Ruthenium Acetylacetonate Research Articles

A MOF-Gel Based Separator for Suppressing Redox Mediator Shuttling in Li-O2 Batteries.

Redox mediators (RMs) are widely utilized in the electrolytes of Li-O2 batteries to catalyze the formation/decomposition of Li2O2, which significantly enhances the cycling performance and reduces the charge overpotential. However, RMs have a shuttle effect by migrating to the Li anode side and inducing Li metal degradation through a parasitic reaction. Herein, a metal-organic framework gel (MOF-gel) separator is proposed to restrain the shuttling of RMs. Compared to traditional MOF nanoparticles, MOF gels form uniform and dense films on the separators. When using Ru(acac)3 (ruthenium acetylacetonate) as an RM, the MOF-gel separator suppresses the shuttling of Ru(acac)3 toward the Li anode side and significantly enhances the performance of Li-O2 batteries. Specifically, Li-O2 batteries exhibit an ultralong cycling life (410 cycles) at a current density of 0.5 A g-1. Moreover, the batteries using the MOF-gel/celgard separator exhibit significantly improved cycling performance (increase by ≈1.6 times) at a high current density of 1.0 A g-1 and a decreased charge/discharge overpotential. This result is expected to guide future development of battery separators and the exploration of redox mediators.

Influences of Ru and ZrO2 interaction on the hydroesterification of styrene.

Interfacial Lewis acid-base pairs are commonly found in ZrO2-supported metal catalysts due to the facile generation of oxygen vacancies of ZrO2. These pairs have been reported to play a crucial role in olefin hydroesterification, especially in the absence of acid promoters and ligands. In this study, a series of ZrO2-supported Ru catalysts with ruthenium(iii) chloride and ruthenium(iii) acetylacetonate as precursors were prepared for the styrene hydroesterification. The catalysts were thoroughly characterized by TPR, TEM, EPR, XPS, and FTIR. The Ru precursors significantly influenced the size and electronic properties of Ru clusters, albeit having minimal impact on oxygen vacancies. Mechanistic studies of styrene hydroesterification over ZrO2-supported Ru catalysts revealed that the carbon monoxide insertion followed the hydrogen transfer step to activated styrene. Higher activity is exhibited over ZrO2-supported Ru catalysts prepared with ruthenium(iii) chloride as a precursor, attributed to the lower adsorption strength of CO over Ru clusters, as evidenced by FTIR and DFT calculations.

Growing clean crystals from dirty precursors: Solid-source metal-organic molecular beam epitaxy growth of superconducting Sr2RuO4 films

Ultra-high purity elemental sources have long been considered a prerequisite for obtaining low impurity concentrations in compound semiconductors in the world of molecular beam epitaxy (MBE) since its inception in 1968. However, we demonstrate that a “dirty” solid precursor, ruthenium(III) acetylacetonate [also known as Ru(acac)3], can yield single-phase, epitaxial, and superconducting Sr2RuO4 films with the same ease and control as III–V MBE. A superconducting transition was observed at ∼0.9 K, suggesting a low defect density and a high degree of crystallinity in these films. In contrast to the conventional MBE, which employs the ultra-pure Ru metal evaporated at ∼2000 °C as a Ru source, along with reactive ozone to obtain Ru → Ru4+ oxidation, the use of the Ru(acac)3 precursor significantly simplifies the MBE process by lowering the temperature for Ru sublimation (less than 200 °C) and by eliminating the need for ozone. Combining these results with the recent developments in hybrid MBE, we argue that leveraging the precursor chemistry will be necessary to realize next-generation breakthroughs in the synthesis of atomically precise quantum materials.

