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Keywords = metal–metal bonding

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12 pages, 2764 KiB  
Article
AlxCoCrFeNi High-Entropy Alloys Enable Simultaneous Electrical and Mechanical Robustness at Thermoelectric Interfaces
by Xiaoxia Zou, Wangjie Zhou, Xinxin Li, Yuzeng Gao, Jingyi Yu, Linglu Zeng, Guangteng Yang, Li Liu, Wei Ren and Yan Sun
Materials 2025, 18(15), 3688; https://doi.org/10.3390/ma18153688 - 6 Aug 2025
Abstract
The interface between high-performance thermoelectric materials and electrodes critically governs the conversion efficiency and long-term reliability of thermoelectric generators under high-temperature operation. Here, we propose AlxCoCrFeNi high-entropy alloys (HEA) as barrier layers to bond Cu-W electrodes with p-type skutterudite (p-SKD) thermoelectric [...] Read more.
The interface between high-performance thermoelectric materials and electrodes critically governs the conversion efficiency and long-term reliability of thermoelectric generators under high-temperature operation. Here, we propose AlxCoCrFeNi high-entropy alloys (HEA) as barrier layers to bond Cu-W electrodes with p-type skutterudite (p-SKD) thermoelectric materials. The HEA/p-SKD interface exhibited excellent chemical bonding with a stable and controllable reaction layer, forming a dense, defect-free (Fe,Ni,Co,Cr)Sb phase (thickness of ~2.5 μm) at the skutterudites side. The interfacial resistivity achieved a low value of 0.26 μΩ·cm2 and remained at 7.15 μΩ·cm2 after aging at 773 K for 16 days. Moreover, the interface demonstrated remarkable mechanical stability, with an initial shear strength of 88 MPa. After long-term aging for 16 days at 773 K, the shear strength retained 74 MPa (only 16% degradation), ranking among the highest reported for thermoelectric materials/metal joints. Remarkably, the joint maintained a shear strength of 29 MPa even after 100 continuous thermal cycles (623–773 K), highlighting its outstanding thermo-mechanical stability. These results validate the AlxCoCrFeNi high-entropy alloys as an ideal interfacial material for thermoelectric generators, enabling simultaneous optimization of electrical and mechanical performance in harsh environments. Full article
(This article belongs to the Section Metals and Alloys)
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12 pages, 12870 KiB  
Article
Direct Glass-to-Metal Welding by Femtosecond Laser Pulse Bursts: I, Conditions for Successful Welding with a Gap
by Qingfeng Li, Gabor Matthäus, David Sohr and Stefan Nolte
Nanomaterials 2025, 15(15), 1202; https://doi.org/10.3390/nano15151202 - 6 Aug 2025
Abstract
We report on the welding of optical borosilicate glass to an unpolished copper substrate (surface Ra of 0.27 µm and Rz of 1.89 µm) using bursts of femtosecond laser pulses. The present paper puts forth the hypothesis that glass–metal welding with a gap [...] Read more.
We report on the welding of optical borosilicate glass to an unpolished copper substrate (surface Ra of 0.27 µm and Rz of 1.89 µm) using bursts of femtosecond laser pulses. The present paper puts forth the hypothesis that glass–metal welding with a gap is contingent upon the ejection of molten jets of glass. We have ascertained the impact of pulse energy and focal position on weldability. This finding serves to substantiate our initial hypothesis and provides a framework for understanding the conditions under which this hypothesis is applicable. Under optimal conditions, but without the assistance of any clamping system, our welded samples maintained a breaking resistance of up to 10.9 MPa. Full article
(This article belongs to the Special Issue Ultrafast Laser Micro-Nano Welding: From Principles to Applications)
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38 pages, 4692 KiB  
Review
Progress and Challenges in the Process of Using Solid Waste as a Catalyst for Biodiesel Synthesis
by Zhaolin Dong, Kaili Dong, Haotian Li, Liangyi Zhang and Yitong Wang
Molecules 2025, 30(15), 3243; https://doi.org/10.3390/molecules30153243 - 1 Aug 2025
Viewed by 201
Abstract
Biodiesel, as one of the alternatives to fossil fuels, faces significant challenges in large-scale industrial production due to its high production costs. In addition to raw material costs, catalyst costs are also a critical factor that cannot be overlooked. This review summarizes various [...] Read more.
