Search

A series of M/NiCo-Ferrite (M: Pt, Pd, Ru, and Rh) nanoparticles were successfully synthesized, through a facile sol–gel auto-combustion followed by impregnation-reduction approach, as a catalyst for hydrogen generation from hydrolysis of NaBH4. All synthesized samples were characterized by XRD, N2 adsorption–desorption method, ICP-OES, FE-SEM, and EDX analysis. Compared to the other samples, it was observed that the Rh/NiCo-Ferrite sample exhibited higher particle distribution and surface area. To evaluate the hydrogen generation rate, the hydrolysis was carried out at a temperature of 35 °C, with an aqueous solution containing 5 wt.% NaBH4 and 3 wt.% NaOH. The experimental findings indicate that the Rh/NiCo-Ferrite sample exhibited a superior rate of hydrogen generation, with an average value of 11,667 mL/min.gcat, compared to the other samples studied. Enhanced catalytic properties may be responsible for its high activity. In addition, the activation energy of hydrolysis of sodium borohydride over the Rh/NiCo-Ferrite sample was 54.5 kJ/mol which is lower than the activation energy of many Ferrite-based catalysts. Moreover, the re-usability test of the Rh/NiCo-Ferrite sample denoted a decline in the catalytic activity after 4 recycling experiments due to the alterations in morphology and the reduction in the quantity of active phase. [ABSTRACT FROM AUTHOR]

Renewable energy‐driven proton exchange membrane water electrolyzer (PEMWE) attracts widespread attention as a zero‐emission and sustainable technology. Oxygen evolution reaction (OER) catalysts with sluggish OER kinetics and rapid deactivation are major obstacles to the widespread commercialization of PEMWE. To date, although various advanced electrocatalysts have been reported to enhance acidic OER performance, Ru/Ir‐based nanomaterials remain the most promising catalysts for PEMWE applications. Therefore, there is an urgent need to develop efficient, stable, and cost‐effective Ru/Ir catalysts. Since the structure‐performance relationship is one of the most important tools for studying the reaction mechanism and constructing the optimal catalytic system. In this review, the recent research progress from the construction of unsaturated sites to gain a deeper understanding of the reaction and deactivation mechanism of catalysts is summarized. First, a general understanding of OER reaction mechanism, catalyst dissolution mechanism, and active site structure is provided. Then, advances in the design and synthesis of advanced acidic OER catalysts are reviewed in terms of the classification of unsaturated active site design, i.e., alloy, core‐shell, single‐atom, and framework structures. Finally, challenges and perspectives are presented for the future development of OER catalysts and renewable energy technologies for hydrogen production. [ABSTRACT FROM AUTHOR]

This document is a compilation of contributions to a special issue on catalysts published in the journal Catalysts. The contributions cover various topics related to catalysis, including the hydrodeoxygenation of lignin-derived compounds, the synthesis of bifunctional catalysts, transfer hydrogenation of biomass-like compounds, and the development of multifunctional catalytic systems. Each contribution presents research findings and discusses the implications and potential applications of the respective catalysts. The authors express their gratitude to the editorial team and reviewers for their support and contributions. [Extracted from the article]

Tuning the chemical and structural environment of Ru-based nanomaterials is a major challenge for achieving active and stable hydrogen evolution reaction (HER) electrocatalysis. Here, we anchored ultrafine Ru nanoparticles (with a size of ~4.2 nm) on a hierarchical Ni2P array (Ru/Ni2P) to enable highly efficient HER. The Ni2P promoter weakened the adsorption of proton on Ru sites by accepting electrons from Ru nanoparticles. Moreover, the hierarchical Ni2P endowed Ru catalysts with a large surface area and stable open structure. Consequently, the as-fabricated Ru/Ni2P electrode displayed a low overpotential of 57 and 164 mV at the HER current densities of 10 and 50 mA cm−2, respectively, comparable to the state-of-the-art Pt catalysts. Moreover, the Ru/Ni2P electrode can operate stably for 96 h at 50 mA cm−2 without performance degradation. After pairing with a commercial RuO2 anode, the Ru/Ni2P anode catalyzed overall water splitting at 1.73 V with a current density of 10 mA cm−2, which was 0.16 V lower than its commercial Ni counterpart. In situ Raman studies further revealed the optimized proton adsorption at the Ru-active sites on Ni2P promoter, thus enhancing the electrocatalytic HER performance. [ABSTRACT FROM AUTHOR]

Organometallic ruthenium complexes with p-cymene = 1-methyl-4-(1-methylethyl)-benzene and N^N = bidentate polypyridyl ligands constitute interesting candidates with biological and catalytic properties. Towards this aim, we have synthesized four ruthenium(II)–arene complexes of the type [Ru(η6-p-cymene)(N^N)Cl][X] (N^N = Br-Qpy = 6-bromo-4-phenyl-2-pyridin-2-yl-quinoline, X = Cl− (1a); PF6− (1b); N^N = OH-Ph-Qpy = 4-(4-phenyl-2-(pyridin-2-yl)quinolin-6-yl)phenol, X = Cl− (2a); PF6− (2b)). This is the first report of ruthenium(II) p-cymene complexes incorporating substituted pyridine–quinoline ligands, with –Br and –C6H4OH groups in the 6-position of quinoline. We also refer to the cytotoxicity of the ligands and their possible effect of modulating the activity of the ruthenium(II) complexes. These were characterized by a combination of spectroscopic methods (ATR-IR, UV–Vis, multinuclear NMR), elemental analysis, and conductivity measurements. The solid-state structure of 2b, determined by single-crystal X-ray diffraction, reveals a three-legged piano-stool geometry. The in vitro cytotoxic activities of the new complexes were evaluated in HEK293T (human embryonic kidney cells) and in HeLa cells (cervical cancer cells), via the MTT assay. Poor in vitro anticancer activities were observed for the HeLa cancer cell line, with 2a being the most potent (IC50 = 75 μΜ). The cytotoxicity of Br-Qpy in HEK293T is comparable to that of cisplatin. Both complexes 1a and 1b successfully catalyze the transfer hydrogenation of benzophenone to benzhydrol by 2-propanol at 82 °C. The catalytic performance of 1a in the ratio of S:Cat:B = 400:1:40 (S = substrate, Cat = catalyst, B = base = KOiPr) leads to a conversion of 94%, within 3 h of reaction. Presumably, catalytic transformation takes place via ruthenium(II) hydride species being the active catalyst. [ABSTRACT FROM AUTHOR]

Electrocatalysis holds the key to enhancing the efficiency and cost-effectiveness of water splitting devices, thereby contributing to the advancement of hydrogen as a clean, sustainable energy carrier. This study focuses on the rational design of Ru nanoparticle catalysts supported on TiN (Ru NPs/TiN) for the hydrogen evolution reaction in alkaline conditions. The as designed catalysts exhibit a high mass activity of 20 A mg−1Ru at an overpotential of 63 mV and long-term stability, surpassing the present benchmarks for commercial electrolyzers. Structural analysis highlights the effective modification of the Ru nanoparticle properties by the TiN substrate, while density functional theory calculations indicate strong adhesion of Ru particles to TiN substrates and advantageous modulation of hydrogen adsorption energies via particle-support interactions. Finally, we assemble an anion exchange membrane electrolyzer using the Ru NPs/TiN as the hydrogen evolution reaction catalyst, which operates at 5 A cm−2 for more than 1000 h with negligible degradation, exceeding the performance requirements for commercial electrolyzers. Our findings contribute to the design of efficient catalysts for water splitting by exploiting particle-support interactions. Designing efficient and stable electrocatalysts for water splitting is of great interest for H2 fuel production. Here, the authors present a Ru nanoparticle catalyst on TiN, achieving 20 A mg−1 Ru at 63 mV in alkaline conditions, and operating at 5 A cm−2 for over 1000 hours in an anion exchange membrane electrolyzer. [ABSTRACT FROM AUTHOR]

