Search Results (951)

The precise synthesis of non-precious metal single-atom electrocatalysts is crucial for enhancing the yield of highly active reactive oxygen species (ROSs). Conventional oxidation methods, such as Fenton or NaClO processes, suffer from poor efficiency, high energy demand, and secondary pollution. In contrast, heterogeneous electro-Fenton systems based on cascade oxygen reduction reactions (ORRs), which require low operational voltage and cause pollutant degradation through both direct electron transfer and ROS generation, have emerged as a promising alternative. Recent studies showed that carbon cathodes decorated with atomically dispersed transition metals can effectively integrate the excellent conductivity of carbon supports with the tunable surface chemistry of metal centers. However, the electronic structure of active sites intrinsically hinders the simultaneous achievement of high activity and selectivity in cascade ORRs. This review summarizes the advances, specifically from 2020 to 2025, in understanding the mechanism of cascade ORRs and the synthesis of transition metal-based single-atom catalysts in cathode electrocatalysis for efficient wastewater treatment, and discusses the key factors affecting treatment performance. While employing atomically engineered cathodes is a promising approach for energy-efficient wastewater treatment, future efforts should overcome the barriers in active site control and long-term stability of the catalysts to fully exploit their potential in addressing water pollution challenges. Full article

This study presents the development of Cu-doped NiMo/TiO₂ photoelectrocatalysts for simultaneous green hydrogen production and pharmaceutical pollutant removal under simulated solar irradiation. The catalysts were synthesized via wet impregnation (15 wt.% total metal loading with 0.6 wt.% Cu) and thermally treated at 400 °C and 900 °C to investigate structural transformations and catalytic performance. Comprehensive characterization (XRD, BET, SEM, XPS) revealed phase transitions, enhanced crystallinity, and redistribution of redox states upon Cu incorporation, particularly the formation of NiTiO₃ and an increase in oxygen vacancies. Crystallite sizes for anatase, rutile, and brookite ranged from 21 to 47 nm at NiMoCu400, while NiMoCu900 exhibited only the rutile phase with 55 nm crystallites. BET analysis showed a surface area of 44.4 m²·g⁻¹ for NiMoCu400, and electrochemical measurements confirmed its higher electrochemically active surface area (ECSA, 2.4 cm²), indicating enhanced surface accessibility. In contrast, NiMoCu900 exhibited a much lower BET surface area (1.4 m²·g⁻¹) and ECSA (1.4 cm²), consistent with its inferior photoelectrocatalytic performance. Compared to previously reported binary NiMo/TiO₂ systems, the ternary NiMoCu/TiO₂ catalysts demonstrated significantly improved hydrogen production activity and more efficient photoelectrochemical degradation of paracetamol. Specifically, NiMoCu400 showed an anodic peak current of 0.24 mA·cm⁻² for paracetamol oxidation, representing a 60% increase over NiMo400 and a cathodic current of −0.46 mA·cm⁻² at −0.1 V vs. RHE under illumination, nearly six times higher than the undoped counterpart (–0.08 mA·cm⁻²). Mott–Schottky analysis further revealed that NiMoCu400 retained n-type behavior, while NiMoCu900 exhibited an unusual inversion to p-type, likely due to Cu migration and rutile-phase-induced realignment of donor states. Despite its higher photosensitivity, NiMoCu900 showed negligible photocurrent, confirming that structural preservation and surface redox activity are critical for photoelectrochemical performance. This work provides mechanistic insight into Cu-mediated photoelectrocatalysis and identifies NiMoCu/TiO₂ as a promising bifunctional platform for integrated solar-driven water treatment and sustainable hydrogen production. Full article