Biodiesel, as one of the alternatives to fossil fuels, faces significant challenges in large-scale industrial production due to its high production costs. In addition to raw material costs, catalyst costs are also a critical factor that cannot be overlooked. This review summarizes various methods for preparing biodiesel catalysts from solid waste. These methods not only enhance the utilization rate of waste but also reduce the production costs and environmental impact of biodiesel. Finally, the limitations of waste-based catalysts and future research directions are discussed. Research indicates that solid waste can serve as a catalyst carrier or active material for biodiesel production. Methods such as high-temperature calcination, impregnation, and coprecipitation facilitate structural modifications to the catalyst and the formation of active sites. The doping of metal ions not only alters the catalyst’s acid-base properties but also forms stable metal bonds with functional groups on the carrier, thereby maintaining catalyst stability. The application of microwave-assisted and ultrasound-assisted methods reduces reaction parameters, making biodiesel production more economical and sustainable. Overall, this study provides a scientific basis for the reuse of solid waste and ecological protection, emphasizes the development potential of waste-based catalysts in biodiesel production, and offers unique insights for innovation in this field, thereby accelerating the commercialization of biodiesel. Full article
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13 pages, 2303 KiB  
Article
A Stable Metal Chalcogenide Cluster-Based Framework Decorated with Transition Metal Complexes for an Efficient Electrocatalytic O2 Reduction Reaction
by Xiang Wang, Juan Li and Tao Wu
Nanomaterials 2025, 15(15), 1186; https://doi.org/10.3390/nano15151186 - 1 Aug 2025
Viewed by 155
Abstract
Highly efficient and stable non-Pt-based electrocatalysts for oxygen reduction reactions (ORRs) are highly desirable in energy conversion and storage systems. Herein, we report a hydrothermally synthesized metal chalcogenide cluster-based framework (NCF-3-Mn), which is decorated with transition metal complexes ([Mn(TEPA)]2+, TEPA = [...] Read more.
Highly efficient and stable non-Pt-based electrocatalysts for oxygen reduction reactions (ORRs) are highly desirable in energy conversion and storage systems. Herein, we report a hydrothermally synthesized metal chalcogenide cluster-based framework (NCF-3-Mn), which is decorated with transition metal complexes ([Mn(TEPA)]2+, TEPA = tetraethylenepentamine), for an electrocatalytic O2 reduction reaction (ORR). Benefitting from the abundant Mn-S bonds and Mn-N-C structures in NCF-3-Mn, it was found that NCF-3-Mn displayed a high onset potential (0.90 V) and an efficient four-electron transfer reaction pathway, which are much better than those of its analogue framework (T2-GaSbS). Moreover, NCF-3-Mn also exhibited a considerable long-term stability and methanol resistance toward ORRs. This work will present new opportunities for exploring the utilization of chalcogenide frameworks as novel non-Pt electrocatalysts for ORRs. Full article
(This article belongs to the Collection Micro/Nanoscale Open Framework Materials (OFMs))
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11 pages, 5112 KiB  
Article
Fabrication of a Porous TiNi3 Intermetallic Compound to Enhance Anti-Corrosion Performance in 1 M KOH
by Zhenli He, Yue Qiu, Yuehui He, Qian Zhao, Zhonghe Wang and Yao Jiang
Metals 2025, 15(8), 865; https://doi.org/10.3390/met15080865 (registering DOI) - 1 Aug 2025
Viewed by 175
Abstract
Porous intermetallic compounds have the properties of porous materials as well as a combination of covalent and metallic bonds, and they exhibit high porosity, structural stability, and corrosion resistance. In this work, a porous TiNi3 intermetallic compound was fabricated through reactive synthesis [...] Read more.
