Search Results (296)

In the water splitting process for sustainable hydrogen production, the oxygen evolution reaction (OER) stands as one of the pivotal half-reactions. Nevertheless, the sluggish four-electron transfer process inherent to OER has emerged as a kinetic bottleneck that impedes water electrolysis. To address this challenge, researchers have been devoting substantial efforts to developing high-performance OER electrocatalysts. Currently, iridium (Ir)-based or ruthenium (Ru)-based oxides are widely acknowledged as benchmark catalysts for OER. However, their scarcity and exorbitant cost render large-scale applications impractical. In recent years, transition metal carbides have garnered extensive attention in the realm of OER electrocatalysts, exhibiting tremendous application prospects owing to their advantages of low cost, high catalytic activity, and excellent stability. This review briefly introduces the fundamental characteristics and synthesis methodologies of transition metal carbides, summarizes the recent research advances in their application as OER catalysts, elaborates on the modification strategies and catalytic mechanisms of transition metal carbide nanomaterials, and finally discusses the challenges confronted by these metal carbides as well as the future research directions. Full article

A comprehensive literature review highlights how the nature of active metals, support materials, promoters, and synthesis methods influences catalytic performance, with particular attention to ruthenium-based catalysts as the current benchmark. Kinetic models are presented to describe the reaction pathway and predict catalyst behavior. Various reactor configurations, including fixed-bed, membrane, catalytic membrane, perovskite-based, and microreactors, are evaluated in terms of their suitability for ammonia decomposition. While ruthenium remains the benchmark catalyst, alternative transition metals such as iron, nickel, and cobalt have also been investigated, although they typically require higher operating temperatures (≥500 °C) to achieve comparable conversion levels. At the industrial scale, catalyst development must balance performance with cost. Inexpensive and scalable materials (e.g., MgO, Al₂O₃, CaO, K, Na) and simple preparation techniques (e.g., wet impregnation, incipient wetness) may offer lower performance than more advanced systems but are often favored for practical implementation. From a reactor engineering standpoint, membrane reactors emerge as the most promising technology for combining catalytic reaction and product separation in a single unit operation. This review provides a critical overview of current advances in ammonia decomposition for hydrogen production, offering insights into both catalytic materials and reactor design strategies for sustainable energy applications. Full article

The global depletion of fossil resources, combined with accelerating climate change and environmental concerns, is driving intensive research into alternative, sustainable sources of energy and raw materials. Particular attention is being paid to lignocellulosic biomass as the most abundant and renewable organic resource. The catalytic conversion of biomass-derived carbohydrates into high-value-added products (fuels and chemicals) aligns with the principles of sustainable development and offers a viable alternative to petroleum-based feedstocks. This review provides a product-oriented perspective on the deep valorization of carbohydrates, focusing on catalytic strategies that enable the production of renewable fuels and chemicals. It highlights two key stages in the valorization of lignocellulosic biomass: (1) the acid-catalyzed conversion of carbohydrates into platform molecules (furfural, 5-hydroxymethylfurfural, and levulinic acid); and (2) the selective hydrogenation and hydrogenolysis of these intermediates to obtain target end products. These target products fall into two major categories: (i) biofuels and fuel additives; and (ii) green chemicals, such as solvents, pharmaceuticals, agrochemicals, cosmetics, and intermediates for the synthesis of biobased polymeric materials, including polyesters, resins, and polyurethanes. Particular emphasis is placed on recent advances in the development of heterogeneous catalysts. Solid acid catalysts used in the synthesis of platform molecules are discussed, along with ruthenium-based catalysts employed in the subsequent hydrogenation and hydrogenolysis steps. Recent efforts toward integrating both catalytic stages into a single one-pot processes using bifunctional metal–acid catalysts and dual catalytic systems based on ruthenium are also reviewed, as they represent a promising route to simplify biomass valorization schemes and improve product selectivity toward fuels and chemicals. Full article