Electrocatalytic nitrate reduction to ammonia holds great promise for developing green technologies for electrochemical ammonia energy conversion and storage. Considering that real nitrate resources often exhibit low concentrations, it is challenging to achieve high activity in low-concentration nitrate solutions due to the competing reaction of the hydrogen evolution reaction, let alone considering the catalyst lifetime. Herein, we present a high nitrate reduction performance electrocatalyst based on a Co nanosheet structure with a gradient dispersion of Ru, which yields a high NH3 Faraday efficiency of over 93% at an industrially relevant NH3 current density of 1.0 A/cm2 in 2000 ppm NO3- electrolyte, while maintaining good stability for 720 h under −300 mA/cm2. The electrocatalyst maintains high activity even in 62 ppm NO3- electrolyte. Electrochemical studies, density functional theory, electrochemical in situ Raman, and Fourier-transformed infrared spectroscopy confirm that the gradient concentration design of the catalyst reduces the reaction energy barrier to improve its activity and suppresses the catalyst evolution caused by the expansion of the Co lattice to enhance its stability. The gradient-driven design in this work provides a direction for improving the performance of electrocatalytic nitrate reduction to ammonia. Achieving stable and high-activity nitrate electroreduction to ammonia in low concentrations nitrate is critical but challenging. Here, the authors present a Co-based electrocatalyst with gradient-doped Ru atoms, showing a continuous ammonia production at −1000 mA/cm2 in 2000 ppm nitrate electrolyte. [ABSTRACT FROM AUTHOR]

Ru single-atom catalysts have great potential to replace toxic mercuric chloride in acetylene hydrochlorination. However, long-term catalytic stability remains a grand challenge due to the aggregation of Ru atoms caused by over-chlorination. Herein, we synthesize an asymmetric Ru-In atomic pair with vinyl chloride monomer yield (>99.5%) and stability (>600 h) at a gas hourly space velocity of 180 h−1, far surpassing those of the Ru single-atom counterparts. A combination of experimental and theoretical techniques reveals that there is a strong d-p orbital interaction between Ru and In atoms, which not only enables the selective adsorption of acetylene and hydrogen chloride at different atomic sites but also optimizes the electron configuration of Ru. As a result, the intrinsic energy barrier for vinyl chloride generation is lowered, and the thermodynamics of the chlorination process at the Ru site is switched from exothermal to endothermal due to the change of orbital couplings. This work provides a strategy to prevent the deactivation and depletion of active Ru centers during acetylene hydrochlorination. Stable operation of acetylene hydrochlorination remains a challenge due to over-chlorination of Ru. Here, the authors propose a Ru-In atom pair with d-p orbital coupling that switches the thermodynamics of chlorination process and improves stability. [ABSTRACT FROM AUTHOR]

Ruthenium complexes with facially coordinating tripodal phosphine ligands are privileged catalysts for a broad range of (de-)hydrogenation-based transformations. Among these, C–O bond hydrogenolysis holds potential for the depolymerisation of both the biopolymer lignin and epoxy resins applied in wind turbine blades, aircrafts and more. However, this methodology is poorly understood in mechanistic terms. Here, we present a detailed investigation on the triphos-Ru catalysed C–O bond scission on a molecular level. A combination of experimental, spectroscopical and theoretical studies elucidates the reactivity of the ruthenium trimethylenemethane precatalyst, revealing the key roles of ruthenium phenolates in both catalyst activation as well as the catalytic cycle itself. Furthermore, a Ru(0)/Ru(II) oxidative addition into the C–O bond is disclosed, with a triphos-Ru(0) dihydrogen complex as entry point. With the molecular nature of the operating triphos-Ru species and the thermodynamics and kinetics of the catalysis unravelled, improvements of established methods as well as design of related transformations may become possible. Ruthenium complexes with facially coordinating tripodal phosphine ligands are privileged catalysts for a broad range of (de-)hydrogenation-based transformations but the mechanism remains poorly understood. Here the authors present a detailed investigation on the triphos-Ru catalysed C–O bond scission on a molecular level. [ABSTRACT FROM AUTHOR]

Carboxylates are ideal directing groups because they are widely available, readily cleavable and excellent linchpins for diverse follow-up reactions. However, their use in meta-selective C−H functionalizations remains a substantial unmet catalytic challenge. Herein, we report the ruthenium-catalyzed meta-C–H alkylation of aromatic carboxylic acids with various functionalized alkyl halides. A bidentate N-ligand increases the electron density at the metal center of ortho-benzoate ruthenacycles to the extent that single-electron reductions of alkyl halides can take place. The subsequent addition of alkyl radicals is exclusively directed to the position para to the CAr–Ru bond, i.e., meta to the carboxylate group. The resulting catalytic meta-C−H alkylation extends to a wide range of (hetero)aromatic carboxylic acids including benzofused five-membered ring heteroarenes but no pyridine derivatives in combination with secondary/tertiary alkyl halides, including fluorinated derivatives. It also allows site-selective C5−H alkylation of 1-naphthoic acids. The products are shown to be synthetic hubs en route to meta-alkylated aryl ketones, nitriles, amides, esters and other functionalized products. Carboxylates are ideal directing groups for aryl C–H functionalizations, given their wide availability and relative ease of functional group interconversion; however, their potential in meta-selective functionalizations has not been fully realized. Here, the authors use carboxylates for meta-selective alkylations via ruthenium catalysis. [ABSTRACT FROM AUTHOR]

Liquid organic hydrogen carrier (LOHC) systems are an excellent alternative to pressurized gas and liquid hydrogen storage technologies due to their high volumetric storage capacities and straightforward adaptation to existing infrastructure. Homogeneous catalysts are promising for the selective and reversible release of hydrogen from LOHC. However, separation from product mixtures and recycling inhibit their use, particularly when comprised of costly low-abundance elements, motivating the development of heterogeneous versions that are more easily recovered and reused. Here, we describe two methods for the heterogenization of molecular Ru catalysts that efficiently dehydrogenate the polyalcohol LOHCs ethylene glycol (EG) and 1,2-propanediol (1,2-PDO). The heterogeneous versions of these catalysts maintain catalytic activity for hydrogen production comparable to the homogeneous complexes, with up to 81% conversion and 99% selectivity. DFT modeling indicates mechanistic similarities for the dehydrogenations of EG and 1,2-PDO, with the rate-limiting steps associated with protonation of the Ru-H bond to form H2 and the alkoxide species coordinated to Ru(II), followed by β-hydride elimination to regenerate the Ru-H bond. Overall, the data suggest these heterogenized molecular catalysts have potential for practical use in polyalcohol-based LOHC systems.

[Display omitted] Catalysts composed of nanocluster and single-atom (SA) were extensively used to enhance electrocatalytic water splitting performance, whereas study of their photocatalytic hydrogen (H 2) evolution activity was limited. Herein, carbon nitride (CN) decorated by ruthenium (Ru) cocatalysts existed as SA + cluster, cluster + nanoparticles (NPs), and NPs were prepared by impregnation and calcination processes. The correlation between existential form, content of Ru cocatalyst and H 2 evolution rate were carefully discussed. It was found that Ru NPs were favor for water molecule adsorption, whereas Ru SAs and clusters facilitated H 2 desorption. Theoretical calculations revealed that Ru clusters + NPs cocatalyst were beneficial for H* intermediate formation. Water splitting tests found that 1.07 wt% Ru NPs + cluster modified CN showed the highest H 2 evolution rate of 13.64 mmol h−1 g−1, which was 266.4 and 1.5 times higher than those of CN and Ru NPs (2.33 wt%) decorated CN, respectively. This work deeply reveals the influences of existential form of Ru cocatalysts on photocatalytic water splitting of CN, and provides thought in designing new cocatalysts to largely enhance H 2 evolution. [ABSTRACT FROM AUTHOR]

Asymmetric sequential hydrogenations of α‐methylene γ‐ or δ‐keto carboxylic acids are established in one‐pot using a bimetallic Ru/Ru catalyst system, achieving the stereodivergent synthesis of all four stereoisomers of both chiral γ‐ and δ‐lactones with two non‐vicinal carbon stereocenters in high yields (up to 99%) and with excellent stereoselectivities (up to >99% ee and >20:1 dr). The compatibility of the two chiral Ru catalyst systems is investigated in detail, and it is found that the basicity of the reaction system plays a key role in the sequential hydrogenation processes. The protocol can be performed on a gram‐scale with a low catalyst loading (up to 11000 S/C) and the resulting products allow for many transformations, particularly for the synthesis of several key intermediates useful for the preparation of chiral drugs and natural products. [ABSTRACT FROM AUTHOR]

