of Δ47 range from 0.576‰ to 0.639‰ (modern), 0.566‰ to 0.621‰ (MPWI), and 0.581‰ to 0.615‰ (early Pleistocene). We show that Mercenaria do not require a species-specific ∆47 calibration. Modern and MPWI ∆47-derived summer/winter temperatures (SST∆47) and seasonal amplitudes are indistinguishable from δ18O-derived temperatures. The early Pleistocene summer SST∆47 is indistinguishable from δ18O-derived temperatures, but the winter SST∆47 is warmer by 5 °C and may reflect within-shell time averaging. The modern summer/winter SST∆47 are indistinguishable from the MPWI, but the MPWI has a lower seasonal amplitude by 5 °C. Compared to our calculated δ18Osw values, modeled values for the MPWI are within error but are much lower, and they are not within error for the early Pleistocene. Full article
(This article belongs to the Special Issue Pliocene Studies in Paleobiology, Paleoenvironment and Paleoclimate)
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17 pages, 3193 KiB  
Article
Effects of Nitrogen and Phosphorus Additions on the Stability of Soil Carbon Fractions in Subtropical Castanopsis sclerophylla Forests
by Yunze Dai, Xiaoniu Xu and LeVan Cuong
Forests 2025, 16(8), 1264; https://doi.org/10.3390/f16081264 - 2 Aug 2025
Viewed by 163
Abstract
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 [...] Read more.
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
(This article belongs to the Section Forest Soil)
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14 pages, 2350 KiB  
Article
Temporal Deformation Characteristics of Hydraulic Asphalt Concrete Slope Flow Under Different Test Temperatures
by Xuexu An, Jingjing Li and Zhiyuan Ning
Materials 2025, 18(15), 3625; https://doi.org/10.3390/ma18153625 - 1 Aug 2025
Viewed by 217
Abstract
To investigate temporal deformation mechanisms of hydraulic asphalt concrete slope flow under evolving temperatures, this study developed a novel temperature-controlled slope flow intelligent test apparatus. Using this apparatus, slope flow tests were conducted at four temperature levels: 20 °C, 35 °C, 50 °C, [...] Read more.
To investigate temporal deformation mechanisms of hydraulic asphalt concrete slope flow under evolving temperatures, this study developed a novel temperature-controlled slope flow intelligent test apparatus. Using this apparatus, slope flow tests were conducted at four temperature levels: 20 °C, 35 °C, 50 °C, and 70 °C. By applying nonlinear dynamics theory, the temporal evolution of slope flow deformation and its nonlinear mechanical characteristics under varying temperatures were thoroughly analyzed. Results indicate that the thermal stability of hydraulic asphalt concrete is synergistically governed by the phase-transition behavior between asphalt binder and aggregates. Temporal evolution of slope flow exhibits a distinct three-stage pattern as follows: rapid growth (0~12 h), where sharp temperature rise disrupts the primary skeleton of coarse aggregates; decelerated growth (12~24 h), where an embryonic secondary skeleton forms and progressively resists deformation; stabilization (>24 h), where reorganization of coarse aggregates is completed, establishing structural equilibrium. The thermal stability temperature influence factor (δ) shows a nonlinear concave growth trend with increasing test temperature. Dynamically, this process transitions sequentially through critical stability, nonlinear stability, period-doubling oscillatory stability, and unsteady states. Full article
(This article belongs to the Special Issue Advances in Material Characterization and Pavement Modeling)
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15 pages, 4578 KiB  
Article
Improving Balance Between Oxygen Permeability and Stability of Ba0.5Sr0.5Co0.8Fe0.2O3−δ Through High-Entropy Design
by Yongfan Zhu, Meng Wu, Guangru Zhang, Zhengkun Liu and Gongping Liu
Membranes 2025, 15(8), 232; https://doi.org/10.3390/membranes15080232 - 1 Aug 2025
Viewed by 240
Abstract
Currently, the trade-off between oxygen permeation flux and structural stability in conventional perovskite oxides restricts the practical application of oxygen permeable membranes. In this study, a high-entropy design was applied to the B-site of BSCF matrix materials, resulting in the successful synthesis of [...] Read more.