Pyridyl-thiourea complexes of formula [(Cym)MCl(κ²N_py,S-H₂NNS)][SbF₆] (Cym = η⁶-p-MeC₆H₄iPr; H₂NNS = N-(p-tolyl)-N′-(2-pyridylmethyl)thiourea); M = Ru (1), Os (2)) were synthesized by reacting the corresponding metal dimers [{(Cym)MCl}₂(μ-Cl)₂] with H₂NNS in the presence of NaSbF₆. Subsequent chloride abstraction with AgSbF₆, followed by NH deprotonation using NaHCO₃, afforded the cationic complexes [(Cym)M(κ³N_py,N_amide,S-HNNS)][SbF₆] (M = Ru (5a), (5c); M = Os (6a, 6c)) and [(Cym)M(κ²N_amide,S-HNNS)][SbF₆] (M = Ru (5b); M = Os (6b)). The proposed structures for the prepared compounds are based on NMR data. Complexes 5a, 5b, and 6a, 6b evolve to the thermodynamically more stable species 5c and 6c, respectively, in which the deprotonated ligand HNNS adopts a κ³N_py,N_amide,S coordination mode. Complexes 5c and 6c activate H₂, behaving as frustrated Lewis pair (FLP) species, and catalyze (5c and/or 6c) the hydrogenation of polar multiple bonds, including the C=N bonds of N-benzylideneaniline and quinoline, the C=C bond of methyl acrylate, and the C=O bond of 2,2,2-trifluoroacetophenone. Full article

Industrial catalysts are accelerating the global transition toward renewable energy, serving as enablers for innovative technologies that enhance efficiency, lower costs, and improve environmental sustainability. This review explores the pivotal roles of industrial catalysts in hydrogen production, biofuel generation, and biomass conversion, highlighting their transformative impact on renewable energy systems. Precious-metal-based electrocatalysts such as ruthenium (Ru), iridium (Ir), and platinum (Pt) demonstrate high efficiency but face challenges due to their cost and stability. Alternatives like nickel-cobalt oxide (NiCo₂O₄) and Ti₃C₂ MXene materials show promise in addressing these limitations, enabling cost-effective and scalable hydrogen production. Additionally, nickel-based catalysts supported on alumina optimize SMR, reducing coke formation and improving efficiency. In biofuel production, heterogeneous catalysts play a crucial role in converting biomass into valuable fuels. Co-based bimetallic catalysts enhance hydrodeoxygenation (HDO) processes, improving the yield of biofuels like dimethylfuran (DMF) and γ-valerolactone (GVL). Innovative materials such as biochar, red mud, and metal–organic frameworks (MOFs) facilitate sustainable waste-to-fuel conversion and biodiesel production, offering environmental and economic benefits. Power-to-X technologies, which convert renewable electricity into chemical energy carriers like hydrogen and synthetic fuels, rely on advanced catalysts to improve reaction rates, selectivity, and energy efficiency. Innovations in non-precious metal catalysts, nanostructured materials, and defect-engineered catalysts provide solutions for sustainable energy systems. These advancements promise to enhance efficiency, reduce environmental footprints, and ensure the viability of renewable energy technologies. Full article

This study examines the surface chemistry of platinum, palladium, rhodium, and ruthenium-substituted lanthanum strontium cobaltate perovskite catalysts in the context of the dry reforming of methane (DRM). The catalysts were synthesized by the solution combustion method and characterized by using a series of techniques. To explore the effect of noble metal ion substitution on the DRM, surface reaction was probed by CH₄/CO₂ TPSR using mass spectroscopy. It was recognized that La_1−xSr_xCo_1−yPd_yO₃ show the best activities for the reaction in terms of the temperature but became deactivated over time. CH₄/CO₂ temperature-programmed surface reactions (TPSRs) were set up to unravel the details of the surface phenomena responsible for the deactivation of the DRM activity on the LSPdCO. The CH₄/CO₂ TPSR analysis conclusively demonstrated the importance of lattice oxygen in the removal of carbon, which is responsible for the stability of the catalysts on the synthesized perovskites upon noble metal ion substitution. Full article