Understanding the structures and reaction mechanisms of interfacial active sites in the Fisher-Tropsch synthesis reaction is highly desirable but challenging. Herein, we show that the ZrO2-Ru interface could be engineered by loading the ZrO2 promoter onto silica-supported Ru nanoparticles (ZrRu/SiO2), achieving 7.6 times higher intrinsic activity and ~45% reduction in the apparent activation energy compared with the unpromoted Ru/SiO2 catalyst. Various characterizations and theoretical calculations reveal that the highly dispersed ZrO2 promoter strongly binds the Ru nanoparticles to form the Zr-O-Ru interfacial structure, which strengthens the hydrogen spillover effect and serves as a reservoir for active H species by forming Zr-OH* species. In particular, the formation of the Zr-O-Ru interface and presence of the hydroxyl species alter the H-assisted CO dissociation route from the formyl (HCO*) pathway to the hydroxy-methylidyne (COH*) pathway, significantly lowering the energy barrier of rate-limiting CO dissociation step and greatly increasing the reactivity. This investigation deepens our understanding of the metal-promoter interaction, and provides an effective strategy to design efficient industrial Fisher-Tropsch synthesis catalysts. Understanding the structures of interfacial active sites is crucial in heterogeneous catalysis. Here the authors demonstrate that a ZrO2-Ru interface site significantly enhances reactivity in the Fischer-Tropsch to olefins process by altering the H-assisted CO dissociation route due to the presence of hydroxy species associated with Zr-OH*. [ABSTRACT FROM AUTHOR]

[Display omitted] • A novel Ru-doped CoNiFe − LDH was prepared by one-step hydrothermal method. • DFT calculations verified that Ru doping improved the electronic structure of LDH. • The optimal Ru-doped CoNiFe − LDH exhibited superior performance for supercapacitor and OER. In recent years, ternary layered double hydroxide (LDH) has become a research hotspot for electrode materials and oxygen evolution reaction (OER) catalyst due to the enhanced synergistic effect between individual elements. However, the application of LDH is greatly limited by its low electrical conductivity and the disadvantage that nanosheets tend to accumulate and mask the active sites. Herein, a novel Ru-doped CoNiFe − LDH was prepared via a facile hydrothermal method. According to the density functional theory (DFT) calculations, the doping of Ru element could improve electron state density and band gaps of LDH and consequently boosted the electrochemical reaction kinetics as well as electrical conductivity. Furthermore, introduction of Ru atom induced the formation of porous flower-like structures in nanosheets. Compared to CoNiFe − LDH (28.9 m2/g), Ru-doped CoNiFe − LDH performed larger specific surface area of 53.1 m2/g, resulting in more electrochemically active sites. In these case, Ru-doped CoNiFe − LDH demonstrated better energy storage performance of 176.0 mAh/g at 1 A/g compared to original CoNiFe − LDH (78.9 mAh/g at 1 A/g). Besides, the assembled Ru-doped CoNiFe − LDH//activated carbon (AC) device delivered a maximum energy density of 36.4 W h kg−1 at the power density of 740.3 W kg−1 and an outstanding cycle life (78.7 % after 10,000 cycles). Meanwhile, Ru-doped CoNiFe − LDH exhibited lower overpotential (339 mV at 50 mA cm−2) and Tafel slope (93.2 mV dec−1). Therefore, this work provided novel and valuable insights into the rational doping of Ru elements for the controlled synthesis of supercapacitor electrode materials and OER catalysts. [ABSTRACT FROM AUTHOR]

Ruthenium (Ru) is a promising electrocatalyst for the hydrogen evolution reaction (HER), despite suffering from low activity in non‐acidic conditions due to the high kinetic energy barrier of H2O dissociation. Herein, the synthesis of carbon nanosheet‐supported RuP/Ru heterostructures (RuP/Ru@CNS) from a natural polysaccharide is reported and demonstrates its behavior as an effective HER electrocatalyst in non‐acidic conditions. The RuP/Ru@CNS exhibits low overpotential (106 mV at 200 mA·cm−2) in alkaline electrolyte, exceeding most reported Ru‐based electrocatalysts. The electron shuttling between Ru atoms at the RuP/Ru interface results in a lowered energy barrier for H2O dissociation by electron‐deficient Ru atoms in the pure Ru phase, as well as optimized H* adsorption of electron‐gaining Ru atoms in the neighboring RuP. A low H* spillover energy barrier between Ru atoms at the RuP/Ru interface further boosts HER kinetics. This study demonstrates a sustainable method for the fabrication of efficient Ru‐based electrocatalysts and provides a more detailed understanding of interface effects in HER catalysis. [ABSTRACT FROM AUTHOR]

[Display omitted] • The Ru/Ni 3 Se 4 /Ni(OH) 2 /NF catalyst was synthesised via two-step hydrothermal method. • Spontaneous reconfiguration of electrons occurs at the heterointerface between Ru and Ni 3 Se 4 /Ni(OH) 2. • Ni 3 Se 4 /Ni(OH) 2 heterojunction facilitates stable catalysis of Ru nanoparticles. • Ru/Ni 3 Se 4 /Ni(OH) 2 /NF catalyst exhibit superior HER/OER activity and strong stability. Properly design and manufacture of bifunctional electrocatalysts with superb performance and endurance are crucial for overall water splitting. The interfacial engineering strategy is acknowledged as a promising approach to enhance catalytic performance of overall water splitting catalysts. Herein, the Ru nanoparticles modified Ni 3 Se 4 /Ni(OH) 2 heterostructured nanosheets catalyst was constructed using a simple two-step hydrothermal process. The experimental results demonstrate that the abundant heterointerfaces between Ru and Ni 3 Se 4 /Ni(OH) 2 can increase the number of active sites and effectively regulate the electronic structure, greatly accelerating the kinetics of the hydrogen evolution reaction (HER)/oxygen evolution reaction (OER). As a result, the Ru/Ni 3 Se 4 /Ni(OH) 2 /NF catalyst exhibits the low overpotential of 102.8 mV and 334.5 mV at 100 mA cm−2 for HER and OER in alkaline medium, respectively. Furthermore, a two-electrode system composed of the Ru/Ni 3 Se 4 /Ni(OH) 2 /NF requires a battery voltage of just 1.51 V at 10 mA cm−2 and remains stable for 200 h at 500 mA cm−2. This work provides an effective strategy for constructing Ru-based heterostructured catalysts with excellent catalytic activity. [ABSTRACT FROM AUTHOR]

Employing catalytic decomposition to break down reducing agents in intermediate-level radioactive waste during nuclear fuel reprocessing offers significant advantages. This study focuses on investigating the deactivation behavior of 5% Ru/C catalysts by two different synthesis processes used for reducing agent destruction. Deactivation experiments were conducted by subjecting the 5% Ru/C catalysts to 100 and 150 reaction cycles. Changes in the concentration of free radicals on the carbon-based carrier were measured to analyze the loading position and loss of Ru ions. Additionally, sorption–desorption curves and pore size distributions of the four catalysts were obtained. Analysis results reveal that Ru ions on the catalyst adsorb onto active free radical sites on the carbon-based carrier. Under ultrasonic conditions, some Ru ions partially desorb from the free radical sites on the carbon-based carrier, and desorbed Ru ions may adsorb onto weak free radical sites, while undesorbed Ru ions may adsorb onto strong free radical sites. After hundreds of hours of reaction, SM1 and SM2 exhibited approximately a 30% decrease in specific surface area and pore volume compared to SM0. However, the catalyst activity remained unchanged, and the catalyst pore size remained essentially unchanged, which primarily means that the micropores on the catalyst's surface have undergone corrosion and damage. [ABSTRACT FROM AUTHOR]

In the present study, a comparison of the dry reforming of a gas mixture containing methane, carbon dioxide and nitrogen without contaminants to a ruthenium-based Ru/Al2O3 catalyst was carried out in a microreactor for the first time. The influence of the contact time, temperature and composition of the feed on the conversion was exhaustively investigated. The optimal operating conditions were found to be a contact time of 80 milliseconds, a temperature of 700 °C and a CH4:CO2 ratio of 1. The assessment of diffusional limitations reveals that there is no resistance to mass transfer, which reveals the potential benefit of the determination of intrinsic reaction kinetics within a microreactor. [ABSTRACT FROM AUTHOR]

