Search Results (315)

With the constant development of new polymer chemistry technologies, it is necessary to find modern synthetic pathways for the synthesis of polymers bearing numerous applicable characteristics, in an easy, efficient and environmentally friendly way. One such possibility is to present the use of metathesis type reactions and more specifically ring-opening metathesis polymerisation (ROMP), which provides the opportunity to produce linear unsaturated functionalised polymeric chains in a ‘living’ yet controlled manner with the use of ruthenium-based carbene (Ru=CHR) Grubbs’ catalysts (initiators: G1, G2, G3). In order to achieve satisfying results and obtain full conversion of the monomers, sterically hindered molecules are preferred, because the process of opening the ring results in simultaneous release of the energy that propagates the whole process. The incorporation of silicon-based substituents (such as silyl ethers) into the norbornene matrix can provide higher thermal stability of polymers, leading to the creation of flame-retardant materials. Other applications include gas separation membranes or biomedicine, upon further modification. This paper focusses on the development and optimisation of the synthetic method of previously not reported exo-norbornene silyl ethers along with their metathesis polymerisation to achieve linear unsaturated polymers with high isolation yields. Full article

Ammonia is indispensable to the fertilizer and chemical industries, yet its manufacture still relies predominantly on the energy-intensive Haber–Bosch process operated at 400–500 °C and 150–250 bar, with a substantial carbon footprint. Single-atom catalysts (SACs) and sub-nanometric clusters have recently emerged as promising alternatives for thermocatalytic ammonia synthesis under milder conditions because they maximize metal utilization and enable precise control of the active site environment. This review first summarizes how the transition from conventional Fe and Ru nanoparticles to isolated or few-atom sites fundamentally alters the kinetic landscape, favoring associative N₂ activation pathways that lower apparent activation energies and alleviate H₂ poisoning. We then discuss Ru-based SACs and SAAs supported on zeolites, carbons, ceria, and MXenes, highlighting how strong metal–support and promoter interactions, tandem single-atom/nanoparticle motifs, and alloying strategies tune N₂ and H₂ binding to deliver high NH₃ productivities at 200–400 °C and ≤30 bar. In parallel, we review emerging non-noble systems based on Fe and Co, including high-loading Fe–N₄ sites prepared via MOF-derived post-metal-replacement routes and Co single atoms or Co₂ clusters on N-doped carbons, which already rival or surpass Ru benchmarks under similar conditions. Collectively, these studies show that tailoring the number of atom metal sites, coordination, and support polarity around isolated metal sites provides a useful tool to mitigate some aspects of volcano and scaling-relation limitations, indicating that SACs could contribute to low-temperature ammonia synthesis when combined with appropriate process design. Full article

The rational design of supported ruthenium catalysts for sustainable energy applications requires precise control over metal nanoparticle size, dispersion, and metal–support interactions. This study investigates the influence of mesoporous silica support topology—SBA-15 (2D hexagonal, cylindrical pores), SBA-12 (3D hexagonal structure), and SBA-3 (2D hexagonal)—on the structure and catalytic performance of 1 wt% ruthenium catalysts in CO₂ methanation and gas-phase toluene hydrogenation. Comprehensive characterization by nitrogen physisorption, low- and high-angle X-ray diffraction (XRD), H₂ temperature-programmed reduction (H₂-TPR), CO chemisorption, and transmission electron microscopy (TEM) revealed that support pore architecture dictates ruthenium particle size (1.2 nm for Ru/SBA-15, 2.8 nm for Ru/SBA-3, 4.3 nm for Ru/SBA-12) and dispersion (80%, 35%, 23%, respectively) through geometric confinement effects. Catalytic testing demonstrated contrasting structure–activity relationships: CO₂ methanation exhibited strong structure sensitivity with turnover frequency (TOF) increasing with particle size (Pearson’s r = 0.96), favoring Ru/SBA-3 and Ru/SBA-12 with near-optimal 3–4 nm particles, while toluene hydrogenation showed weaker structure sensitivity, with Ru/SBA-12 achieving the highest TOF owing to its larger particle size and higher crystallinity. These findings underscore the critical importance of tailoring mesoporous support topology to match reaction-specific structure sensitivity, providing fundamental insights for the design of bifunctional catalysts for hydrogenation reactions. Full article