Searching for new and efficient transfer hydrogenation catalysts, a series of new organometallic ruthenium(II)-arene complexes of the formulae [Ru(η⁶-p-cymene)(L)Cl][PF₆] (1–8) and [Ru(η⁶-p-cymene)(L)Cl][Ru(η⁶-p-cymene)Cl₃] (9–11) were synthesized and fully characterized. These were prepared from the reaction of pyridine–quinoline and biquinoline-based ligands (L) with [Ru(η⁶-p-cymene)(μ-Cl)Cl]₂, in 1:2 and 1:1, metal (M) to ligand (L) molar ratios. Characterization includes a combination of spectroscopic methods (FT-IR, UV-Vis, multi nuclear NMR), elemental analysis and single-crystal X-ray crystallography. The pyridine–quinoline organic entities encountered, were prepared in high yield either via the thermal decarboxylation of the carboxylic acid congeners, namely 2,2′-pyridyl-quinoline-4-carboxylic acid (pqca), 8-methyl-2,2′-pyridyl-quinoline-4-carboxylic acid (8-Mepqca), 6′-methyl-2,2′-pyridyl-quinoline-4-carboxylic acid (6′-Mepqca) and 8,6′-dimethyl-2,2′-pyridyl-quinoline-4-carboxylic acid (8,6′-Me₂pqca), affording the desired ligands pq, 8-Mepq, 6′-Mepq and 8,6′-Me₂pq, or by the classical Friedländer condensation, to yield 4,6′-dimethyl-2,2′-pyridyl-quinoline (4,6′-Me₂pq) and 4-methyl-2,2′-pyridyl-quinoline (4-Mepq), respectively. The solid-state structures of complexes 1–4, 6, 8 and 9 were determined showing a distorted octahedral coordination geometry. The unit cell of 3 contains two independent molecules (Ru-3), (Ru′-3) in a 1:1 ratio, due to a slight rotation of the arene ring. All complexes catalyze the transfer hydrogenation of acetophenone, using 2-propanol as a hydrogen donor in the presence of KOiPr. Among them, complexes 1 and 5 bearing methyl groups at the 8 and 4 position of the quinoline moiety, convert acetophenone to 1-phenylethanol quantitatively, within approximately 10 min with final TOFs of 1600 h⁻¹. The catalytic performance of complexes 1–11, towards the transfer hydrogenation of p-substituted acetophenone derivatives and benzophenone, ranges from moderate to excellent. An inner-sphere mechanism has been suggested based on the detection of ruthenium(II) hydride species. Full article

Ammonia is increasingly recognised as a promising carbon-free fuel and hydrogen carrier due to its high hydrogen content, ease of liquefaction, and existing global infrastructure. However, its direct utilisation in combustion systems poses significant challenges, including low flame speed, high ignition temperature, and the formation of nitrogen oxides (NO_X). This review explores catalytic ammonia cracking as a viable method to enhance combustion through in situ hydrogen production. It evaluates traditional catalytic burner designs originally developed for hydrocarbon fuels and assesses their adaptability for ammonia-based applications. Special attention is given to ruthenium- and nickel-based catalysts supported on various oxides and nanostructured materials, evaluating their ammonia conversion efficiency, resistance to sintering, and thermal stability. The impact of the main operational parameters, including reaction temperature and gas hourly space velocity (GHSV), is also discussed. Strategies for combining partial ammonia cracking with stable combustion are studied, with practical issues such as catalyst degradation, NO_X regulation, and system scalability. The analysis highlights recent advancements in structural catalyst support, which have potential for industrial-scale application. This review aims to provide future development of low-emission, high-efficiency catalytic burner systems and advance ammonia’s role in next-generation hydrogen energy technologies. Full article

Unsaturated macrolactones (UMs) have long attracted researchers’ attention due to a combination of a reactive ester fragment and C=C bond in their structures. UMs of natural origin are comparatively few in number, and the task of developing synthetic approaches to new UMs is relevant. Recent advances in the synthesis of UMs cannot be dissociated from the progress in design of metathesis catalysts, since this catalytic approach is an atom-economy alternative to conventional organochemical methods. In the present review, we summarized and discussed the use of ring-closing metathesis, catalyzed by Ru and Group 6 metal complexes, in the synthesis of Ums and the advantages and shortcomings of the catalytic approach to UMs in comparison with organochemical methods. In a separate section, the use of UMs in the synthesis of unsaturated polyesters, the functionalization of these (co)polymers, and the prospects for practical use of the material obtained are also presented. It is essential that the actual approaches to UMs are often based on the use of renewable feedstocks, thereby meeting Green Chemistry principles. Full article