Spectroelectrochemical sensing of reaction intermediates and products in an affordable fully 3D printed device

Recent advances in fused deposition modelling 3D printing (FDM 3DP) and synthesis of printable electrically conductive materials enabled the manufacture of customized electrodes and electrochemical devices by this technique. The past couple of years have seen a boom in applying approaches of FDM 3DP in the realm of spectroelectrochemistry (SEC). Despite significant progress, reported designs of SEC devices still rely on conventionally manufactured optical components such as quartz windows and cuvettes. To bridge this technological gap, in this work we apply bi-material FDM 3DP combining electrically conductive and optically translucent filaments to manufacture working electrodes and cells, constituting a fully integrated microfluidic platform for transmission absorption UV–Vis SEC measurements. The cell design enables de-aeration of samples and their convenient handling and analysis. Employing cyclic voltammetric measurements with ruthenium(III) acetylacetonate, ethylviologen dibromide and ferrocenemethanol redox-active probes as model analytes, we demonstrate that the presented platform allows SEC sensing of reactants, intermediates and products of charge transfer reactions, including the inspection of their long-term stability. Approaches developed and presented in this work pave the way for manufacturing customized SEC devices with dramatically reduced costs compared to currently available commercial platforms.

Effect of Precursors on the Electrochemical Properties of Mixed RuOx/MnOx Electrodes Prepared by Thermal Decomposition.

Growing thin layers of mixed-metal oxides on titanium supports allows for the preparation of versatile electrodes that can be used in many applications. In this work, electrodes coated with thin films of ruthenium (RuOx) and manganese oxide (MnOx) were fabricated via thermal decomposition of a precursor solution deposited on a titanium substrate by spin coating. In particular, we combined different Ru and Mn precursors, either organic or inorganic, and investigated their influence on the morphology and electrochemical properties of the materials. The tested salts were: Ruthenium(III) acetylacetonate (Ru(acac)3), Ruthenium(III) chloride (RuCl3·xH2O), Manganese(II) nitrate (Mn(NO3)2·4H2O), and Manganese(III) acetylacetonate (Mn(acac)3). After fabrication, the films were subjected to different characterization techniques, including scanning electron microscopy (SEM), polarization analysis, open-circuit potential (OCP) measurements, electrochemical impedance spectroscopy (EIS), linear sweep voltammetry (LSV), cyclic voltammetry (CV), and galvanostatic charge-discharge (GCD) experiments. The results indicate that compared to the others, the combination of RuCl3 and Mn(acac) produces fewer compact films, which are more susceptible to corrosion, but have outstanding capacitive properties. In particular, this sample exhibits a capacitance of 8.3 mF cm-2 and a coulombic efficiency of higher than 90% in the entire range of investigated current densities.

An integrated strategy for upgrading Li-CO2 batteries: Redox mediator and separator modification

In Li-CO2 battery, redox mediators (RMs) are considered to have bright prospects due to their advantages of optimizing the mediated reaction pathway and reducing over-potential. However, some inherent defects caused by RMs, such as induced Li anode degradation and electron shuttle, limit its application in Li-CO2 battery. In this work, ruthenium acetylacetonate (Ru(acac)3) was innovatively applied as an efficient RM to boost the performance of Li-CO2 battery, and the “shuttle effect” of Ru(acac)3 to Li anode was also confirmed. To avoid the anode degradation caused by “shuttle effect” of RM, a novel Zn-MOF nanoplate modified glass fiber (M-GF) separator is skillfully prepared and used as a dual-function separator for Li-CO2 battery. Experiments coupled with density functional theory simulations verifies that M-GF can protect Li anode by preventing Ru(acac)3 from entering Li anode by physical and chemical interactions. Moreover, the highly ordered micropores in Zn-MOF also induce uniform deposition of Li+ on the Li anode to delay the degradation process of anode, and thus prolonged the cycle life of the battery. Thanks to the bidirectional support of Ru(acac)3 and M-GF strategy, the electrochemical performances of the Li-CO2 battery, especially the round-trip efficiency and cycle life, has been greatly improved.