Porous intermetallic compounds have the properties of porous materials as well as a combination of covalent and metallic bonds, and they exhibit high porosity, structural stability, and corrosion resistance. In this work, a porous TiNi3 intermetallic compound was fabricated through reactive synthesis of elemental powders. Next, detailed studies of its phase composition and pore structure characteristics at different sintering temperatures, as well as its corrosion behavior against an alkaline environment, were carried out. The results show that the as-prepared porous TiNi3 intermetallic compound has abundant pore structures, with an open porosity of 56.5%, which can be attributed to a combination of the bridging effects of initial powder particles and the Kirkendall effect occurring during the sintering process. In 1 M KOH solution, a higher positive corrosion potential (−0.979 VSCE) and a lower corrosion current density (1.18 × 10−4 A∙cm−2) were exhibited by the porous TiNi3 intermetallic compound, compared to the porous Ni, reducing the thermodynamic corrosion tendency and the corrosion rate. The corresponding corrosion process is controlled by the charge transfer process, and the increased charge transfer resistance value (713.9 Ω⋅cm2) of TiNi3 makes it more difficult to charge-transfer than porous Ni (204.5 Ω⋅cm2), thus decreasing the rate of electrode reaction. The formation of a more stable passive film with the incorporation of Ti contributes to this improved corrosion resistance performance. Full article
(This article belongs to the Special Issue Advanced Ti-Based Alloys and Ti-Based Materials)
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35 pages, 3599 KiB  
Review
Recent Advances in Borylation and Suzuki-Type Cross-Coupling—One-Pot Miyaura-Type C–X and C–H Borylation–Suzuki Coupling Sequence
by Nouhaila Bahyoune, Mohammed Eddahmi, Perikleia Diamantopoulou, Ioannis D. Kostas and Latifa Bouissane
Catalysts 2025, 15(8), 738; https://doi.org/10.3390/catal15080738 - 1 Aug 2025
Viewed by 398
Abstract
In the last decades, numerous approaches have been explored for the cross-coupling of biaryl building blocks depending on the presence of boron sources. In fact, these changes have been catalyzed by transition metal complexes. This review focuses on the progress of the last [...] Read more.
In the last decades, numerous approaches have been explored for the cross-coupling of biaryl building blocks depending on the presence of boron sources. In fact, these changes have been catalyzed by transition metal complexes. This review focuses on the progress of the last decade in transition metal-catalyzed C–X borylation and direct C–H borylation, with emphasis on nickel-catalyzed C–H borylation, as effective and affordable protocols for the borylation of aryl substrates. In addition, Suzuki-type cross-coupling by activation of C–H, C–C, or C–N bonds is also reported. This study then offers an overview of recent advances for the synthesis of bi- and multi-aryls found in synthetic molecular complexes and natural products using the transition metal-catalyzed one-pot Miyaura-type C–X and C–H borylation–Suzuki coupling sequence. Full article
(This article belongs to the Section Catalysis in Organic and Polymer Chemistry)
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18 pages, 5529 KiB  
Article
Thermal Characterization Methods of Novel Substrate Materials Utilized in IGBT Modules
by János Hegedüs, Péter Gábor Szabó, László Pohl, Gusztáv Hantos, Gyula Lipák, Andrea Reolon and Ferenc Ender
Electron. Mater. 2025, 6(3), 9; https://doi.org/10.3390/electronicmat6030009 (registering DOI) - 31 Jul 2025
Viewed by 86
Abstract
In this article, thermal investigation methods for electrically insulating and thermally conductive substrate materials will be presented. The investigations were performed in their real-world application environment, i.e., in the form of IGBT (insulated gate bipolar transistor) module substrate plates. First, the overall thermal [...] Read more.
In this article, thermal investigation methods for electrically insulating and thermally conductive substrate materials will be presented. The investigations were performed in their real-world application environment, i.e., in the form of IGBT (insulated gate bipolar transistor) module substrate plates. First, the overall thermal resistance and thermal structure function of the system in a multivariable parameter space were revealed using CFD (computational fluid dynamics) simulations. Afterwards, thermal transient testing was performed on real samples, with the help of which the thermal resistance values of the modules were determined using the thermal dual interface test method. The presented tests are not intended to determine material parameters, but to rank different substrate materials based on their thermal performance. Full article
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22 pages, 5351 KiB  
Article
Hydrometallurgical Leaching of Copper and Cobalt from a Copper–Cobalt Ore by Aqueous Choline Chloride-Based Deep Eutectic Solvent Solutions
by Emmanuel Anuoluwapo Oke, Yorkabel Fedai and Johannes Hermanus Potgieter
Minerals 2025, 15(8), 815; https://doi.org/10.3390/min15080815 - 31 Jul 2025
Viewed by 124
Abstract
The sustainable recovery of valuable metals such as Cu and Co from ores is a pressing need considering environmental and economic challenges. Therefore, this study evaluates the effectiveness of deep eutectic solvents (DESs) as alternative leaching agents for Cu and Co extraction. Four [...] Read more.