Broccoli, a highly valued Brassica vegetable, is renowned for its rich content of bioactive substances, including glucosinolates, phenolic compounds, vitamins, and essential minerals. Glucosinolates (GSLs), secondary plant metabolites, are particularly abundant in broccoli. The global consumption of broccoli has increased due to its high nutritional value. This review examines the essential bioactive compounds in broccoli and their biological properties. Numerous in vitro and in vivo studies have demonstrated that broccoli exhibits various biological activities, including antioxidant, anticancer, antimicrobial, anti-inflammatory, anti-obesity and antidiabetic effects. This review analyzes several aspects of the chemical and biological activity of GSLs and their hydrolysis products, isothiocyanates such as sulforaphane, as well as phenolic compounds. Particular emphasis is placed on sulforaphane’s chemical structure, the reactivity of its isothiocyanate fraction (-NCS), and given the different behavior of SFN enantiomers, a wide and detailed review of the chemical synthesis methods described, by microbial oxidation, or using a chiral ruthenium catalyst and more widely using chiral auxiliaries for synthesizing sulforaphane enantiomers. In addition, the methods of chiral resolution of racemates by HPLC are reviewed, explaining the different chiral fillers used for this resolution and a third section on resolution using the formation of diastereomeric complexes and subsequent separation on achiral columns. Additionally, this review highlights the presence of antimicrobial peptides in broccoli, which have shown potential applications in food preservation and as natural alternatives to synthetic antibiotics. The antimicrobial peptides (AMPs) derived from broccoli target bacterial membranes, enzymes, oxidative stress pathways and inflammatory mediators, contributing to their effectiveness against a wide range of pathogens and with potential therapeutic applications. Full article

The transition from fossil resources to renewable raw materials derived from lignocellulosic waste is crucial for economic and environmental sustainability. Advancing toward a bio-based economy necessitates the development of innovative heterogeneous catalysts. This study explores the use of modified sugarcane bagasse biochar, embedded with ruthenium and iron particles, as a green catalyst for converting levulinic acid (LA) to γ-valerolactone (GVL). The efficiency of both raw and modified biochar in the LA to GVL conversion process, utilizing formic acid (FA) exclusively as the hydrogen source, was systematically assessed through characterization techniques, including XRD, TGA, XPS, and SEM/EDS. The gelification method using alginate enhanced the ruthenium and iron content on the surface of the biochar. The results demonstrate that the modified material has significant potential for efficient LA-to-GVL conversion, achieving a yield of 73.0 ± 9.2% under optimized conditions (0.5 g of BC₅₀₀Fe/3%Ru at 180 °C for 3 h, with 4 mmol LA, 8 mmol FA, and 10 mL of water). Iron on the biochar surface facilitated the formation of adsorption sites for LA, supporting the notion of this novel catalyst for LA conversion in an aqueous medium in the presence of FA. This research underscores the potential of this green catalyst in advancing sustainable biomass conversion and contributes to the ongoing shift towards a bio-based economy. Full article

Sub-nano metal clusters have important physicochemical features that lead to a wide range of applications. Herein, we point out an unfailing reproducible protocol to synthesize ruthenium single-atom catalysts and ultra-small clusters supported on various silica–alumina mixed oxides. The catalysts were synthesized via a dendrimer-free, sonication-assisted route, with ruthenium loadings up to 2 wt%. Raman spectroscopy mapping revealed a wide coverage of the materials’ surfaces by ruthenium, while HAADF-STEM evidenced that 100% of the ruthenium was at the sub-nano scale, with up to 74% of the single atoms and metal clusters having an average size between 0.3 and 0.7 nm, independently of the support or the metal’s loading. These materials exhibited highly selective size-dependent catalytic performances in upgrading biomass-derived furfural into transportation biofuel additive 2,2′-difurfurylether, with turnover frequencies up to 1148 h⁻¹. Ruthenium single atoms and sub-nano clusters showed an exceptional resistance to sintering, with a size variation of ±0.1 nm before and after reaction, and no metal leaching was observed. Full article