Soot Formation and Growth in Toluene/Ethylene Combustion Catalyzed by Ruthenium Acetylacetonate

ABSTRACT Ruthenium-based compounds are efficient catalysts to enhance combustion performance and suppress soot emission. However, systematic mechanism and in-situ research on reducing soot are rarely addressed. In this study, ruthenium acetylacetonate (Ru(C5H7O2)3, Ru(acac)3) was utilized as the catalyst precursor in different concentration conditions to investigate its impacts on the size, volume, and morphology of the soot particles in the ethylene flames with central toluene injection. The soot particles were detected by in-situ small-angle X-ray scattering (SAXS) and ex-situ transmission electron microscopy (TEM). This study confirms that Ru(acac)3 can suppress the surface growth for the primary soot particles, but no significant change of the morphology has been discovered for the aggregates. Compared with the undoped flame, the volume of the soot particles in the Ru(acac)3-doped flames is lower and the particle size is smaller, indicating a valid inhibition effect of Ru(acac)3 on the soot emission by affecting its surface growth and oxidation process. Despite the remarkable distinction between the undoped and doped flames, no obvious difference is found between the flames with different catalyst concentrations.

Ethanol Oxidation at Pt Nanoparticles Supported on Titanium Modified by Thermal Decomposition of Tin and Ruthenium Acetylacetonate Complexes

Sn and Ru oxides prepared by thermal decomposition of metal acetylacetonate (acac) complexes on Ti have a substantial support effect on platinum catalyzed oxidation of ethanol. Sn and Ru oxides and mixed Sn–Ru oxides (Ru-doped SnO2) deposited onto Ti foils were drop coated with preformed Pt nanoparticles. Cyclic voltammetry in H2SO4(aq) showed a strong synergistic effect between Ru and Sn oxide for ethanol oxidation, with a 2:1 ratio of Ru(acac)3 to Sn(acac)2 in the oxide precursor solution producing the most active catalyst. X-ray photoelectron spectroscopy revealed a significant transfer of electron density from the Ru-doped SnO2 to the Pt nanoparticles (electronic/ligand effect), and increased Pt oxide formation. Both of these effects can promote the oxidation of adsorbed CO, while the electronic effect also influences the adsorption strength of ethanol. The variation of the balance of these effects with the level of Ru doping is a plausible explanation for the dependence the ethanol oxidation activity on the composition of the oxide layer.

Highly selective and robust single-atom catalyst Ru1/NC for reductive amination of aldehydes/ketones

Single-atom catalysts (SACs) have emerged as a frontier in heterogeneous catalysis due to the well-defined active site structure and the maximized metal atom utilization. Nevertheless, the robustness of SACs remains a critical concern for practical applications. Herein, we report a highly active, selective and robust Ru SAC which was synthesized by pyrolysis of ruthenium acetylacetonate and N/C precursors at 900 °C in N2 followed by treatment at 800 °C in NH3. The resultant Ru1-N3 structure exhibits moderate capability for hydrogen activation even in excess NH3, which enables the effective modulation between transimination and hydrogenation activity in the reductive amination of aldehydes/ketones towards primary amines. As a consequence, it shows superior amine productivity, unrivalled resistance against CO and sulfur, and unexpectedly high stability under harsh hydrotreating conditions compared to most SACs and nanocatalysts. This SAC strategy will open an avenue towards the rational design of highly selective and robust catalysts for other demanding transformations.

High-Performance Ru 2 P Anodic Catalyst for Alkaline Polymer Electrolyte Fuel Cells

High-Performance Ru ₂ P Anodic Catalyst for Alkaline Polymer Electrolyte Fuel Cells

Gold Nanorod@Ruthenium Oxide Core–Shell Heterostructures: Synthesis, Single‐Particle Characterizations, and Enhanced Hot Electron Generation

AbstractA synthetic approach has been developed towards encapsulating gold nanorods (AuNRs) with conductive ruthenium oxide (RuO2) by the hydrolysis of ruthenium (III) acetylacetonate in the presence of cetyltrimethylammonium bromide (CTAB) in an autoclave. The reaction conditions are investigated systematically. The resultant AuNR@RuO2 heterostructures are encapsulated with uniform RuO2 shells and are monodispersed in aqueous solutions. Correlated dark‐field microscopic (DFM) and scanning electron microscopic (SEM) characterizations on AuNR@RuO2 nanostructures are performed at single‐particle level, providing the plasmonic properties in correspondence with the size and structure details of the core–shell nanostructures. The complex refractive indexes of RuO2 shell on single nanostructures are further determined by fitting the calculated spectra to the measured ones. Hot electron (HE) photocurrent measurement employing a photoelectrochemical cell shows the encapsulation of the AuNR with 8.2‐nm RuO2 shell results in a 2.9‐fold enhancement at 638 nm, in good agreement with the theoretical calculation. The calculation indicates enhancement ratio exceeding 50 at 800 nm. The mechanism behind is the substantial enhancement of the electric field inside the RuO2 shell as well as less loss in comparison to plasmonic metals, while the conductive nature of RuO2 allows for the transfer of HEs generated inside the shell to the environment.