Currently, the trade-off between oxygen permeation flux and structural stability in conventional perovskite oxides restricts the practical application of oxygen permeable membranes. In this study, a high-entropy design was applied to the B-site of BSCF matrix materials, resulting in the successful synthesis of a high-entropy perovskite, Ba0.5Sr0.5Co0.71Fe0.2Ta0.03Ni0.03Zr0.03O3−δ. The crystal structure, microstructure, and elemental composition of the material were systematically characterized and analyzed. Theoretical analysis and experimental characterization confirm that the material exhibits a stable single-phase high-entropy perovskite oxide structure. Under He as the sweep gas, the membrane achieved an oxygen permeation flux of 1.28 mL·cm−2·min−1 and operated stably for over 100 h (1 mm thick, 900 °C). In a 20% CO2/He atmosphere, the flux remained above 0.92 mL·cm−2·min−1 for over 100 h, demonstrating good CO2 tolerance. Notably, when the sweep gas is returned to the pure He atmosphere, the oxygen permeation flux fully recovers to 1.28 mL·cm−2·min−1, with no evidence of leakage. These findings indicate that the proposed B-site doping strategy can break the trade-off between oxygen permeability and structural stability in conventional perovskite membranes. This advancement supports the industrialization of oxygen permeable membranes and offers valuable theoretical guidance for the design of high-performance perovskite materials. Full article
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21 pages, 5409 KiB  
Article
Sustainable Rubber Solutions: A Study on Bio-Based Oil and Resin Blends
by Frances van Elburg, Fabian Grunert, Claudia Aurisicchio, Micol di Consiglio, Auke Talma, Pilar Bernal-Ortega and Anke Blume
Polymers 2025, 17(15), 2111; https://doi.org/10.3390/polym17152111 - 31 Jul 2025
Viewed by 330
Abstract
One of the most important challenges the tire industry faces is becoming carbon-neutral and using 100% sustainable materials by 2050. Utilizing materials from renewable sources and recycled substances is a key aspect of achieving this goal. Petroleum-based oils, such as Treated Distillate Aromatic [...] Read more.
One of the most important challenges the tire industry faces is becoming carbon-neutral and using 100% sustainable materials by 2050. Utilizing materials from renewable sources and recycled substances is a key aspect of achieving this goal. Petroleum-based oils, such as Treated Distillate Aromatic Extract (TDAE), are frequently used in rubber compounds, and a promising strategy to enhance sustainability is to use bio-based plasticizer alternatives. However, research has shown that the replacement of TDAE oil with bio-based oils or resins can significantly alter the glass transition temperature (Tg) of the final compound, influencing the tire properties. In this study, the theory was proposed that using a plasticizer blend, comprising oil and resin, in a rubber compound would result in similar Tg values as the reference compound containing TDAE. To test this, the cycloaliphatic di-ester oil Hexamoll DINCH, which can be made out of bio-based feedstock by the BioMass Balance approach, was selected and blended with the cycloaliphatic hydrocarbon resin Escorez 5300. Various oil-to-resin ratios were investigated, and a linear increase in the Tg of the vulcanizate was obtained when increasing the resin content and decreasing the oil content. Additionally, a 50/50 blend, consisting of 18.75 phr Hexamoll DINCH and 18.75 phr Escorez 5300, resulted in the same Tg of −19 °C as a compound containing 37.5 phr TDAE. Furthermore, this blend resulted in similar curing characteristics and cured Payne effect as the reference with TDAE. Moreover, a similar rolling resistance indicator (tan δ at 60 °C = 0.115), a slight deterioration in wear resistance (ARI = 83%), but an improvement in the stress–strain behavior (M300 = 9.18 ± 0.20 MPa and Ts = 16.3 ± 0.6 MPa) and wet grip indicator (tan δ at 0 °C = 0.427) were observed. The results in this work show the potential of finding a balance between optimal performance and sustainability by using plasticizer blends. Full article
(This article belongs to the Special Issue Exploration and Innovation in Sustainable Rubber Performance)
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12 pages, 3668 KiB  
Article
The Study on the Electrochemical Efficiency of Yttrium-Doped High-Entropy Perovskite Cathodes for Proton-Conducting Fuel Cells
by Bingxue Hou, Xintao Wang, Rui Tang, Wenqiang Zhong, Meiyu Zhu, Zanxiong Tan and Chengcheng Wang
Materials 2025, 18(15), 3569; https://doi.org/10.3390/ma18153569 - 30 Jul 2025
Viewed by 266
Abstract
The commercialization of proton-conducting fuel cells (PCFCs) is hindered by the limited electroactivity and durability of cathodes at intermediate temperatures ranging from 400 to 700 °C, a challenge exacerbated by an insufficient understanding of high-entropy perovskite (HEP) materials for oxygen reduction reaction (ORR) [...] Read more.