The sustainable recovery of valuable metals such as Cu and Co from ores is a pressing need considering environmental and economic challenges. Therefore, this study evaluates the effectiveness of deep eutectic solvents (DESs) as alternative leaching agents for Cu and Co extraction. Four DESs were prepared using choline chloride (ChCl) as a hydrogen bond acceptor (HBA) and oxalic acid (OA), ethylene glycol (EG), urea (U) and thiourea (TU) as hydrogen bond donors (HBDs). Leaching experiments were conducted with DESs supplemented with 30 wt.% water at varying temperatures, various solid-to-liquid ratios, and time durations. The ChCl:OA DES demonstrated the highest leaching efficiencies among the DESs tested on pure CuO and CoO, achieving 89.2% for Cu and 92.4% for Co (60 °C, 400 rpm, 6 h, −75 + 53 µm particle size, and 1:10 solid-to-liquid ratio). In addition, the dissolution kinetics, analysed using the shrinking core model (SCM), showed that the leaching process was mainly controlled by surface chemical reactions. The activation energy values for Cu and Co leaching were 46.8 kJ mol−1 and 51.4 kJ mol−1, respectively, supporting a surface chemical control mechanism. The results highlight the potential of ChCl:OA as a sustainable alternative for metal recovery. Full article
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13 pages, 1761 KiB  
Article
Copper(I) Complexes with Terphenyl-Substituted NPN Ligands Bearing Pyridyl Groups: Synthesis, Characterization, and Catalytic Studies in the S-Arylation of Thiols
by M. Trinidad Martín, Ana Gálvez del Postigo, Práxedes Sánchez, Eleuterio Álvarez, Celia Maya, M. Carmen Nicasio and Riccardo Peloso
Molecules 2025, 30(15), 3167; https://doi.org/10.3390/molecules30153167 - 29 Jul 2025
Viewed by 421
Abstract
In this study, three new terphenyl-substituted NPN ligands bearing pyridyl groups, two phosphonites and one diaminophosphine, were synthesized and fully characterized. Their coordination chemistry with copper(I) was investigated using CuBr and [Cu(NCMe)4]PF6 as metal precursors, affording six mononuclear Cu(I) complexes, [...] Read more.
In this study, three new terphenyl-substituted NPN ligands bearing pyridyl groups, two phosphonites and one diaminophosphine, were synthesized and fully characterized. Their coordination chemistry with copper(I) was investigated using CuBr and [Cu(NCMe)4]PF6 as metal precursors, affording six mononuclear Cu(I) complexes, which were characterized using NMR spectroscopy and, in selected cases, single-crystal X-ray diffraction (SCXRD) analysis. The NPN ligands adopt a κ3-coordination mode, stabilizing the copper centers in distorted tetrahedral geometries. The catalytic performance of these complexes in the S-arylation of thiols with aryl iodides was evaluated. Under optimized conditions, complexes 2a and 2b exhibited excellent activity and broad substrate scope, tolerating both electron-donating and electron-withdrawing groups, as well as sterically hindered and heteroaryl substrates. The methodology also proved effective for aliphatic thiols and demonstrated high chemoselectivity in the presence of potentially reactive functional groups. In contrast, aryl bromides and chlorides were poorly reactive under the same conditions. These findings highlight the potential of well-defined Cu(I)–NPN complexes as efficient and versatile precatalysts for C–S bond formation. Full article
(This article belongs to the Special Issue Inorganic Chemistry in Europe 2025)
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22 pages, 5743 KiB  
Article
Effect of Grain Boundary Characteristics on Mechanical Properties and Irradiation Response in 3C-SiC: A Molecular Dynamics Simulation Study
by Wenying Liu, Fugen Deng, Jiajie Yu, Lin Chen, Yuyang Zhou, Yulu Zhou and Yifang Ouyang
Materials 2025, 18(15), 3545; https://doi.org/10.3390/ma18153545 - 29 Jul 2025
Viewed by 234
Abstract
Molecular dynamics (MD) simulations have been performed on the energetics, mechanical properties, and irradiation response of seventy-three 3C-SiC symmetric tilt grain boundaries (STGBs) with three tilt axes (<100>, <110> and <111>). The effect of GB characteristics on the STGB properties has been investigated. [...] Read more.