Isomerization Metathesis (ISOMET) reaction is an emerging tool for "open loop" chemical recycling of polyethylene to propylene. Novel, latent N‐Alkyl substituted Cyclic(Alkyl)(Amino)Carbene (CAAC)–ruthenium catalysts (5a‐Ru, 3b‐Ru – 6c‐Ru) are developed rendering "inverted" chemical structure while showing enhanced ISOMET activity in combination with (RuHCl)(CO)(PPh3)3 (RuH) double bond isomerization co‐catalyst. Systematic investigations reveal that the steric hindrance of the substituents on nitrogen and carbon atom adjacent to carbene moiety in the CAAC ligand have significantly improved the catalytic activity and robustness. In contrast to the NHC‐Ru and CAAC‐Ru catalyst systems known so far, these systems show higher isomerization metathesis (ISOMET) activity (TON: 7400) on the model compound 1‐octadecene at as low as 3.0 bar optimized pressure, using technical grade (3.0) ethylene. The propylene content formed in the gas phase can reach up to 20% by volume. [ABSTRACT FROM AUTHOR]

The electrocatalytic nitrogen reduction reaction (NRR) for synthesizing ammonia holds promise as an alternative to the traditional high-energy-consuming Haber–Bosch method. Rational and accurate catalyst design is needed to overcome the challenge of activating N2 and to suppress the competitive hydrogen evolution reaction (HER). Single-atom catalysts have garnered widespread attention due to their 100% atom utilization efficiency and unique catalytic performance. In this context, we constructed theoretical models of metal single-atom catalysts supported on titanate nanosheets (M-TiNS). Initially, density functional theory (DFT) was employed to screen 12 single-atom catalysts for NRR- and HER-related barriers, leading to the identification of the theoretically optimal NRR catalyst, Ru-TiNS. Subsequently, experimental synthesis of the Ru-TiNS single-atom catalyst was successfully achieved, exhibiting excellent performance in catalyzing NRR, with the highest NH3 yield rate reaching 15.19 μmol mgcat−1 h−1 and a Faradaic efficiency (FE) of 15.3%. The combination of experimental results and theoretical calculations demonstrated the efficient catalytic ability of Ru sites, validating the effectiveness of the constructed theoretical screening process and providing a theoretical foundation for the design of efficient NRR catalysts. [ABSTRACT FROM AUTHOR]

Fischer-Tropsch (FT) synthesis is an important module for the production of clean and sustainable fuels and chemicals, making it a topic of considerable interest in energy research. This mini-review covers the current literature on FT catalysis and offers insights into the primary products, the nuances of the FT reaction, and the product distribution, with particular attention to the Anderson-Schulz-Flory distribution (ASFD) and known deviations from this fundamental concept. Conventional FT catalysts, particularly Fe- and Co-based catalysis systems, are reviewed, highlighting their central role and the influence of water and water-gas shift (WGS) activity on their catalytic behavior. Various mechanisms of catalyst deactivation are also investigated, and the high methanation activity of Co-based catalysts is illustrated. To make this complex field accessible to a broader audience, we explain conjectured reaction mechanisms, namely, the carbide mechanism and CO insertion. We discuss the complex formation of a wide range of products, including olefins, kerosenes, branched hydrocarbons, and by-products such as alcohols and oxygenates. The article goes beyond the traditional scope of FT catalysis by addressing topics of current interest, including the direct hydrogenation of CO2 for power-to-X applications and the use of bifunctional catalysts to produce tailored FT products, most notably for the production of sustainable aviation fuel (SAF). This mini-review provides a holistic overview of the evolving landscape of FT catalysts and is aimed at both experienced researchers and those new to the field while covering current and emerging trends in this important area of energy research. [ABSTRACT FROM AUTHOR]

Bio-based polymers are attracting increasing interest as alternatives to harmful and environmentally concerning non-biodegradable fossil-based products. In particular, bio-based polymers may be employed as ligands for the preparation of metal nanoparticles (M(0)NPs). In this study, chitosan (CS) was used for the stabilization of Ru(0) and Rh(0) metal nanoparticles (MNPs), prepared by simply mixing RhCl3 × 3H2O or RuCl3 with an aqueous solution of CS, followed by NaBH4 reduction. The formation of M(0)NPs-CS was confirmed by Fourier Transform Infrared Spectroscopy (FT-IR), Differential Scanning Calorimetry (DSC), Thermal Gravimetric Analysis (TGA), Scanning Electron Microscopy (SEM), Energy-Dispersive X-ray Analysis (EDX), Transmission Electron Microscopy (TEM) and X-ray Diffraction (XRD). Their size was estimated to be below 40 nm for Rh(0)-CS and 10nm for Ru(0)-CS by SEM analysis. M(0)NPs-CS were employed for the hydrogenation of (E)-cinnamic aldehyde and levulinic acid. Easy recovery by liquid-liquid extraction made it possible to separate the catalyst from the reaction products. Recycling experiments demonstrated that M(0)NPs-CS were highly efficient up to four times in the best hydrogenation conditions. The data found in this study show that CS is an excellent ligand for the stabilization of Rh(0) and Ru(0) nanoparticles, allowing the production of some of the most efficient, selective and recyclable hydrogenation catalysts known in the literature. [ABSTRACT FROM AUTHOR]

The porous architectures of oxygen cathodes are highly desired for high-capacity lithium–oxygen batteries (LOBs) to support cathodic catalysts and provide accommodation for discharge products. However, controllable porosity is still a challenge for laminated cathodes with cathode materials and binders, since polymer binders usually shield the active sites of catalysts and block the pores of cathodes. In addition, polymer binders such as poly(vinylidene fluoride) (PVDF) are not stable under the nucleophilic attack of intermediate product superoxide radicals in the oxygen electrochemical environment. The parasitic reactions and blocking effect of binders deteriorate and then quickly shut down the operation of LOBs. Herein, the present work proposes a binder-free three-dimensional (3D) porous graphene (PG) cathode for LOBs, which is prepared by the self-assembly and the chemical reduction of GO with triblock copolymer soft templates (Pluronic F127). The interconnected mesoporous architecture of resultant 3D PG cathodes achieved an ultrahigh capacity of 10,300 mAh g−1 for LOBs. Further, the cathodic catalysts ruthenium (Ru) and manganese dioxide (MnO2) were, respectively, loaded onto the inner surface of PG cathodes to lower the polarization and enhance the cycling performance of LOBs. This work provides an effective way to fabricate free-standing 3D porous oxygen cathodes for high-performance LOBs. [ABSTRACT FROM AUTHOR]

We report on Ru-doped self-supported honeycomb nickel molybdate nanoflakes (Ru-NiMoO 4 /NF) with abundant OV on Ni foam and its application in both electrocatalytic NO 2 –RR and Zn-NO 2 – battery. The catalytic activity of Ru-NiMoO 4 /NF was significantly enhanced due to the Ru doping and the existence of oxygen vacancies, achieving high Faraday efficiency of 95.56 ± 0.72% and large ammonia yield of 17192.52 ± 1136.64 μg h−1 cm−2 at –0.6V vs. RHE in 0.5 M Na 2 SO 4 and 0.1 M NO 2 – solution, as well as preferable long-term stability. In addition, it was verified that Zn-NO 2 – battery with Ru-NiMoO 4 /NF as cathode delivers a good energy supply (13.87 mW cm−2), as well as simultaneously ammonium yield of 1524.74 μg h−1 cm−2 and Faradaic efficiency of 96.15% at 15 mA cm−2. [Display omitted] The electrocatalytic reduction of nitrite to recyclable ammonia (NH 3) is essential to maintain nitrogen balance and meet growing energy requirements. Herein, we report that Ru doped honeycomb NiMoO 4 nanosheet with copious oxygen vacancies grown on nickel foam substrate has been prepared by a facile hydrothermal synthesis and immersion process, which can act as an efficient electrocatalyst for NH 3 synthesis by reduction of nitrite. By optimizing the concentration of RuCl 3 solution, 0.01Ru-NiMoO 4 /NF possesses excellent NO 2 −RR performance with NH 3 yield of 20249.17 ± 637.42 μg h−1 cm−2 at −0.7 V and FE of 95.56 ± 0.72 % at −0.6 V. When assembled into a Zn–NO 2 − battery, it provides a remarkable level of power density of 13.89 mW cm−2, outperforming the performance of virtually all previous reports. The efficient adsorption and activation of NO 2 − over Ru-doped NiMoO 4 with oxygen vacancy have been verified by density functional theory calculations, as well as the possible reaction pathway. [ABSTRACT FROM AUTHOR]

Robert H Grubbs (1942–2021), Nobel laureate and former professor of Caltech, USA, is celebrated for his path breaking discovery of a series of ruthenium carbene based organometallic catalysts, well known as Grubbs catalysts. These catalysts are widely used by chemists across the world for carrying out a variety of olefin metathesis reactions under mild and ambient conditions. The article describes the synthesis and development of Grubbs ruthenium carbene catalysts and their closely related analogues. Their differences in structure, reactions and properties, their advantages and disadvantages when applied as catalysts in olefin metathesis reactions are briefly highlighted. [ABSTRACT FROM AUTHOR]