The commercialization of proton-conducting fuel cells (PCFCs) is hindered by the limited electroactivity and durability of cathodes at intermediate temperatures ranging from 400 to 700 °C, a challenge exacerbated by an insufficient understanding of high-entropy perovskite (HEP) materials for oxygen reduction reaction (ORR) optimization. This study introduces an yttrium-doped HEP to address these limitations. A comparative analysis of Ce0.2−xYxBa0.2Sr0.2La0.2Ca0.2CoO3−δ (x = 0, 0.2; designated as CBSLCC and YBSLCC) revealed that yttrium doping enhanced the ORR activity, reduced the thermal expansion coefficient (19.9 × 10−6 K−1, 30–900 °C), and improved the thermomechanical compatibility with the BaZr0.1Ce0.7Y0.1Yb0.1O3−δ electrolytes. Electrochemical testing demonstrated a peak power density equal to 586 mW cm−2 at 700 °C, with a polarization resistance equaling 0.3 Ω cm2. Yttrium-induced lattice distortion promotes proton adsorption while suppressing detrimental Co spin-state transitions. These findings advance the development of durable, high-efficiency PCFC cathodes, offering immediate applications in clean energy systems, particularly for distributed power generation. Full article
(This article belongs to the Section Energy Materials)
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18 pages, 1800 KiB  
Article
Chemometric Evaluation of Official and Advanced Methods for Detecting Olive Oil Authenticity in Canned Tuna
by Marjeta Mencin, Milena Bučar-Miklavčič, Maja Podgornik and Nives Ogrinc
Foods 2025, 14(15), 2667; https://doi.org/10.3390/foods14152667 - 29 Jul 2025
Viewed by 263
Abstract
This study evaluated the authenticity of olive oil in canned tuna products from the Slovenian market using both official methods, including fatty acid (FA) profiling, determination of the equivalent carbon number difference (ΔECN42), and sterol analysis, and an advanced method: stable carbon isotope [...] Read more.
This study evaluated the authenticity of olive oil in canned tuna products from the Slovenian market using both official methods, including fatty acid (FA) profiling, determination of the equivalent carbon number difference (ΔECN42), and sterol analysis, and an advanced method: stable carbon isotope analysis (δ13C) of FAs obtained through compound-specific isotope analysis (CSIA). Results from both methods confirmed that all 10 samples were authentic, as per the limits set by EU Regulation 2022/2104 and supported by the scientific literature. Method performance was further evaluated by adulterating the olive oil from the canned tuna with 5–20% vegetable oil (VO) or hazelnut oil (HO). While FA analysis struggled to differentiate adulterants with similar FA profiles, CSIA of FAs significantly improved detection. However, distinguishing between VO and HO blended samples remained challenging. PLS-DA analysis further supported the potential of using δ13C values of FA for food authentication. Storage of adulterated samples also influenced FA composition, leading to significant changes in MUFA/PUFA ratios and δ13C values, which became less negative, likely due to oxidative degradation. In summary, the combination of official and advanced methods, supported by chemometric analysis, offers a robust approach to ensuring the authenticity of olive oil in canned tuna. Full article
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16 pages, 2131 KiB  
Article
A Comparative Study on ZrO2- and MgO-Based Sulfonic Acid Materials for the Reactive Adsorption of o-Xylene
by Hongmei Wang, Xiaoxu Zhang, Ziqi Shen and Zichuan Ma
Molecules 2025, 30(15), 3171; https://doi.org/10.3390/molecules30153171 - 29 Jul 2025
Viewed by 223
Abstract
The recovery and abatement of volatile organic compounds (VOCs) have received increasing attention due to their significant environmental and health impacts. Supported sulfonic acid materials have shown great potential in converting aromatic VOCs into their non-volatile derivatives through reactive adsorption. However, the anchoring [...] Read more.