Molecular dynamics (MD) simulations have been performed on the energetics, mechanical properties, and irradiation response of seventy-three 3C-SiC symmetric tilt grain boundaries (STGBs) with three tilt axes (<100>, <110> and <111>). The effect of GB characteristics on the STGB properties has been investigated. The GB energy is positively and linearly correlated with the excess volume, but the linearity in SiC is not as good as in metals, which stems from the inhomogeneous structural relaxation near GBs induced by orientation-sensitive covalent bonding. For <110>STGBs, the shear strength exhibits symmetry with respect to the misorientation angle of 90°, which is consistent with ab initio calculations for Al in similar shear orientations. Cascades are performed with 8 keV silicon as the primary knock-on atom (PKA). No direct correlation is found between the sink efficiency of GBs for defects and GB characteristics, which comes from the complexity of the diatomic system during the recovery phase. For GBs with smaller values of Σ, the GBs exhibit a weaker blocking effect on the penetration of irradiated defects, resulting in a lower number of defects in GBs and a higher number of total surviving defects. In particular, it is seen that the percentage decrease in tensile strength after irradiation is positively correlated with the Σ value. Taken together, these results help to elucidate the impact of GB behavior on the mechanical properties of as well as the primary irradiation damage in SiC and provide a reference for creating improved materials through GB engineering. Full article
(This article belongs to the Section Materials Simulation and Design)
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28 pages, 14491 KiB  
Article
Catalytically Active Oxidized PtOx Species on SnO2 Supports Synthesized via Anion Exchange Reaction for 4-Nitrophenol Reduction
by Izabela Ðurasović, Robert Peter, Goran Dražić, Fabio Faraguna, Rafael Anelić, Marijan Marciuš, Tanja Jurkin, Vlasta Mohaček Grošev, Maria Gracheva, Zoltán Klencsár, Mile Ivanda, Goran Štefanić and Marijan Gotić
Nanomaterials 2025, 15(15), 1159; https://doi.org/10.3390/nano15151159 - 28 Jul 2025
Viewed by 323
Abstract
An anion exchange-assisted technique was used for the synthesis of platinum-decorated SnO2 supports, providing nanocatalysts with enhanced activity for the reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP). In this study, a series of SnO2 supports, namely SnA (synthesized almost at room [...] Read more.
An anion exchange-assisted technique was used for the synthesis of platinum-decorated SnO2 supports, providing nanocatalysts with enhanced activity for the reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP). In this study, a series of SnO2 supports, namely SnA (synthesized almost at room temperature), SnB (hydrothermally treated at 180 °C), and SnC (annealed at 600 °C), are systematically investigated, all loaded with 1 mol% Pt from H2PtCl6 under identical mild conditions. The chloride ions from the SnCl4 precursors were efficiently removed via a strong-base anion exchange reaction, resulting in highly dispersed, crystalline ~5 nm cassiterite SnO2 particles. All Pt/SnO2 composites displayed mesoporous structures with type IVa isotherms and H2-type hysteresis, with SP1a (Pt on SnA) exhibiting the largest surface area (122.6 m2/g) and the smallest pores (~3.5 nm). STEM-HAADF imaging revealed well-dispersed PtOx domains (~0.85 nm), while XPS confirmed the dominant Pt4+ and Pt2+ species, with ~25% Pt0 likely resulting from photoreduction and/or interactions with Sn–OH surface groups. Raman spectroscopy revealed three new bands (260–360 cm−1) that were clearly visible in the sample with 10 mol% Pt and were due to the vibrational modes of the PtOx species and Pt-Cl bonds introduced due the addition and hydrolysis of H2PtCl6 precursor. TGA/DSC analysis revealed the highest mass loss for SP1a (~7.3%), confirming the strong hydration of the PtOx domains. Despite the predominance of oxidized PtOx species, SP1a exhibited the highest catalytic activity (kapp = 1.27 × 10−2 s−1) and retained 84.5% activity for the reduction of 4-NP to 4-AP after 10 cycles. This chloride-free low-temperature synthesis route offers a promising and generalizable strategy for the preparation of noble metal-based nanocatalysts on oxide supports with high catalytic activity and reusability. Full article
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30 pages, 3715 KiB  
Article
The Inhibitory Effect and Adsorption Properties of Testagen Peptide on Copper Surfaces in Saline Environments: An Experimental and Computational Study
by Aurelian Dobriţescu, Adriana Samide, Nicoleta Cioateră, Oana Camelia Mic, Cătălina Ionescu, Irina Dăbuleanu, Cristian Tigae, Cezar Ionuţ Spînu and Bogdan Oprea
Molecules 2025, 30(15), 3141; https://doi.org/10.3390/molecules30153141 - 26 Jul 2025
Viewed by 458
Abstract
Experimental and theoretical studies were applied to investigate the adsorption properties of testagen (KEDG) peptide on copper surfaces in sodium chloride solution and, implicitly, its inhibition efficiency (IE) on metal corrosion. The tetrapeptide synthesized from the amino acids lysine (Lys), glutamic acid (Glu), [...] Read more.