The present study elucidates the oxidation of alcohols to terpene ketones using dichloro(p-cymene) ruthenium (II) dimer catalyst by continuous flow process using a metal plate reactor. The synthesized products were separated and validated using GC, GCMS, 1H-NMR, and 13C-NMR techniques. The reaction process exhibited product yield in the range of 80-95% on a scale of 1-80 grams. Optimization studies were conducted to calibrate the reaction conditions to improve the product yield. The scope of the reaction was explored using aromatic, cyclic, and aliphatic alcohols under optimized conditions, which resulted in high yields of terpene ketones. A reaction mechanism is proposed for the oxidation of alcohols by a continuous flow process. The significant advantages of the current protocol include synthesis at mild conditions, safer handling of reagents, flexibility to tune reaction conditions, and straightforward scale-up in the range of 1-80 grams with high efficiency and reproducibility. [ABSTRACT FROM AUTHOR]

The development of direct dimethyl ether (DME) solid oxide fuel cells (SOFCs) has several drawbacks, due to the low catalytic activity and carbon deposition of conventional Ni–zirconia-based anodes. In the present study, the insertion of 2.0 wt.% Ru-Ce0.7Zr0.3O2−δ (ruthenium–zirconium-doped ceria, Ru-CZO) as an anode catalyst layer (ACL) is proposed to be a promising solution. For this purpose, the CZO powder was prepared by the sol–gel synthesis method, and subsequently, nanoparticles of Ru (1.0–2.0 wt.%) were synthesized by the impregnation method and calcination. The catalyst powder was characterized by BET-specific surface area, X-ray diffraction (XRD), field emission scanning electron microscopy with an energy-dispersive spectroscopy detector (FESEM-EDS), and transmission electron microscopy (TEM) techniques. Afterward, the catalytic activity of Ru-CZO catalyst was studied using DME partial oxidation. Finally, button anode-supported SOFCs with Ru-CZO ACL were prepared, depositing Ru-CZO onto the anode support and using an annealing process. The effect of ACL on the electrochemical performance of cells was investigated under a DME and air mixture at 750 °C. The results showed a high dispersion of Ru in the CZO solid solution, which provided a complete DME conversion and high yields of H2 and CO at 750 °C. As a result, 2.0 wt.% Ru-CZO ACL enhanced the cell performance by more than 20% at 750 °C. The post-test analysis of cells with ACL proved a remarkable resistance of Ru-CZO ACL to carbon deposition compared to the reference cell, evidencing the potential application of Ru-CZO as a catalyst as well as an ACL for direct DME SOFCs. [ABSTRACT FROM AUTHOR]

This work focuses on the study of biodiesel production from commercial rapeseed oil and methanol via transesterification reactions on monometallic copper and bimetallic copper–noble metal (platinum, ruthenium) catalysts supported on BEA zeolite. The catalysts were prepared by wet impregnation method on the hydrogen form of BEA zeolite. As part of the study, the physicochemical and catalytic properties of the prepared catalytic materials were determined. The catalytic activity tests were carried out in the transesterification reaction over prepared catalysts at 220 °C for 2 h in an autoclave. The physicochemical properties of the obtained catalysts were investigated by X-ray diffraction (XRD), specific surface area and porosity (BET), a scanning electron microscope equipped with an energy dispersive spectrometer (SEM–EDS) and temperature-programmed desorption of ammonia (TPD-NH3) method. The results of the catalytic activity showed the promotional effect of the noble metal on the TG conversion and FAME efficiency of copper catalysts in the biodiesel production process. The most active catalyst turned out to be the calcined 5%Cu–1%Ru/BEA catalyst, which showed the highest TG conversion of 85.7% and the second highest FAME efficiency of 58.4%. The high activity of this system is explained by its surface acidity and large specific surface area. [ABSTRACT FROM AUTHOR]

The preparation of basalt and S‐glass fiber‐reinforced poly(dicyclopentadiene) via ring‐opening metathesis polymerization using a thermally latent pre‐catalyst, that is, Mo(N‐3,5‐Me2‐C6H3)(= CH‐(2‐MeO‐C6H4))(IMes)(OTf)2 (1, IMes = 1,3‐dimesitylimidazol‐2‐ylidene; OTf = SO3CF3) is reported. Complementarily, the non‐latent first‐generation Grubbs initiator RuCl2(PPh3)2(CHPh) (2) is used. 2 can be rendered latent by the addition of ppm amounts of triphenylphosphine (PPh3). Both 1 and 2/PPh3 allow the realization of thermally latent single‐component systems with sufficient pot life that do not require pre‐mixing of the individual components shortly before use. The prepared fiber matrix composites are characterized in terms of mechanical, thermal, and chemical stability. [ABSTRACT FROM AUTHOR]

The Fe(OH) x -Ru/Ni(OH) 2 nanosheets array electrocatalysts are prepared by an acid etching assisted electrodeposition method, which shows outstanding catalytic activity with a low voltage of 1.649 V at 500 mA cm−2 for overall water splitting. [Display omitted] • Fe(OH)x-Ru/Ni(OH)2 nanosheets arrays were synthesized by a simple acid etching assisted electrodeposition method at room temperature. • Fe(OH)x-Ru/Ni(OH)2 nanosheets arrays exihibit an excellent activity to both HER and OER. • Fe(OH)x-Ru/Ni(OH)2 nanosheets arrays pair achieve 500 mA cm − 2 at 1.649 V. Developing highly active electrocatalysts for overall water splitting is of remarkable significance for industrial production of H 2. Herein, exceptionally active Fe(OH) x modified ultra-small Ru nanoparticles on Ni(OH) 2 nanosheets array (Fe(OH) x -Ru/Ni(OH) 2) for both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) are reported. The Fe(OH) x -Ru/Ni(OH) 2 nanosheets array prepared with Fe/Ru molar ratio of 5 only requires extremely low overpotentials of 61, 127 and 170 mV to reach current densities of 100, 500 and 800 mA cm−2 in 1 M KOH, respectively, exceeding Pt/C catalyst (75, 160 and 177 mV). Meanwhile, the Fe(OH) x /Ni(OH) 2 nanosheets array derived from Fe(OH) x -Ru/Ni(OH) 2 exhibits excellent OER activity. It gains current densities of 100, 500 and 800 mA cm−2 at considerably low overpotentials of 265, 285 and 296 mV, respectively, much lower than those of RuO 2 and most reported electrocatalysts. The introduction of Fe(OH) x significantly improves the HER activity of Ru nanoparticles by tunning the electronic structure and forming interfaces between Ru and Fe(OH) x. Dramatically, the integrated alkaline electrolyzer based on Fe(OH) x -Ru/Ni(OH) 2 and Fe(OH) x /Ni(OH) 2 nanosheets array pair just needs 1.649 V to yield a current density up to 500 mA cm−2, exceeding most reported water-splitting electrocatalysts. The strategy reported in this work can be facilely extended to prepare other similar Ru based materials and their derivatives with outstanding catalytic performance for water splitting. [ABSTRACT FROM AUTHOR]

[Display omitted] • Novel sulfates supported binary RuIrO x be synthesized. • A strong catalyst-support interaction between RuIrO x and BaSrSO 4. • The RuIrO x /BSS exhibits a high OER mass activity of only 324 mV overpotential at 1000 A/g Ru + Ir. • It shows outstanding CER activity and stability. Electrolysis for producing hydrogen powered by renewable electricity can be dramatically expanded by adapting different electrolytes (brine, seawater or pure water), which means the anode materials must stand up to complex electrolyte conditions. Here, a novel catalyst/support hybrid of binary Ru 3.5 Ir 1 O x supported by barium strontium sulfate (BaSrSO 4) was synthesized (RuIrO x /BSS) by exchanging the anion ligands of support. The as-synthesized RuIrO x /BSS exhibits compelling oxygen evolution (OER) and chlorine evolution (CER) performances, which affords to 10 mA cm−2 with only overpotential of 244 mV and 38 mV, respectively. The performed X-ray adsorption spectra clearly indicate the presence of an interface charge transfer effect, which results in the assignment of more electrons to the d orbitals of the Ru and Ir sites. The theoretical calculations demonstrated that the electronic structures of the catalytic active sites were modulated to give a lower overpotential, confirming the intrinsically high OER and CER catalytic activity. [ABSTRACT FROM AUTHOR]