5-Hydroxymethylfurfural (HMF) serves as an important bridge connecting biomass resources with fossil fuels. Its downstream product, 2,5-furandicarboxylic acid (FDCA), is a renewable alternative to terephthalic acid (TPA) in the synthesis of various polymer materials. In this study, we successfully synthesized four ruthenium-based catalysts with varying valence states supported on carbon nanotubes (CNTs) and compared the performance of HMF electrooxidation. Among these, the Ru^+2.9 catalyst demonstrated the highest activity for the electrochemical oxidation of HMF to FDCA in the neutral medium (0.1 M K₂SO₄). Notably, the FDCA yield reached 90.2% under an applied potential of 0.95 V (vs. Ag/AgCl) after 24 h. Mechanistic analysis revealed that the superior specific capacitance of the Ru^+2.9 catalyst significantly facilitated the reaction process. This work represents a more cost-effective approach to avoid the need for excessive alkaline additives during catalyst preparation and the HMF oxidation process, and FDCA separated easily after cooling the reaction solution down. Full article

Chemical recycling of plastic waste, especially polyolefins, into valuable liquid fuels is of considerable significance to address the serious issues raised by their threat on environmental and human health. Nevertheless, the construction of efficient and economically viable catalytic systems remains a significant hurdle. Herein, we developed an efficient bifunctional catalyst system comprising γ-Al₂O₃-supported ruthenium nanoparticles (Ru/γ-Al₂O₃) and β-zeolite for the conversion of polyolefins into gasoline-range hydrocarbons. A yield of C_5–12 paraffins up to 73.4% can be obtained with polyethene as the reactant at 250 °C in hydrogen. The Ru sites primarily activate the initial cleavage of C–H bonds of polymer towards the formation of olefin intermediates, which subsequently go through further cracking and isomerization over the acid sites in β-zeolite. Employing in situ infrared spectroscopy and probe–molecule model reactions, our investigation reveals that the optimized proportion and spatial distribution of the dual catalytic sites are pivotal in the tandem conversion process. This optimization synergistically regulates the cracking kinetics and accelerates intermediate transfer, thereby minimizing the production of side C_1–4 hydrocarbons resulting from over-cracking at the Ru sites and enhancing the yield of liquid fuels. This research contributes novel insights into catalyst design for the chemical upgrading of polyolefins into valuable chemicals, advancing the field of plastic waste recycling and sustainable chemical production. Full article

This study reports the synthesis, characterization, and catalytic performance of a series of catalysts of Ru supported on CeO₂-Y₂O₃ composites (Ru/CeYX; X = 0, 33, 66, and 100 wt.% Y₂O₃) for CO₂ hydrogenation. Supported material modification (Y₂O₃-CeO₂), by the Y₂O₃ incorporation, allowed a change in selectivity from methane to RWGS of the CO₂ hydrogenation reaction. This change in selectivity is correlated with the variation in the physicochemical properties caused by Y₂O₃ addition. X-ray diffraction (XRD) analysis confirmed the formation of crystalline fluorite-phase CeO₂ and α-Y₂O₃. High-resolution transmission electron microscopy (HR-TEM) and energy-dispersive X-ray spectroscopy (EDS) elemental mapping revealed the formation of a homogeneous CeO₂-Y₂O₃ nanocomposite. As the Y₂O₃ content increased, the specific surface area, measured by BET, showed a decreasing trend from 106.3 to 51.7 m² g⁻¹. X-ray photoelectron spectroscopy (XPS) of Ce3d indicated a similar Ce³⁺/Ce⁴⁺ ratio across all CeO₂-containing materials, while the O1s spectra showed a reduction in oxygen vacancies with increasing Y₂O₃ content, which is attributed to the decreased surface area upon composite formation. Catalytically, the addition of Y₂O₃ influenced both conversion and selectivity. CO₂ conversion decreased with increasing Y₂O₃ content, with the lowest conversion observed for Ru/CeY100. Regarding selectivity, methane was the dominant product for Ru/CeY0 (pure CeO₂), while CO was the main product for Ru/CeY33, Ru/CeY66, and Ru/CeY100, indicating a shift towards the reverse water–gas shift (RWGS) reaction. The highest RWGS reaction rate was observed with the Ru/CeY33 catalyst under all tested conditions. The observed differences in conversion and selectivity are attributed to a reduction in active sites due to the decrease in surface area and oxygen vacancies, both of which are important for CO₂ adsorption. In order to verify the surface species catalytically active for RWGS, the samples were characterized by FTIR spectroscopy under reaction conditions. Full article