Experimental and theoretical studies were applied to investigate the adsorption properties of testagen (KEDG) peptide on copper surfaces in sodium chloride solution and, implicitly, its inhibition efficiency (IE) on metal corrosion. The tetrapeptide synthesized from the amino acids lysine (Lys), glutamic acid (Glu), aspartic acid (Asp), and glycine (Gly), named as H-Lys-Glu-Asp-Gly-OH, achieved an inhibition efficiency of around 86% calculated from electrochemical measurements, making KEDG a promising new copper corrosion inhibitor. The experimental data were best fitted to the Freundlich adsorption isotherm. The standard free energy of adsorption (ΔGadso) reached the value of −30.86 kJ mol−1, which revealed a mixed action mechanism of tetrapeptide, namely, chemical and physical spontaneous adsorption. The copper surface characterization was performed using optical microscopy and SEM/EDS analysis. In the KEDG presence, post-corrosion, SEM images showed a network surface morphology including microdeposits with an acicular appearance, and EDS analysis highlighted an upper surface layer consisting of KEDG, sodium chloride, and copper corrosion compounds. The computational study based on DFT and Monte Carlo simulation confirmed the experimental results and concluded that the spontaneous adsorption equilibrium establishment was the consequence of the contribution of noncovalent (electrostatic, van der Waals) interactions and covalent bonds. Full article
(This article belongs to the Section Computational and Theoretical Chemistry)
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16 pages, 6618 KiB  
Review
N-Heterocyclic Carbene-Catalyzed Aerobic Oxidation of Aromatic Aldehydes into Carboxylic Acids: A Critical Review
by Alain Favre-Réguillon
Catalysts 2025, 15(8), 708; https://doi.org/10.3390/catal15080708 - 25 Jul 2025
Viewed by 429
Abstract
N-heterocyclic carbenes (NHCs) have demonstrated their versatility as catalysts for new activations and synthetic transformations of aldehydes. NHCs were originally applied in benzoin condensation and the Stetter reaction, while the development of new protocols under oxidative conditions has further expanded the potential of [...] Read more.
N-heterocyclic carbenes (NHCs) have demonstrated their versatility as catalysts for new activations and synthetic transformations of aldehydes. NHCs were originally applied in benzoin condensation and the Stetter reaction, while the development of new protocols under oxidative conditions has further expanded the potential of this methodology for the formation of carbon−carbon and carbon−heteroatom bonds. Among these reactions, NHCs are recognized as promising organocatalysts for the aerobic oxidation of aldehydes to carboxylic acids. However, to our knowledge, a comparison with other metal-free protocols has never been conducted. This review is intended to provide a perspective on aldehyde oxidation into the corresponding carboxylic acid catalyzed by NHCs, from its first practical description in 2009 until the beginning of 2025, and to compare it with other metal-free methods. Full article
(This article belongs to the Section Catalysis in Organic and Polymer Chemistry)
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17 pages, 4225 KiB  
Article
Comparative Nitrene-Transfer Chemistry to Olefins Mediated by First-Row Transition Metal Catalysts Supported by a Pyridinophane Macrocycle with N4 Ligation
by Himanshu Bhatia, Lillian P. Adams, Ingrid Cordsiemon, Suraj Kumar Sahoo, Amitava Choudhury, Thomas R. Cundari and Pericles Stavropoulos
Molecules 2025, 30(15), 3097; https://doi.org/10.3390/molecules30153097 - 24 Jul 2025
Viewed by 410
Abstract
A 12-membered pyridinophane scaffold containing two pyridine and two tertiary amine residues is examined as a prototype ligand (tBuN4) for supporting nitrene transfer to olefins. The known [(tBuN4)MII(MeCN)2]2+ (M = Mn, Fe, Co, and [...] Read more.