Graphdiyne (GDY) is considered a very attractive support for metal nanocatalysts due to its unique structure and superior properties. The metal–GDY interaction can significantly affect the performance of catalysts. Herein, GDY nanotubes abundant in in situ formed Cu quantum dots (QDs) (Cu-GDYNT) are prepared using the electrospun polyacrylonitrile nanofibers collected on the surface of electrolytic Cu foil as templates. The diameter of the Cu-GDYNT is controllable and the uniform size of the embedded Cu QDs is about 2.2 nm. And then, the uniformly dispersed and highly active supported catalysts of ruthenium nanoparticles (Rux/Cu-GDYNT) are produced using the Cu-GDYNT as the support. Among them, the Ru3/Cu-GDYNT exhibit outstanding HER performance at all pH levels. Only 17, 67 and 83 mV overpotential is required to reach a current density of 10 mA cm−2 in 1.0 M KOH, 0.5 M H2SO4 and 1.0 M neutral PBS solutions, respectively. The sample exhibits 3000 CV cycle stability and 20 h continuous electrolysis without performance degradation in an alkaline medium. This work provides a new idea for constructing the GDY-supported metal nanocatalysts. [ABSTRACT FROM AUTHOR]

Electrons are transferred from RuO 2 to Co 3 O 4 through the amorphous-crystalline heterointerface, realizing electron redistribution and moving the d-band center upward. RuO 2 /Co 3 O 4 undergoes surface reconstruction during the HER/OER process and has excellent catalytic performance. [Display omitted] • RuO 2 /Co 3 O 4 amorphous-crystalline heterointerface is prepared. • Electrons are transferred from RuO 2 to Co 3 O 4 through the amorphous-crystalline heterointerface to achieve electron redistribution. • RuO 2 /Co 3 O 4 reconstructed into Ru-Co(OH) 2 and RuO 2 -COOOH as active centers to enhance HER and OER catalytic activity, respectively. • RuO 2 /Co 3 O 4 exhibits excellent overall water splitting performance. The rational construction of amorphous-crystalline heterointerface can effectively improve the activity and stability of hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). Herein, RuO 2 /Co 3 O 4 (RCO) amorphous-crystalline heterointerface is prepared via oxidation method. The optimal RCO-10 exhibits low overpotentials of 57 and 231 mV for HER and OER at 10 mA cm−2, respectively. Experimental characterization and density functional theory (DFT) results show that the optimized electronic structure and surface reconstruction endow RCO-10 with excellent catalytic activity. DFT results show that electrons transfer from RuO 2 to Co 3 O 4 through the amorphous-crystalline heterointerface, achieving electron redistribution and moving the d-band center upward, which optimizes the adsorption free energy of the hydrogen reaction intermediate. Moreover, the reconstructed Ru/Co(OH) 2 during the HER process has low hydrogen adsorption free energy to enhance HER activity. The reconstructed RuO 2 /CoOOH during the OER process has a low energy barrier for the elementary reaction (O*→*OOH) to enhance OER activity. Furthermore, RCO-10 requires only 1.50 V to drive 10 mA cm−2 and maintains stability over 200 h for overall water splitting. Meanwhile, RCO-10 displays stability for 48 h in alkaline solutions containing 0.5 M NaCl. The amorphous-crystalline heterointerface may bring new breakthroughs in the design of efficient and stable catalysts. [ABSTRACT FROM AUTHOR]

In response to the vital requirement for renewable energy alternatives, this research delves into the complex interactions between ruthenium (Ru3) clusters and rutile titanium dioxide (TiO2) (110) interfaces, with the aim of enhancing photocatalytic water splitting processes to produce environmentally friendly hydrogen. As the world shifts away from traditional fossil fuels, this study utilizes the density functional theory (DFT) and the HSE06 hybrid functional to thoroughly assess the geometric and electronic properties of Ru3 clusters on rutile TiO2 (110) surfaces. Given TiO2's renown role as a photocatalyst and its limitations in visible light absorption, this research investigates the potential of metals like Ru to serve as additional catalysts. The results indicate that the triangular Ru3 cluster exhibits exceptional stability and charge transfer effectiveness when loaded on rutile TiO2 (110). Under ideal adsorption scenarios, the cluster undergoes oxidation, leading to subsequent changes in the electronic configuration of TiO2. Further exploration into TiO2 surfaces with defects shows that Ru3 clusters influence the creation of oxygen vacancies, resulting in a greater stabilization of TiO2 and an increase in the energy required for creating oxygen vacancies. Moreover, the attachment of the Ru3 cluster and the creation of oxygen vacancies lead to the emergence of polaronic and hybrid states centered on specific titanium atoms. These states are vital for enhancing the photocatalytic performance of the material within the visible light spectrum. This DFT study provides essential insights into the role of Ru3 clusters as potential supplementary catalysts in TiO2-based photocatalytic systems, setting the stage for practical experiments and the development of highly efficient photocatalysts for sustainable hydrogen generation. The observed effects on electronic structures and oxygen vacancy generation underscore the intricate relationship between Ru3 clusters and TiO2 interfaces, offering a valuable direction for future research in the pursuit of clean and sustainable energy solutions. [ABSTRACT FROM AUTHOR]

On-site hydrogen generation from ammonia decomposition is a promising technology to address the challenges of direct transportation and storage of hydrogen. The main problems with the existing support materials for ammonia decomposition catalysts are their high cost and time-consuming preparation process. In this work, ammonia decomposition catalysts consisting of in situ-formed nano-Ru particles supported on a naturally abundant mineral fiber, attapulgite (ATP), were proposed and studied. Also, 1 wt.% Ru was uniformly dispersed and anchored onto the surface of ATP fibers via the chemical method. We found that the calcination temperatures of the ATP support before the deposition of Ru resulted in little difference in catalytic performance, while the calcination temperatures of the 1Ru/ATP precursor were found to significantly influence the catalytic performance. The prepared 1 wt.% Ru/ATP catalyst (1Ru/ATP) without calcination achieved an ammonia conversion efficiency of 51% at 500 °C and nearly 100% at 600 °C, with the flow rate of NH3 being 10 sccm (standard cubic centimeter per minute). A 150 h continuous test at 600 °C showed that the 1Ru/ATP catalyst exhibited good stability with a degradation rate of about 0.01% h−1. The 1Ru/ATP catalyst was integrated with proton ceramic fuel cells (PCFCs). We reported that PCFCs at 650 °C offered 433 mW cm−2 under H2 fuel and 398 mW cm−2 under cracked NH3 fuel. The overall results suggest low-level Ru-loaded ATP could be an attractive, low-cost, and efficient ammonia decomposition catalyst for hydrogen production. [ABSTRACT FROM AUTHOR]

The synthesis of nylon 6 and nylon 66 can be performed, starting with the selective hydrogenation of benzene to cyclohexene, which is deemed to be environmentally friendly and cost-saving and to have higher atom efficiency. Nano-Ru catalyst was synthesized via a precipitation method. The prepared catalyst was evaluated in the selective hydrogenation of benzene toward cyclohexene generation in the presence of ZnSO4 in a liquid batch reactor. The promotion effect of the addition of amines, i.e., ethylenediamine, ethanolamine, diethanolamine, and triethanolamine, was investigated. The fresh and spent catalysts were thoroughly characterized by XRD, TEM, AES, N2-sorption, FT-IR, and TPR. It was found that the addition of amines could significantly improve the catalytic selectivity toward cyclohexene formation in the presence of ZnSO4. This was attributed to the formation of (Zn(OH)2)5(ZnSO4)(H2O)x (x = 0.5, 3 or 4) through the reaction between ZnSO4 and the amines, which could be chemisorbed on the Ru surface. This led to retarding the formation of cyclohexane from the complete hydrogenation of benzene and, thus, increased the catalytic selectivity toward cyclohexene synthesis. Therefore, with the presence of ZnSO4, the amount of chemisorbed (Zn(OH)2)5(ZnSO4)(H2O)x increased with increasing amounts of added amines, leading to a decline in the catalytic activity toward benzene conversion and selectivity toward cyclohexene generation. When 7.6 mmol of diethanolamine and 10 g of ZrO2 were applied, the highest cyclohexene yields of 61.6% and 77.0% of benzene conversion were achieved over the Ru catalyst. Promising stability was demonstrated after six runs of catalytic experiments without regeneration. These achievements are not only promising for industrial application but also beneficial for designing other catalytic systems for selective hydrogenation. [ABSTRACT FROM AUTHOR]