Catalytic materials are central to the advancement of hydrogen generation technologies, playing a pivotal role in enabling sustainable, carbon-neutral energy systems. Hydrogen can be produced via electrochemical water splitting, thermochemical reforming, or photocatalysis—each imposing unique performance requirements on catalysts in terms of activity, selectivity, stability, and efficiency. While traditional noble metals (e.g., platinum, ruthenium, iridium) provide benchmark catalytic activity, their widespread use is hindered by scarcity, high cost, and limited long-term durability. Consequently, researchers have increasingly focused on earth-abundant alternatives such as transition metals (Ni, Co, Fe, Mo), alloys, metal oxides, carbides, sulfides, nitrides, and carbon-based systems. Among these, two-dimensional materials, particularly the MXene family, have attracted significant attention due to their metallic conductivity, layered structure, and tunable surface chemistry. These features enable rapid charge transfer and abundant active sites, making MXenes and related nanostructured catalysts promising for both the Hydrogen Evolution Reaction (HER) and Oxygen Evolution Reaction (OER) across a wide range of electrochemical conditions. Parallel efforts have integrated novel semiconductors, plasmonic nanomaterials, and hybrid heterostructures to improve the efficiency of solar-to-hydrogen energy conversion. This paper reviews the main types of catalytic materials used in hydrogen production, explains their design strategies and structure–performance relationships, and discusses key engineering challenges such as integrating renewable energy sources, scaling up manufacturing, and ensuring long-term durability in real-world systems. Future research goals are also highlighted, including the development of affordable non-noble catalysts, enhancing catalyst stability through surface and defect engineering, and coupling hydrogen production with circular economy principles, all of which are essential to making hydrogen generation more efficient, scalable, and cost-effective as the world transitions to clean and sustainable energy. Full article

The CO₂ hydrogenation reaction is a cornerstone reaction in catalytic conversion technologies, with Ru/TiO₂ catalysts being amongst the most active and selective for CH₄ formation. A key factor in the preparation of such catalysts is the choice of chemical precursor for Ru impregnation, as it can substantially influence the physicochemical properties and catalytic performance. In this study, we deliberately employ a simple incipient wetness impregnation method to isolate the effect of the Ru precursor itself, using two different Ru precursors for the synthesis of Ru/TiO₂ catalysts intended for CO₂ hydrogenation and evaluating their properties using analytical techniques such as XRF, XRD, TEM, XPS and H₂-TPR. Our results show that catalysts prepared from ruthenium nitrosyl nitrate solutions display enhanced reducibility and slightly stronger metal–support interactions compared to those prepared from ruthenium chloride solutions. These features enable higher CO₂ conversion and CH₄ selectivity. The results of this work provide grounds for the targeted chemical precursor selection, while clarifying the reason behind the observed effects on catalytic performance. Full article

Noble metal-catalyzed C–H activation has transformed synthetic methodology by enabling direct modification of inert C–H bonds with high levels of efficiency, selectivity, and functional group tolerance. This mini-review provides a focused overview of the mechanistic foundations and emerging advances in C–H functionalization mediated by ruthenium, iridium, rhodium and palladium catalysts. Key activation modes including oxidative addition, concerted metalation deprotonation (CMD), and electrophilic pathways are discussed alongside the roles of high-valent intermediates and ligand control in determining reactivity and regioselectivity. Special emphasis is placed on recent electrochemical strategies, where anodic oxidation replaces traditional chemical oxidants, granting access to unique redox manifolds and expanding the scope of C–C, C–N, C–O, and C–X bond-forming reactions. Representative transformations highlight the versatility of noble metals in constructing heterocycles, enabling enantioselective processes, and facilitating late-stage functionalization of complex molecules. Current challenges and future perspectives are outlined, including the need for improved nondirected activation, deeper mechanistic insight, and enhanced scalability. Collectively, this review underscores the central role of noble metals in advancing sustainable and innovative C–H functionalization chemistry. Full article

Gamma-valerolactone (GVL) can be used as a renewable solvent, flavoring agent, and precursor to produce liquid fuels and fine chemicals. GVL is mainly produced by the efficient hydrogenation of levulinic acid and its esters over a wide range of bifunctional catalysts under harsh conditions because high temperature is generally required for GVL formation. So far, the hydrogenation of levulinic acids/esters under mild conditions remains a great challenge. In this study, 2 wt.% Ru was loaded onto ZSM-5 zeolite (MFI) via a deposition–precipitation method and further wrapped by crystallization, forming a core–shell structure. Moreover, the wrapped Ru catalyst was coated with a petal-like layer of Mg₃Si₄O₉(OH)₄ (MgSiO₃) via a hydrothermal reaction in a Mg(NO₃)₂ solution, thereby introducing alkalinity and achieving spatial separation of Mg and Ru. This dual-functional catalyst reduces the inhibitory effect of Mg on the Ru active center and enables efficient preparation of GVL from ethyl levulinate (EL) under mild conditions, achieving 100% EL conversion and 98% GVL selectivity in the aqueous phase at 80 °C in 2 h under 0.5 MPa of H₂. Full article