The overall efficiency of combining denitrification and volatile organic compound (VOC) removal through selective catalytic reduction (SCR) technology is currently mainly limited by the VOC removal aspect. However, existing studies have not studied the microscopic mechanism of the interaction between VOCs and catalysts, failing to provide a theoretical basis for catalysts. Therefore, this work explored the interaction mechanisms between SCR catalysts doped with different additives and typical VOCs (acetone and toluene) in flue gas based on density functional theory (DFT) calculations. The results showed that the VNi-TiO₂ surface exhibited a high adsorption energy of −0.80 eV for acetone and a high adsorption energy of −1.02 eV for toluene on the VMn-TiO₂ surface. Electronic structure analysis revealed the VMn-TiO₂ and VNi-TiO₂ surfaces exhibited more intense orbital hybridization with acetone and toluene, promoting charge transfer between the two and resulting in stronger interactions. The analysis of temperature on adsorption free energy showed that VMn-TiO₂ and VNi-TiO₂ still maintained high activity at high temperatures. This work contributes to clarifying the interaction mechanism between SCR and VOCs and enhancing the VOC removal efficiency. Full article

This review examines the research progress on non-noble-metal-based catalysts for formaldehyde (HCHO) oxidation at room temperature. It begins with an introduction to the hazards of HCHO as an indoor pollutant and the urgency of its removal, comparing several HCHO removal technologies and highlighting the advantages of room-temperature catalytic oxidation. It delves into the classification, preparation methods, and regulation strategies for non-precious metal catalysts, with a focus on manganese-based, cobalt-based, and other transition metal-based catalysts. The effects of catalyst preparation methods, morphological structure, and specific surface area on catalytic performance are discussed, and the catalytic oxidation mechanisms of HCHO, including the Eley–Rideal, Langmuir–Hinshelwood, and Mars–van Krevelen mechanisms, are analyzed. Finally, the challenges faced by non-precious metal catalysts are summarized, such as issues related to the powder form of catalysts in practical applications, lower catalytic activity at room temperature, and insufficient research in the presence of multiple VOC molecules. Suggestions for future research directions are also provided. Full article

Hydrogen, as a renewable and clean energy with a high energy density, is of great significance to the realization of carbon neutrality. In recent years, extensive research has been conducted on the electrocatalytic hydrogen evolution reaction (HER) by splitting water, with a focus on developing efficient electrocatalysts that can perform the HER at an overpotential with minimal power consumption. Tungsten oxide (WO₃), a non-noble-metal-based material, has great potential in hydrogen evolution due to its excellent redox capability, low cost, and high stability. However, it cannot meet practical needs because of its poor electrical conductivity and the limited number of active sites; thus, it is necessary to further improve HER performance. In this review, recent advances related to WO3-based electrocatalysts for the HER are introduced. Most importantly, several tactics for optimizing the electrocatalytic HER activity of WO₃ are summarized, such as controlling its morphology, phase transition, defect engineering (anion vacancies, cation doping, and interstitial atoms), constructing a heterostructure, and the microenvironment effect. This review can provide insight into the development of novel catalysts with high activity for the HER and other renewable energy applications. Full article

The transition to clean and renewable energy sources is critically dependent on efficient hydrogen production technologies. This review surveys recent advances in photocatalytic water splitting, focusing on MNb₂O₆ nanomaterials, which have emerged as promising photocatalysts due to their tunable band structures, chemical robustness, and tailored morphologies. The objectives of this work are to (i) encompass the current synthesis strategies for MNb₂O₆ compounds; (ii) assess their structural, electronic, and optical properties in relation to photocatalytic performance; and (iii) elucidate the mechanisms underpinning enhanced hydrogen evolution. Main data collection methods include a literature review of experimental studies reporting bandgap measurements, structural analyses, and hydrogen production metrics for various MNb₂O₆ compositions—especially those incorporating transition metals such as Mn, Cu, Ni, and Co. Novelty stems from systematically detailing the relationships between synthesis routes (hydrothermal, solvothermal, electrospinning, etc.), crystallographic features, conductivity type, and bandgap tuning in these materials, as well as by benchmarking their performance against more conventional photocatalyst systems. Key findings indicate that MnNb₂O₆, CuNb₂O₆, and certain engineered heterostructures (e.g., with g-C₃N₄ or TiO₂) display significant visible-light-driven hydrogen evolution, achieving hydrogen production rates up to 146 mmol h⁻¹ g⁻¹ in composite systems. The review spotlights trends in heterojunction design, defect engineering, co-catalyst integration, and the extension of light absorption into the visible range, all contributing to improved charge separation and catalytic longevity. However, significant challenges remain in realizing the full potential of the broader MNb₂O₆ family, particularly regarding efficiency, scalability, and long-term stability. The insights synthesized here serve as a guide for future experimental investigations and materials design, advancing the deployment of MNb₂O₆-based photocatalysts for large-scale, sustainable hydrogen production. Full article