We report an investigation of catalyst performance for the decomposition of ammonia under industrially relevant conditions (high temperatures of up to 800 °C and an elevated pressure of 5 bar) with further emphasis on their stability at high reaction temperatures. The catalysts were applied and tested as coatings in 500 µm wide channels of microreactors. Nickel-based catalysts were studied and compared to a ruthenium-based catalyst supported on SiO2. The effect of the support on the catalytic performance was investigated, and CeO2-supported nickel catalysts were found to exhibit the highest activity. Promoters were applied to increase the NH3 decomposition activity of the Ni/CeO2 catalysts. The addition of cesium led to a slight reduction in activity, while lanthanum, calcium, and barium doping resulted in increased activity. In particular, the barium-doped Ni/CeO2 catalyst showed very high ammonia conversion and closed the activity gap with respect to ruthenium catalysts at reactor temperatures of 650 °C and higher. The hydrogen production rates achieved in this work were compared to values in the literature and were shown to exceed values found earlier for both nickel- and ruthenium-based catalysts. Furthermore, the ruthenium-based catalysts under investigation were rapidly deactivated at 700 °C, while the nickel-based catalysts did not show deactivation after 220 h on time on stream at 700 °C. [ABSTRACT FROM AUTHOR]

[Display omitted] Bimetallic catalysts often outperform monometallic catalysts due to changeable structural orientation, synergistic effects, and integration of two different metal or metal oxide properties. Here, a series of CeO 2 nanorods (NR) supported bimetallic CuO x and RuO x catalysts (Cu: Ru ratios of 9:1, 7:3, and 5:5) were prepared using a wet impregnation method. In situ DRIFTS, H 2 temperature programmed reduction (H 2 -TPR), CO temperature programmed desorption (CO-TPD), and other characterization techniques were used to investigate the effect of the Cu:Ru ratio on the activity of low-temperature CO oxidation. Among three catalysts, CeO 2 NR supported 7 wt% Cu-3 wt% Ru catalyst after a reduction activation treatment showed the best performance with 100 % CO conversion at 166 °C and the lowest activation energy of 18.37 kJ mol−1. Raman and XPS profiles revealed that the origin of the superior performance is at least partially related to the high surface oxygen vacancy concentration and other distinct oxygen species (physi-/chemi-sorbed oxygen and bulk lattice oxygen), leading to outstanding adsorption and oxidation property of CO. [ABSTRACT FROM AUTHOR]

Support effect is an important issue in heterogeneous catalysis, while the explicit role of a catalytic support is often unclear for catalytic reactions. A systematic density functional theory computational study is reported in this paper to elucidate the effect of a model boron nitride (BN) support on the first N-H bond activation step of NH3 on Run (n = 1, 2, 3) metal clusters. Geometry optimizations and energy calculations were carried out using density functional theory (DFT) calculation for intermediates and transition states from the starting materials undergoing the N-H activation process. The primary findings are summarized as follows. The involvement of the model BN support does not significantly alter the equilibrium structure of intermediates and transition states in the most favorable pathway (MFP). Moreover, the involvement of BN support decreases the free energy of activation, ΔG≠, thus improving the reaction rate constant. This improvement is more obvious at high temperatures like 673 K than low temperatures like 298 K. The BN support effect leading to the ΔG≠ decrease is most significant for the single Ru atom case among all three cases studied. Finally, the involvement of the model BN may change the spin transition behavior of the reaction system during the N-H bond activation process. All these findings provide a deeper insight into the support effect on the N-H bond activation of NH3 for the supported Ru catalyst in particular and for supported transition metal catalysts in general. [ABSTRACT FROM AUTHOR]

The state-of-the-art alkaline hydrogen evolution catalyst of united ruthenium single atoms and small ruthenium nanoparticles has sparked considerable research interest. However, it remains a serious problem that hydrogen evolution primarily proceeds on the less active ruthenium single atoms instead of the more efficient small ruthenium nanoparticles in the catalyst, hence largely falling short of its full activity potential. Here, we report that by combining highly oxophilic cerium single atoms and fully-exposed ruthenium nanoclusters on a nitrogen functionalized carbon support, the alkaline hydrogen evolution centers are facilely reversed to the more active ruthenium nanoclusters driven by the strong oxophilicity of cerium, which significantly improves the hydrogen evolution activity of the catalyst with its mass activity up to −10.1 A mg−1 at −0.05 V. This finding is expected to shed new light on developing more efficient alkaline hydrogen evolution catalyst by rational regulation of the active centers for hydrogen evolution. The Ru single atom-nanocluster alkaline hydrogen evolution catalyst suffers from that hydrogen forms on its less active single atom side. Here, the authors report that oxophilic Ce single atom can reverse the hydrogen formation site to more active Ru nanocluster, enabling enhanced hydrogen evolution capabilities. [ABSTRACT FROM AUTHOR]

The three typical oxygen-containing functional groups on C-dots have been selectively deactivated to elucidate their impact on the co-reactant behavior of C-dots, and the carboxyl groups on C-dots are revealed for the first time as co-reactant sites for Ru(bpy) 3 2+-ECL. [Display omitted] Carbon nanodots (C-dots) with good biocompatibility have been extensively utilized as co-reactants for electrochemiluminescence (ECL) of the tris(2,2′-bipyridine)ruthenium(II) (Ru(bpy) 3 2+) system. However, the ECL intensity of this system is still relatively low and the mechanism of C-dots as co-reactants remains unclear, which greatly limits its further application in bio-analysis. In this work, we revealed that the carboxyl groups on C-dots are co-reactant sites for Ru(bpy) 3 2+ ECL by systematically investigating the contribution of carboxyl, hydroxyl and carbonyl groups on the surface of C-dots to the ECL intensity. Further treatment with hydrogen peroxide to increase the carboxyl-group content on C-dots resulted in a 10-fold increase in ECL intensity over the original Ru(bpy) 3 2+/C-dots system. This work provides new insights for the rational design of ECL systems with C-dots as co-reactants and offers new chances for further applications of C-dots in the field of ECL. [ABSTRACT FROM AUTHOR]

The integration of dual asymmetric catalysis is highly beneficial for the synthesis of organic molecules with multiple stereocenters. However, two major issues that need to be addressed are the intrinsic deactivation of dual-species and the extrinsic conflict of reaction conditions. To overcome these concerns, we have utilized the compartmental and thermoresponsive properties of poly(N-isopropylacrylamide) (PNIPAM) to develop a cross-linked PNIPAM-hydrogel-supported bifunctional catalyst. This catalyst is designed with Rh(diene) species situated on the outer surface and Ru(diamine) species positioned within the interior of the hydrogel. The compartmental function of PNIPAM in the middle overcomes intrinsic mutual deactivations between the dual-species. The thermoresponsive nature of PNIPAM allows for precise control of catalytic pathways in resolving external conflicts by controlling the reaction switching between an Rh-catalyzed enantioselective 1,4-addition at 50°C and a Ru-catalyzed asymmetric transfer hydrogenation (ATH) at 25°C. As we envisioned, this sequential 1,4-addition/reduction dual enantioselective cascade reaction achieves a transformation from incompatibility to compatibility, resulting in direct access to γ-substituted cyclic alcohols with dual stereocenters in high yields and enantio/diastereoselectivities. Mechanistic investigation reveals a reversible temperature transition between 50°C and 25°C, ensuring a cascade process comprising a 1,4-addition followed by the ATH process. Dual asymmetric catalysis is powerful for the synthesis of multi-stereocenter molecules, however, the integration of dual catalysts remains challenging due to the intrinsic deactivation of dual-species and extrinsic conflict of reaction conditions. Here, the authors develop a compartmental and thermoresponsive poly(N-isopropylacrylamide)-hydrogel-supported bifunctional catalyst to overcome these challenges. [ABSTRACT FROM AUTHOR]