The recovery and abatement of volatile organic compounds (VOCs) have received increasing attention due to their significant environmental and health impacts. Supported sulfonic acid materials have shown great potential in converting aromatic VOCs into their non-volatile derivatives through reactive adsorption. However, the anchoring state of sulfonic acid groups, which is closely related to the properties of the support, greatly affects their performance. In this study, two supported sulfonic acid materials, SZO and SMO, were prepared by treating ZrO2 and MgO with chlorosulfonic acid, respectively, to investigate the influence of the support properties on the anchoring state of sulfonic acid groups and their reactive adsorption performance for o-xylene. The supports, adsorbents, and adsorption products were extensively characterized, and the reactivity of SZO and SMO towards o-xylene was systematically compared. The results showed that sulfonic acid groups are anchored on the ZrO2 surface through covalent bonding, forming positively charged sulfonic acid sites ([O1.5Zr-O]δ−-SO3Hδ+) with a loading of 3.6 mmol/g. As a result, SZO exhibited excellent removal efficiency (≥91.3%) and high breakthrough adsorption capacity (ranging from 38.59 to 82.07 mg/g) for o-xylene in the temperature range of 130 –150 °C. In contrast, sulfonic acid groups are anchored on the MgO surface via ion-paired bonding, leading to the formation of negatively charged sulfonic acid sites ([O0.5Mg]+:OSO3H), which prevents their participation in the electrophilic sulfonation reaction with o-xylene molecules. This work provides new insights into tuning and enhancing the performance of supported sulfonic acid materials for the resource-oriented treatment of aromatic VOCs. Full article
(This article belongs to the Special Issue Applied Chemistry in Asia)
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12 pages, 1916 KiB  
Article
Electrical Conductivity of High-Entropy Calcium-Doped Six- and Seven-Cation Perovskite Materials
by Geoffrey Swift, Sai Ram Gajjala and Rasit Koc
Crystals 2025, 15(8), 686; https://doi.org/10.3390/cryst15080686 - 28 Jul 2025
Viewed by 264
Abstract
Novel high-entropy perovskite oxide powders were synthesized using a sol-gel process. The B-site contained five cations: chromium, cobalt, iron, manganese, and nickel. The B-site cations were present on an equiatomic basis. The A-site cation was lanthanum, with calcium doping. The amount of A-site [...] Read more.
Novel high-entropy perovskite oxide powders were synthesized using a sol-gel process. The B-site contained five cations: chromium, cobalt, iron, manganese, and nickel. The B-site cations were present on an equiatomic basis. The A-site cation was lanthanum, with calcium doping. The amount of A-site doping varied from 0 to 30 at%, yielding a composition of La1−xCax(Co0.2Cr0.2Fe0.2Mn0.2Ni0.2)O3−δ. The resulting perovskite powders were pressurelessly sintered in air at 1400 °C for 2 h. Sintered densities were measured, and the grain structure was imaged via scanning electron microscopy to investigate the effect of doping. Samples were cut and polished, and their resistance was measured at varying temperatures in air to obtain the electrical conductivity and the mechanism that governs it. Plots of electrical conductivity as a function of composition and temperature indicate that the increased configurational entropy of the perovskite materials has a demonstrable effect. Full article
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16 pages, 3885 KiB  
Article
Synthesis and Properties of Bi1.8Mn0.5Ni0.5Ta2O9-Δ Pyrochlore
by Sergey V. Nekipelov, Olga V. Petrova, Alexandra V. Koroleva, Mariya G. Krzhizhanovskaya, Kristina N. Parshukova, Nikolay A. Sekushin, Boris A. Makeev and Nadezhda A. Zhuk
Chemistry 2025, 7(4), 119; https://doi.org/10.3390/chemistry7040119 - 25 Jul 2025
Viewed by 192
Abstract
Pyrochlore Bi1.8Mn0.5Ni0.5Ta2O9-Δ (sp.gr. Fd-3m, a = 10.5038(9) Å) was synthesized by the solid-phase reaction method and characterized by vibrational and X-ray spectroscopy. According to scanning electron microscopy, the ceramics are characterized by a [...] Read more.