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)M^II(MeCN)₂]²⁺ (M = Mn, Fe, Co, and Ni) and [(^tBuN4)Cu^I(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

Our work introduces a facile and efficient metal-free [3+3] annulation approach for the synthesis of polysubstituted pyridines via the reaction between β-enaminonitriles and β,β-dichloromethyl peroxides. This strategy operates under mild conditions, demonstrating broad substrate scope and excellent functional group tolerance. Mechanistic investigations suggest that the reaction proceeds through a Kornblum–De La Mare rearrangement followed by S_NV-type C-Cl bond cleavage and intramolecular cyclization/condensation. By circumventing the need for transition metal catalysts or radical initiators, our method offers practical utility in organic synthesis and provides a new avenue for the rapid construction of complex pyridine scaffolds. Full article

Against the backdrop of global energy transition and strict environmental regulations, supercritical carbon dioxide (scCO₂) fracturing and oil displacement technologies have emerged as pivotal green approaches in shale gas exploitation, offering the dual advantages of zero water consumption and carbon sequestration. However, the inherent low viscosity of scCO₂ severely restricts its sand-carrying capacity, fracture propagation efficiency, and oil recovery rate, necessitating the urgent development of high-performance thickeners. The current research on scCO₂ thickeners faces a critical trade-off: traditional fluorinated polymers exhibit excellent philicity CO₂, but suffer from high costs and environmental hazards, while non-fluorinated systems often struggle to balance solubility and thickening performance. The development of new thickeners primarily involves two directions. On one hand, efforts focus on modifying non-fluorinated polymers, driven by environmental protection needs—traditional fluorinated thickeners may cause environmental pollution, and improving non-fluorinated polymers can maintain good thickening performance while reducing environmental impacts. On the other hand, there is a commitment to developing non-noble metal-catalyzed siloxane modification and synthesis processes, aiming to enhance the technical and economic feasibility of scCO₂ thickeners. Compared with noble metal catalysts like platinum, non-noble metal catalysts can reduce production costs, making the synthesis process more economically viable for large-scale industrial applications. These studies are crucial for promoting the practical application of scCO₂ technology in unconventional oil and gas development, including improving fracturing efficiency and oil displacement efficiency, and providing new technical support for the sustainable development of the energy industry. This study innovatively designed an amphiphilic modified amino silicone oil polymer (MA-co-MPEGA-AS) by combining maleic anhydride (MA), methoxy polyethylene glycol acrylate (MPEGA), and amino silicone oil (AS) through a molecular bridge strategy. The synthesis process involved three key steps: radical polymerization of MA and MPEGA, amidation with AS, and in situ network formation. Fourier transform infrared spectroscopy (FT-IR) confirmed the successful introduction of ether-based CO₂-philic groups. Rheological tests conducted under scCO₂ conditions demonstrated a 114-fold increase in viscosity for MA-co-MPEGA-AS. Mechanistic studies revealed that the ether oxygen atoms (Lewis base) in MPEGA formed dipole–quadrupole interactions with CO₂ (Lewis acid), enhancing solubility by 47%. Simultaneously, the self-assembly of siloxane chains into a three-dimensional network suppressed interlayer sliding in scCO₂ and maintained over 90% viscosity retention at 80 °C. This fluorine-free design eliminates the need for platinum-based catalysts and reduces production costs compared to fluorinated polymers. The hierarchical interactions (coordination bonds and hydrogen bonds) within the system provide a novel synthetic paradigm for scCO₂ thickeners. This research lays the foundation for green CO₂-based energy extraction technologies. Full article