Alcoxotechnology for obtaining heat-resistant materials based on rhenium and ruthenium

Objectives. To develop physical and chemical bases and methods to obtain rhenium–ruthenium isoproxide Re4-yRuyO6(OPri)10 —a precursor for obtaining a high-temperature alloy—from ruthenium acetylacetonate and rhenium isoproxide acquired by electrochemical methods.Methods. IR spectroscopy (EQUINOX 55 Bruker, Germany), X-ray phase and elemental analyses, energy-dispersive microanalysis (EDMA, SEM JSM5910-LV, analytical system AZTEC), powder X-ray diffraction (diffractometer D8 Advance Bruker, Germany), experimental station XSA beamline at the Kurchatov Synchrotron Radiation Source.Results. The isoproxide complex of rhenium–ruthenium Re4-yRuyO6(OPri)10 was obtained, and its composition and structure were established. Previously conducted quantum chemical calculations on the possibility of replacing rhenium atoms with ruthenium atoms in the isopropylate complex were experimentally proven, and the influence of the electroconductive additive on the composition of the obtained alloy was revealed.Conclusions. Physical and chemical bases and methods for obtaining rhenium–ruthenium isoproxide Re4-yRuyO6(OPri)10 were developed. The possibility of using rhenium–ruthenium Re4-yRuyO6(OPri)10 as a precursor in the production of ultra- and nanodisperse rhenium–ruthenium alloy powders at a record low temperature of 650°C were shown.

UV/VIS spectroelectrochemistry with 3D printed electrodes

Recent years have witnessed a boom in applying 3D printing technologies to manufacture customized prototypes in various fields of science. In electrochemistry, fused deposition modelling (FDM) 3D printing employing composite filaments based on thermoplastic materials and conductive allotropes of carbon enabled rapid, routine, inexpensive and operationally safe fabrication of conductive electrodes. Nevertheless, results of cyclovoltammetric measurements reported in the literature indicate that 3D printed electrodes give rise to considerable intrinsic kinetic barriers for electron transfer through the electrode/electrolyte interface. In this work we employ FDM-based 3D printing followed by a simple anodic activation procedure to manufacture electrodes from commercially available composites of polylactic acid (PLA) and carbon nanotubes (CNTs). Employing cyclic voltammetry with ruthenium(III) acetylacetonate as the electroactive probe we demonstrate that the previously reported kinetic barrier is almost completely removed upon the activation process. We apply such devised procedure to manufacture electrodes with optical windows allowing UV/VIS absorption spectroscopic detection of electrogenerated products. We are thus the first to perform a UV/VIS absorption spectroelectrochemical experiment employing 3D printed optically transparent working electrodes.

In situ generation of COx-free H2 by catalytic ammonia decomposition over Ru-Al-monoliths

Ru catalysts supported on alumina coated monoliths has been prepared employing three different precursor, which are ruthenium chloride, ruthenium nitrosyl nitrate and ruthenium acetyl acetonate, by an equilibrium adsorption method. The Ru particle sizes could be controlled varying the metal precursor salt. Among the prepared catalysts, Ru catalyst prepared from nytrosyl nitrate exhibited the highest activity which is concomitant to the largest mean Ru particle size of 3.5 nm. The values of the apparent activation energy calculated from the Arrhenius equation are according to the Temkin-Phyzev model, indicating that the recombinative desorption of N ad-atoms is the rate-determining step of the reaction. However, the ratio between the kinetic orders with respect to ammonia and hydrogen (−α/β), is not in agreement to the valued predict by Temkin formalism. This fact could be related to the different operational conditions used during the reaction, and/or catalyst nature, but not to any change on the controlling step of the reaction.