Platinum group metals (PGMs)—comprising platinum (Pt), palladium (Pd), rhodium (Rh), iridium (Ir), ruthenium (Ru), and osmium (Os)—are indispensable strategic materials for key industries, including automotive manufacturing, petrochemical engineering, and the new energy sector. Given the uneven global distribution of primary PGM reserves and the widening supply–demand gap, recovering PGMs from secondary sources—primarily metallurgical by-products and spent catalysts—has become a strategic priority. synergistic smelting, leveraging “multi-feedstock complementarity” and “multi-technology coupling,” offers an efficient approach to overcoming challenges associated with secondary resources, such as low grades, complex matrices, and refractory separation. This paper systematically reviews the technological evolution of synergistic smelting for PGMs recovery, focusing on three aspects: the characteristics and processing bottlenecks of PGMs-bearing secondary resources, the development trajectory of traditional metallurgical technologies, and innovative breakthroughs in microwave-assisted synergistic smelting. A comparative analysis between traditional and microwave-based technologies is conducted across four dimensions: resource adaptability, technical performance, environmental sustainability, and industrial maturity. Finally, the core challenges currently confronting microwave-assisted synergistic smelting and future directions for industrial demonstration are elaborated on. This study serves as a comprehensive reference for the efficient and sustainable recovery of PGMs, with significant implications for the circular economy and strategic resource security. Full article

Ruthenium, a critical metal, plays an increasingly important role in modern applications, such as catalysts for chemical synthesis and the production of hard disk drives. As a result, the supply has struggled to meet the growing demand in recent years. The economic position of ruthenium presents an opportunity to examine the methods of its extraction, particularly given that it is a lesser-known platinum group metal. This article explores the concentration of ruthenium in natural sources and the methods used in primary production, with a particular focus on hydrometallurgical techniques applied at an industrial scale. It also discusses secondary ruthenium-containing materials, including spent catalysts, metallurgical by-products, wastewaters, spent nuclear fuel. The article provides a detailed analysis of the composition of these materials, emphasizing hydrometallurgical methods like leaching and separation processes, along with the recovery of final products. Full article

The field of electrochemical devices, encompassing energy storage, fuel cells, electrolysis, and sensing, is fundamentally reliant on the electrode materials that govern their performance, efficiency, and sustainability. Traditional materials, while foundational, often face limitations such as restricted reaction kinetics, structural deterioration, and dependence on costly or scarce elements, driving the need for continuous innovation. Emerging electrode materials are designed to overcome these challenges by delivering enhanced reaction activity, superior mechanical robustness, accelerated ion diffusion kinetics, and improved economic feasibility. In energy storage, for example, the shift from conventional graphite in lithium-ion batteries has led to the exploration of silicon-based anodes, offering a theoretical capacity more than tenfold higher despite the challenge of massive volume expansion, which is being mitigated through nanostructuring and carbon composites. Simultaneously, the rise of sodium-ion batteries, appealing due to sodium’s abundance, necessitates materials like hard carbon for the anode, as sodium’s larger ionic radius prevents efficient intercalation into graphite. In electrocatalysis, the high cost of platinum in fuel cells is being addressed by developing Platinum-Group-Metal-free (PGM-free) catalysts like metal–nitrogen–carbon (M-N-C) materials for the oxygen reduction reaction (ORR). Similarly, for the oxygen evolution reaction (OER) in water electrolysis, cost-effective alternatives such as nickel–iron hydroxides are replacing iridium and ruthenium oxides in alkaline environments. Furthermore, advancements in materials architecture, such as MXenes—two-dimensional transition metal carbides with metallic conductivity and high volumetric capacitance—and Single-Atom Catalysts (SACs)—which maximize metal utilization—are paving the way for significantly improved supercapacitor and catalytic performance. While significant progress has been made, challenges related to fundamental understanding, long-term stability, and the scalability of lab-based synthesis methods remain paramount for widespread commercial deployment. The future trajectory involves rational design leveraging advanced characterization, computational modeling, and machine learning to achieve holistic, system-level optimization for sustainable, next-generation electrochemical devices. Full article