A 12-membered pyridinophane scaffold containing two pyridine and two tertiary amine residues is examined as a prototype ligand (tBuN4) for supporting nitrene transfer to olefins. The known [(tBuN4)MII(MeCN)2]2+ (M = Mn, Fe, Co, and Ni) and [(tBuN4)CuI(MeCN)]+ cations are synthesized with the hexafluorophosphate counteranion. The aziridination of para-substituted styrenes with PhI=NTs (Ts = tosyl) in various solvents proved to be high yielding for the Cu(I) and Cu(II) reagents, in contrast to the modest efficacy of all other metals. For α-substituted styrenes, aziridination is accompanied by products of aziridine ring opening, especially in chlorinated solvents. Bulkier β-substituted styrenes reduce product yields, largely for the Cu(II) reagent. Aromatic olefins are more reactive than aliphatic congeners by a significant margin. Mechanistic studies (Hammett plots, KIE, and stereochemical scrambling) suggest that both copper reagents operate via sequential formation of two N–C bonds during the aziridination of styrene, but with differential mechanistic parameters, pointing towards two distinct catalytic manifolds. Computational studies indicate that the putative copper nitrenes derived from Cu(I) and Cu(II) are each associated with closely spaced dual spin states, featuring high spin densities on the nitrene N atom. The computed electrophilicity of the Cu(I)-derived nitrene reflects the faster operation of the Cu(I) manifold. Full article
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17 pages, 8715 KiB  
Article
Experimental Investigation of Failure Behaviors of CFRP–Al Lap Joints with Various Configurations Under High- and Low-Temperature Conditions
by Mingzhen Wang, Qiaosheng Huang, Qingfeng Duan, Wentao Yang, Yue Cui and Hongqiang Lyu
Materials 2025, 18(15), 3467; https://doi.org/10.3390/ma18153467 - 24 Jul 2025
Viewed by 305
Abstract
The failure behaviors of CFR–aluminum lap joints with diverse configurations through quasi-static tensile tests were conducted at −40 °C, 25 °C, and 80 °C. Four specimen types were examined: CFRP–aluminum alloy two-bolt single-lap joints (TBSL), two-bolt double-lap joints (TBDL), two-bolt bonded–bolted hybrid single-lap [...] Read more.
The failure behaviors of CFR–aluminum lap joints with diverse configurations through quasi-static tensile tests were conducted at −40 °C, 25 °C, and 80 °C. Four specimen types were examined: CFRP–aluminum alloy two-bolt single-lap joints (TBSL), two-bolt double-lap joints (TBDL), two-bolt bonded–bolted hybrid single-lap joints (BBSL), and two-bolt bonded–bolted hybrid double-lap joints (BBDL). The analysis reveals that double-lap joints possess a markedly higher strength than single-lap joints. The ultimate loads of the TBSL (single-lap joints) at temperatures of −40 °C and 25 °C are 29.5% and 26.20% lower, respectively, than those of the TBDL (double-lap joints). Similarly, the ultimate loads of the BBSL (hybrid single-lap joints) at −40 °C, 25 °C, and 80 °C are 19.8%, 31.66%, and 40.05% lower, respectively, compared to the corresponding data of the TBDL. In bolted–bonded hybrid connections, the adhesive layer enhances the joint’s overall stiffness but exhibits significant temperature dependence. At room and low temperatures, the ultimate loads of the BBDL are 46.97 kN at −40 °C and 50.30 kN at 25 °C, which are significantly higher than those of the TBDL (42.24 kN and 44.63 kN, respectively). However, at high temperatures, the load–displacement curves of the BBDL and TBDL are nearly identical. This suggests that the adhesive layers are unable to provide a sufficient shear-bearing capacity due to their low modulus at elevated temperatures. This research provides valuable insights for designing composite–metal connections in aircraft structures, highlighting the impacts of different joint configurations and temperature conditions on failure modes and load-bearing capacities. Full article
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