HYDROLYTIC HYDROGENATION OF INULIN WITH USE MAGNETIC-SEPARATE Ru-CONTAINING CATALYST

The combined hydrolysis and hydrogenation of inulin was studied on Ru-containing magnetically recoverable catalyst, using subcritical water as solvent. The Ru−Fe3O4−SiO2 catalysts are synthesized by incorporation of magnetite nanoparticles (NPs) in mesoporous silica pores followed by formation of 2 nm Ru NPs. The latter was obtained by thermal decomposition of ruthenium acetylacetonate in the pores. Magnetic properties of Fe3O4−SiO2 are typical for superparamagnetic iron oxide NPs of comparable size and allow to make a fast magnetic separation of the catalyst. The results of liquid nitrogen adsorption measurements are typical for mesoporous materials. The BET surface area of catalyst is 280 m2/g, what is allowed for mesoporous catalytic materials. The XPS spectra of Ru-Fe3O4-SiO2 demonstrate a good homogeneity of the sample. The catalyst was tested in hydrolytic hydrogenation of inulin. Inulin is hydrolyzed with formation of fructose and a small amount of glucose. There is a hydrogenation of fructose and glucose in hydrogen with receiving a mannitol and sorbitol, respectively. Mannitol is widely used in production of medicines and pharmaceutics, liquid fuel, the chemical and food industry, biotechnology and production of cosmetics. Mannitol presents in many plants and seaweeds. However, the extraction of mannitol from these raw materials is not a profitable process. Instead, fermentation and catalytic hydrogenation processes are used industrially. Nowadays, mannitol can be obtained by catalytic hydrogenation of monosaccharides like fructose or from glucose-fructose mixtures, using heterogeneous catalyst. During the researches key parameters of process, such as temperature and time of reaction, partial pressure of hydrogen are varied. At optimum reaction conditions: temperature of 150 °C, partial pressure of hydrogen of 60 bars in 45 min, – conversion of inulin was achieved of 100 %, a mannitol yield was 44.3 %. The used catalyst has shown high activity and stability in hydrothermal conditions. Stable magnetic properties of the catalyst cause his easy separation from reactionary mixture by means of external magnetic field.Forcitation:Ratkevich E.A., Manaenkov O.V., Matveeva V.G., Kislitza O.V., Sulman E.M. The hydrolytic hydrogenation of inulin catalyzed by Ru-containing magnetically recoverable catalyst. Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol. 2018. V. 61. N 4-5. P. 76-81

Ruthenium acetylacetonate in interface engineering for high performance planar hybrid perovskite solar cells.

As it already made huge effect in the commercialization of silicon and other photovoltaics, interface engineering is dispensable in the current and future evolution of hybrid perovskite solar cells (PSCs) techniques. In order to solve carriers' recombination and detention at the cathode side of planar PSCs, in this work, Ruthenium acetylacetonate (RuAcac) was successfully adopted as a reliable and stable cathode interfacial layer (CIL) to improve the inverted planar PSCs. The power conversion efficiency of the optimal devices was enhanced from 12.74% for the control device without RuAcac, to 17.15% for the RuAcac based devices, with an open circuit voltage of 1.077 V, a short circuit current density of 21.28 mA/cm2, and fill factor of 74.7% correspondingly. A series of photon-physics and microscopy protocols, including EQE, UPS, XPS, PL and SKPM, were used to discover the function of RuAcac CIL. Those results confirms an identical conclusion that RuAcac enables the formation of quasi-ohmic contact at the cathode side by eliminating the energy level barrier between the LUMO of PCBM and Fermi level of silver electrode. The low temperature and facile processed Ruthenium acetylacetonate in this work definitely offer us a robust interface-engineering way for the perovskite solar cells and also their commercialization.