Crystalline phase engineering is a prominent strategy for synergistically optimizing the surface–body phases of a catalyst. In this work, TiO2 nanosheets assembled into nanotubes (TNSTs) with two phases, anatase and rutile, were firstly synthesized via crystal engineering by simple thermal annealing. These were subsequently loaded with Ru nanoparticles, with a mean size of 5.0 nm, to create the efficient benzene hydrogenation catalyst Ru/TNSTs. The well-designed nanosheet-tube structure boasts a large specific surface area and excellent transmission channels, which effectively prevents the agglomeration and deactivation of loaded Ru nanoparticles, as well as promoting the internal diffusion in the reaction process of benzene hydrogenation to cyclohexene. Furthermore, titanium dioxide nanosheet-tubes contain numerous Ti3+ defects, which not only improves the overall conversion rate of cyclohexene but also enhances the suppression of cyclohexene adsorption. Most importantly, the titanium dioxide with its two-phase composition of 75 wt% anatase and 25 wt% rutile increases the ratio of electron deficiencies of Ru and promotes cyclohexene desorption. These synergistic properties enhance the selectivity and efficiency of the Ru/TNSTs catalysts, resulting in excellent performance in the hydrogenation of benzene to cyclohexene. In particular, the Ru/TNSTs-4 catalyst (annealed for 4 h), under the specific conditions of 140 °C temperature and 5 MPa hydrogen pressure for the hydrogenation process, achieves a 95% initial selectivity and 51% yield of cyclohexene in the reaction, outperforming most supported Ru-based catalysts. This work may provide new perspectives for designing efficient benzene hydrogenation catalysts via crystalline phase engineering. [ABSTRACT FROM AUTHOR]

The structure and electrocatalytic activity of the Ru-doped cobalt oxides derived from the metal–organic frameworks (MOFs) for large-current–density water splitting are highly dependent on the preorganized structure and chemistry of the MOFs. [Display omitted] The influence of the preorganized structure and chemical composition of metal-organic frameworks (MOFs) on the morphology, surface properties, and catalytic activity of the MOFs-derived metal oxides is yet to be revealed. In this work, two types of Co-MOFs with different coordination configurations are synthesized for the preparation of the structure-engineered ruthenium (Ru)-doped cobalt oxides. The effect of the preorganized coordination structure of the MOFs on the morphology and surface properties is investigated. Interestingly, the oxalate-based MOFs derived Ru-doped cobalt oxide (OX-Co 3 O 4 -Ru) exhibits much better surface wettability and more oxygen vacancies than the zeolitic imidazolate framework-67 derived Ru-doped cobalt oxide. As expected, the OX-Co 3 O 4 -Ru owns excellent catalytic properties towards both hydrogen evolution reaction and oxygen evolution reaction with an overpotential of 49 and 286 mV, respectively at a current density of 100 mA cm−2 in 1.0 M KOH. Importantly, the bifunctional OX-Co 3 O 4 -Ru catalyst offers an extremely high current density of 500 mA cm−2 at a cell voltage of 1.71 V for overall water splitting and as well demonstrates robust working stability. [ABSTRACT FROM AUTHOR]

The title compound, [RuCl2(C33H43N3O)], is an example of a new generation of N,N-dialkyl ruthenium catalysts with an N--Ru coordination bond as part of a six-membered chelate ring. The Ru atom has an Addison parameter of 0.244, which indicates a geometry intermediate between square-based pyramidal and trigonal-bipyramidal. The complex shows the usual trans arrangement of the two chlorides, with Ru--Cl bond lengths of 2.3515 (8) and 2.379 (7) Å, and a Cl--Ru--Cl angle of 158.02 (3)°. One of the chlorine atoms and the atoms of the 2-methoxy-N-methyl-N-[(2-methylphenyl)methyl]ethane-1-amine group of the title complex display disorder over two positions in a 0.889 (2): 0.111 (2) ratio. [ABSTRACT FROM AUTHOR]

Ar, Ar/H2 (95:5), and Ar/O2 (95:5) plasmas are used for treating the NiCo metal–organic framework (MOF), and the plasma-processed NiCo MOF is applied for catalyzing the oxygen evolution reaction (OER) in a 1 M KOH electrolyte. Linear sweep voltammetry measurements show that after plasma treatment with Ar/H2 (95:5) and Ar gases, the overpotential reaches 552 and 540 mV, respectively, at a current density of 100 mA/cm2. The increase in the double-layer capacitance further confirms the enhanced oxygen production activity. We test the Ar plasma-treated NiCo MOF as an electrocatalyst at the OER electrode and Ru as an electrocatalyst at the hydrogen evolution reaction (HER) electrode in the alkaline water electrolysis module. The energy efficiency of the electrolyzer with the Ar plasma-processed NiCo-MOF catalyst increases from 54.7% to 62.5% at a current density of 500 mA/cm2 at 25 °C. The alkaline water electrolysis module with the Ar plasma-processed catalyst also exhibits a specific energy consumption of 5.20 kWh/m3 and 4.69 kWh/m3 at 25 °C and 70 °C, respectively. The alkaline water electrolysis module performance parameters such as the hydrogen production rate, specific energy consumption, and energy efficiency are characterized at temperatures between 25 °C and 70 °C. Our experimental results show that the NiCo MOF is an efficient OER electrocatalyst for the alkaline water electrolysis module. [ABSTRACT FROM AUTHOR]

Xylose is nowadays converted into xylitol, a popular special chemical sweetener. Xylitol can be used not only in the pharmaceutical and food industries, but also in cosmetics and synthetic resins because of its countless properties. Conventionally, xylitol is produced by slurry reactors operating in batch with dispersed or supported catalysts. Hydrogen is continuously fed to maintain a constant pressure. In this work, the kinetics of the reaction were investigated to find the optimal operating conditions to minimize the by-products obtained. Given the great performances shown by the new Ru/SiO2 sol–gel derived catalyst in glucose hydrogenation, in this work the mentioned catalyst was tested in the hydrogenation of xylose to xylitol both in batch and in continuous production to prove its stability and activity. [ABSTRACT FROM AUTHOR]

Developing cost‐efficient bifunctional water splitting catalysts is crucial for sustainable hydrogen energy applications. Herein, ruthenium (Ru)‐incorporated and phosphorus (P)‐doped nickel molybdate (Ru‐NiMoO(P)4) nanosheet array catalysts are synthesized. Due to the synergy of Ru clusters and NiMoO(P)4 by the modulated electronic structure and the rich active sites, impressively, Ru‐NiMoO(P)4 exhibits superior OER (194 mV @ 50 mA cm−2) and HER (24 mV @ 10 mA cm−2) activity in alkaline media, far exceeding that of commercial Pt/C and RuO2 catalysts. Meanwhile, as bifunctional catalyst, to drive the overall water splitting at the current density of 10 mA cm−2, Ru‐NiMoO(P)4 requires only 1.45 V and maintaining stable output for 100 h. Furthermore, Ru‐NiMoO(P)4 also possesses excellent capability for seawater electrolysis hydrogen production. Moreover, the successful demonstration of wind and solar hydrogen production systems provide the feasibility of the ultra‐low Ru loading catalyst for large‐scale hydrogen production in the future. [ABSTRACT FROM AUTHOR]

The in-situ activation process alleviates the strong ruthenium-hydrogen and ruthenium-hydroxyl bonds, optimizing hydrogen and hydroxyl desorption energy. [Display omitted] • Partially oxidized Ru nanoparticles dispersed Ni 3 N nanosheet electrocatalyst was developed. • The in-situ electrochemical activation effectively promoted hydrogen evolution. • The controlled oxidation alleviates the strong Ru-H and Ru-OH bonds. • The catalysts show superior performance for HER and urea-assisted water splitting. The rational design of electrocatalysts with exceptional performance and durability for hydrogen production in alkaline medium is a formidable challenge. In this study, we have developed in-situ activated ruthenium nanoparticles dispersed on Ni 3 N nanosheets, forming a bifunctional electrocatalyst for hydrogen evolution and urea oxidation. The results of experimental analysis and theoretical calculations reveal that the enhanced hydrogen evolution reaction (HER) performance of O-Ru-Ni 3 N stems primarily from the optimized hydrogen adsorption and hydroxyl adsorption on Ru sites. The O-Ru-Ni 3 N on nickel foam (NF) electrode exhibits excellent HER performance, requiring only 29 mV to reach 10 mA cm−2 in an alkaline medium. Notably, when this O-Ru-Ni 3 N/NF catalyst is employed for both HER and urea oxidation reaction (UOR) to create an integrated H 2 production system, a current density of 50 mA cm−2 can be generated at the cell voltage of 1.41 V. This report introduces an energy-efficient catalyst for hydrogen production and proposes a viable strategy for anodic activation in energy chemistry. [ABSTRACT FROM AUTHOR]