Ruthenium-based catalysts supported on TiO₂, SnO₂, and WO₃ were synthesized via a microwave-assisted rapid reduction method and evaluated for the hydrogen evolution reaction (HER) in acidic media. The Ru species existed as highly dispersed nanoclusters, as confirmed by XRD and TEM, and the catalytic activity was strongly dependent on the oxide support. Ru/TiO₂ exhibited the best HER performance, achieving an overpotential of 187 mV at 10 mA·cm⁻² and a Tafel slope of 97.56 mV·dec⁻¹. While particle size differences (1.8–3.7 nm) did not account for the activity trend, XPS revealed distinct metal–support interactions that modulated the electronic state of Ru. Ru/TiO₂ showed an intermediate electron depletion that optimizes the Ru-H binding strength, explaining its superior kinetics. Regulation of Ru loading further identified Ru/15TiO₂ as the optimal catalyst, exhibiting low charge transfer resistance and excellent stability over 17 h. This study highlights the critical role of support-induced electronic modulation and loading engineering in designing efficient Ru-based electrocatalysts for acidic HER. Full article

In the quest for cheap and abundant feedstocks for sustainable hydrogen production, glycerol is emerging as a cost-effective, promising liquid organic hydrogen-rich carrier (LOHC) that can be catalytically activated to produce hydrogen alongside valuable organic products. Selective catalytic acceptorless dehydrogenation of glycerol to lactate and hydrogen gas was achieved with a maximum turnover number (TON_max) of ca. 1600, using a pincer-type ruthenium(II) complex bearing a bis(aminophosphine)pyridine PN³P ligand as a homogeneous catalyst under moderate reaction conditions (24 h, 140 °C) in the presence of KOH as base. NMR experiments and DFT calculations provided insights into key steps of the catalytic process and the energetics of the proposed reaction pathway. Full article

The ruthenium-catalysed silylative coupling (SC) reaction is a useful method for obtaining selectively functionalised organosilicon compounds, which have a wide range of applications in organometallic and organic chemistry. It is possible to prepare such compounds with norbornene matrices, which can be used for ring-opening metathesis polymerisation (ROMP) in the synthesis of linear-type polymers. Herein, we present a method for the synthesis of the aforementioned matrices by a condensation reaction between diol and vinylphenylboronic acids. Furthermore, these compounds were subsequently modified by SC reaction and polymerised by ROMP. To assess the possibility of using styryl-based silyl-derived monomers as building blocks in further organic transformations, the process of bromodesilylation was also investigated. We would also like to perform a comparative study on the selectivity of hydrosilylation and silylative coupling processes in the case of discovered materials. Full article

The synergistic combination of the ruthenium-based tetranuclear dendrimer photosensitizer with the highly efficient water oxidation catalyst Ru(bda)(pic)₂ enables effective water oxidation under low-energy light irradiation in phosphate buffer 20 mM/acetonitrile 3% (pH 7). This study demonstrates that the integrated system can produce a significant amount of oxygen using visible light at wavelengths greater than 650 nm (up to 160 nmol), achieving quite good turnover number (3.5 × 10⁻³), high quantum yields (0.23) and enhanced stability. These results highlight the potential of this approach to efficiently drive solar water splitting for fuel production, even with low-energy illumination, thereby advancing the development of sustainable photochemical systems for solar energy conversion. Full article

High-valent metal species (iron, manganese, cobalt, copper, and ruthenium) based advanced oxidation processes (AOPs) have emerged as sustainable technologies for water remediation. These processes offer high selectivity, electron transfer efficiency, and compatibility with circular chemistry principles compared to conventional systems. This comprehensive review discusses recent advances in the synthesis, stabilization, and catalytic applications of high-valent metals in aqueous environments. This study highlights their dual functionality, not only as conventional oxidants but also as mechanistic mediators within redox cycles that underpin next-generation AOPs. In this review, the formation mechanisms of these species in various oxidant systems are critically evaluated, highlighting the significance of ligand design, supramolecular confinement, and single-atom engineering in enhancing their stability. The integration of high-valent metal-based AOPs into photocatalysis, sonocatalysis, and electrochemical regeneration is explored through a newly proposed classification framework, highlighting their potential in the development of energy efficient hybrid systems. In addition, this work addresses the critical yet underexplored area of environmental fate, elucidating the post-oxidation transformation pathways of high-valent species, with particular attention to their implications for metal recovery and nutrient valorization. This review highlights the potential of high-valent metal-based AOPs as a promising approach for zero wastewater treatment within circular economies. Future frontiers, including bioinspired catalyst design, machine learning-guided optimization, and closed loop reactor engineering, will bridge the gap between laboratory research and real-world applications. Full article