To investigate the application potential of amorphous transition metal chalcogenides in catalysis, this study successfully synthesized amorphous molybdenum telluride (MoTe_x) materials and systematically explored their structural characteristics, compositional modulation, and catalytic performance. Experimental results indicate that the synthesized amorphous system consists of particles of approximately 200–300 nm in size. This distinct microstructure facilitates the exposure of abundant active sites and enhances physical adsorption capacity. The amorphous MoTe₂/MoTe₃ catalysts achieve an approximately 30%/40% degradation of methylene blue (MB) within 90 min, demonstrating significantly enhanced photocatalytic efficiency compared to that of crystalline MoTe₂ (≈20% degradation under identical conditions). Furthermore, when integrated with titanium dioxide (TiO₂), the composite exhibits exceptional co-catalytic performance, achieving a 90% degradation of MB within 90 min under visible-light irradiation, representing a catalytic efficiency improvement exceeding 160% compared to the results for pristine TiO₂. Furthermore, through comparative analysis of the catalytic behavior and microstructural variations between amorphous MoTe₃ (a-MoTe₃) and MoTe₂ (a-MoTe₂), we observed that the catalytic activity of molybdenum tellurides exhibits a weak correlation with the tellurium content, with co-catalytic efficacy jointly governed by the density of the active sites and the physical adsorption properties. This research provides new methods and insights for the study and improvement of catalytic performance in chalcogenide materials. Full article

Mechanochemical and transition-metal-catalyzed reactions of alkynes, exhibiting significant advantages like short reaction time, solvent-free, high yield and good selectivity, were considered to be green and sustainable pathways to access functionalized molecules and obtained increasing attention due to the superiorities of mechanochemical processes and the reactivities of alkynes. The ball milling and CuI-catalyzed Sonogashira coupling of alkyne and aryl iodide avoided the use of common palladium catalysts. The mechanochemical Rh(III)- and Au(I)-catalyzed C–H alkynylations of indoles formed the 2-alkynylated and 3-alkynylated indoles selectively. The mechanochemical and copper-catalyzed azide-alkyne cycloaddition (CuAAC) between alkynes and azides were developed to synthesize 1,2,3-triazoles. Isoxazole could be formed through ball-milling-enabled and Ru-promoted cycloaddition of alkyne and hydroxyimidel chloride. In this review, the generation of mechanochemical and transition-metal-catalyzed reactions of alkynes was highlighted. Firstly, the superiority and application of transition-metal-catalyzed reactions of alkynes were briefly introduced. After presenting the usefulness of green chemistry and mechanochemical reactions, mechanochemical and transition-metal-catalyzed reactions of alkynes were classified and demonstrated in detail. Based on different kinds of reactions of alkynes, mechanochemical and transition-metal-catalyzed coupling, cycloaddition and alkenylation reactions were summarized and the proposed reaction mechanisms were disclosed if available. Full article

Axially chiral compounds play a pivotal role in organic synthesis, materials science, and pharmaceutical development. Among the various strategies for their construction, enantioselective iodination and bromination have emerged as powerful and versatile approaches, enabling the introduction of halogen functionalities that serve as valuable synthetic handles for further transformations. This review highlights recent advances in atroposelective iodination and bromination, with a particular focus on the synthesis of axially chiral biaryl and heterobiaryl frameworks. Key catalytic systems are discussed, including transition metal complexes, small-molecule organocatalysts, and high-valent metal catalysts in combination with chiral ligands or transient directing groups. Representative case studies are presented to elucidate mechanistic pathways, stereochemical induction models, and synthetic applications. Despite notable progress, challenges remain, such as expanding substrate scope, improving atom economy, and achieving high levels of regio- and stereocontrol in complex molecular settings. This review aims to provide a comprehensive overview of these halogenation strategies and offers insights to guide future research in the atroposelective synthesis of axially chiral molecules. Full article