Pyrochlore Bi1.8Mn0.5Ni0.5Ta2O9-Δ (sp.gr. Fd-3m, a = 10.5038(9) Å) was synthesized by the solid-phase reaction method and characterized by vibrational and X-ray spectroscopy. According to scanning electron microscopy, the ceramics are characterized by a porous microstructure formed by randomly oriented oblong grains. The average crystallite size determined by X-ray diffraction is 65 nm. The charge state of transition element cations in the pyrochlore was analyzed by soft X-ray spectroscopy using synchrotron radiation. For mixed pyrochlore, a characteristic shift of Bi4f and Ta4f and Ta5p spectra to the region of lower energies by 0.25 and 0.90 eV is observed compared to the binding energy in Bi2O3 and Ta2O5 oxides. XPS Mn2p spectrum of pyrochlore has an intermediate energy position compared to the binding energy in MnO and Mn2O3, which indicates a mixed charge state of manganese (II, III) cations. Judging by the nature of the Ni2p spectrum of the complex oxide, nickel ions are in the charge state of +(2+ζ). The relative permittivity of the sample in a wide temperature (up to 350 °C) and frequency range (25–106 Hz) does not depend on the frequency and exhibits a constant low value of 25. The minimum value of 4 × 10−3 dielectric loss tangent is exhibited by the sample at a frequency of 106 Hz. The activation energy of conductivity is 0.7 eV. The electrical behavior of the sample is modeled by an equivalent circuit containing a Warburg diffusion element. Full article
(This article belongs to the Section Inorganic and Solid State Chemistry)
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15 pages, 1897 KiB  
Article
Dual Mechanisms of Nitrate in Alleviating Ammonium Toxicity: Enhanced Photosynthesis and Optimized Ammonium Utilization in Orychophragmus violaceus
by Kaiyan Zhang, Haitao Li, Hongtao Hang, Xinhua He and Yanyou Wu
Agronomy 2025, 15(8), 1789; https://doi.org/10.3390/agronomy15081789 - 25 Jul 2025
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Abstract
Ammonium (NH4+) toxicity impairs plant growth, but nitrate (NO3) can mitigate this effect through unresolved mechanisms. Using leaf δ13C values (photosynthetic capacity) and a bidirectional 15N tracer (NH4+ assimilation efficiency and source [...] Read more.
Ammonium (NH4+) toxicity impairs plant growth, but nitrate (NO3) can mitigate this effect through unresolved mechanisms. Using leaf δ13C values (photosynthetic capacity) and a bidirectional 15N tracer (NH4+ assimilation efficiency and source utilization), this study investigated these mechanisms in 35-day-old Orychophragmus violaceus plantlets grown in modified Murashige and Skoog media under varying NH4+:NO3 ratios. 15N isotope fractionation during NH4+ (same fixed 20 mM NH4Cl) assimilation decreased with increasing NO3 supply (10, 20, and 40 mM NaNO3). Under 20 mM NH4+15N = −2.64‰) at two 15NO3-labels (δ15N-NO3 = 8.08‰, low 15N, L) and (δ15N-NO3 = 22.67‰, high 15N, H), increasing NO3 concentrations enhanced NO3 assimilation, alleviating acidic stress from NH4+ and improving photosynthesis. Higher NO3 levels also increased NH4+ utilization efficiency, reducing futile NH4+ cycling and decreasing associated 15N fractionation during assimilation. Our results demonstrate that NO3 alleviates NH4+ toxicity primarily by enhancing photosynthetic performance and optimizing NH4+ utilization efficiency. Full article
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