One of the key challenges in commercializing proton exchange membrane (PEM) electrolyzer technology is reducing the production costs while maintaining high efficiency and operational stability. Significant contributors to the overall cost of the device are the electrode catalysts with IrO₂ and Pt/C. Due to the high cost and limited availability of noble metals, there is growing interest in developing alternative, low-cost catalytic materials. In recent years, two-dimensional transition metal dichalcogenides (2D TMDCs), such as molybdenum disulfide (MoS₂) and rhenium disulfide (ReS₂), have attracted considerable attention due to their promising electrochemical properties for hydrogen evolution reactions (HERs). These materials exhibit unique properties, such as a high surface area or catalytic activity localized at the edges of the layered structure, which can be further enhanced through defect engineering or phase modulation. To increase the catalytically active surface area, the investigated materials were deposited on a carbon-based support—Vulcan XC-72R—selected for its high electrical conductivity and large specific surface area. This study investigated the physicochemical and electrochemical properties of six catalyst samples with varying MoS₂ and ReS₂ to carbon support ratios. Among the composites analyzed, the best sample on MoS₂ (containing the most carbon soot) and the best sample on ReS₂ (containing the least carbon soot) were selected. These were then used as cathode catalysts in an experimental PEM electrolyzer setup. The results confirmed satisfactory catalytic activity of the tested materials, indicating their potential as alternatives to conventional noble metal-based catalysts and providing a foundation for further research in this area. Full article

Fluorinated organic molecules have become indispensable in modern chemistry, owing to the unique properties imparted by fluorine to other compounds, including enhanced metabolic stability, controlled lipophilicity, and improved bioavailability. The site-selective incorporation of fluorine atoms into organic frameworks is essential in pharmaceutical, agrochemical, and material science research. In recent years, catalytic fluorination has become an important methodology for the efficient and selective incorporation of fluorine atoms into complex molecular architectures. This review highlights advances in catalytic fluorination reactions over the past six years and describes the contributions of transition metal catalysts, photocatalysts, organocatalysts, and electrochemical systems that have enabled site-selective fluorination under a variety of conditions. Particular attention is given to the use of well-defined fluorinating agents, including Selectfluor, N-fluorobenzenesulfonimide (NFSI), AlkylFluor, Synfluor, and hypervalent iodine reagents. These reagents have been combined with diverse catalytic systems, such as AgNO₃, Rh(II), Mo-based complexes, Co(II)-salen, and various organocatalysts, including β,β-diaryl serine catalysts, isothiourea catalysts, and chiral phase-transfer catalysts. This review summarizes proposed mechanisms reported in the original studies and discusses examples of electrophilic, nucleophilic, radical, photoredox, and electrochemical fluorination pathways. Recent developments in stereoselective and more sustainable protocols are also examined. By consolidating these strategies, this article provides an up-to-date perspective on catalytic fluorination and its impact on synthetic organic chemistry. Full article

This study addresses the efficiency and cost challenges of hydrogen evolution reaction (HER) catalysts in the context of carbon neutrality strategies by employing a synergistic approach that combines cation vacancy anchoring and transition metal doping on two-dimensional (2D) MXenes. Using an in situ LiF/HCl etching process, the aluminum layers in Ti₃AlC₂ were precisely removed, resulting in a few-layer Ti₃C₂T_x MXene with an increased interlayer spacing of 12.3 Å. Doping with the transition metals Fe, Co, Ni, and Cu demonstrated that Fe@Ti₃C₂ provided the optimal HER performance, characterized by an overpotential (η₁₀) of 81 mV at 10 mA cm⁻², a low Tafel slope of 33.03 mV dec⁻¹, and the lowest charge transfer resistance (R_ct = 5.6 Ω cm²). Mechanistic investigations revealed that Fe’s 3d⁶ electrons induce an upward shift in the d-band center of MXene, improving hydrogen adsorption free energy and reducing lattice distortion. This research lays a solid foundation for the design of non-precious metal catalysts using MXenes and highlights future avenues in bimetallic synergy and scalability. Full article