Characterization of Structural and Electronic Transitions During Reduction and Oxidation of Ru(acac)3 Flow Battery Electrolytes by using X‐ray Absorption Spectroscopy

AbstractMetal acetylacetonates possess several very attractive electrochemical properties; however, their cyclabilities fall short of targets for use in nonaqueous redox flow batteries. This paper describes structural and compositional changes during the reduction and oxidation of ruthenium(III) acetylacetonate [Ru(acac)3], a representative acetylacetonate. Voltammetry, bulk electrolysis, and in situ X‐ray absorption spectroscopy (XAS) results are complemented by those from density functional theory (DFT) calculations. The reduction of Ru(acac)3 in acetonitrile is highly reversible, producing a couple at −1.1 V versus Ag/Ag+. In situ XAS and DFT indicate the formation of [Ru(acac)3]− with Ru−O bonds lengthened relative to Ru(acac)3, nearly all of the charge localized on Ru, and no ligand shedding. The oxidation of Ru(acac)3 is quasireversible, with a couple at 0.7 V. The initial product is likely [Ru(acac)3]+; however, this species is short‐lived, converting to a product with a couple at −0.2 V, a structure that is nearly identical to that of Ru(acac)3 within 3 Å of Ru, and approximately 70 % of the charge extracted from Ru (balance from acetylacetone). This non‐innocence likely contributes to the instability of [Ru(acac)3]+. Taken together, the results suggest that the stabilities and cyclabilities of acetylacetonates are determined by the degree of charge transfer to/from the metal.

Ru-Containing Magnetically Recoverable Catalysts: A Sustainable Pathway from Cellulose to Ethylene and Propylene Glycols

Biomass processing to value-added chemicals and biofuels received considerable attention due to the renewable nature of the precursors. Here, we report the development of Ru-containing magnetically recoverable catalysts for cellulose hydrogenolysis to low alcohols, ethylene glycol (EG) and propylene glycol (PG). The catalysts are synthesized by incorporation of magnetite nanoparticles (NPs) in mesoporous silica pores followed by formation of 2 nm Ru NPs. The latter are obtained by thermal decomposition of ruthenium acetylacetonate in the pores. The catalysts showed excellent activities and selectivities at 100% cellulose conversion, exceeding those for the commercial Ru/C. High selectivities as well as activities are attributed to the influence of Fe3O4 on the Ru(0)/Ru(4+) NPs. A facile synthetic protocol, easy magnetic separation, and stability of the catalyst performance after magnetic recovery make these catalysts promising for industrial applications.

Pt-doped In2O3 nanoparticles prepared by flame spray pyrolysis for NO2 sensing

Undoped In2O3 and 0.25–1.00 wt% M (M=Pt, Nb, and Ru)-doped/loaded In2O3 nanoparticles were successfully synthesized in a single-step flame spray pyrolysis technique using indium nitrate, platinum (II) acetylacetonate, niobium ethoxide, and ruthenium (III) acetylacetonate precursors. The undoped In2O3 and M-doped In2O3 nanoparticles were characterized by Brunauer–Emmett–Teller (BET) analysis, X-ray diffraction (XRD), and scanning and transmission electron microscopy (SEM & TEM). The BET average diameter of spherical nanoparticles was found to be in the range of 10.2–15.2 nm under 5/5 (precursor/oxygen) flame conditions. All XRD peaks were confirmed to correspond to the cubic structure of In2O3. TEM images showed that there is no Pt nanoparticle loaded on In2O3 surface, suggesting that Pt should form solid solution with the In2O3 lattice. Gas sensing studies showed that 0.5 wt% Pt doping in In2O3 nanoparticles gave a significant enhancement of NO2 sensing performances in terms of sensor response and selectivity. 0.5 wt% Pt/In2O3 exhibited a high NO2 response of ~1904 to 5 ppm NO2 at 250 °C and good NO2 selectivity against NO, H2S, H2, and C2H5OH. In contrast, Nb and Ru loading resulted in deteriorated NO2 response. Therefore, Pt is demonstrated to be an effective additive to enhance NO2 sensing performances of In2O3-based sensors.

Ruthenium nanoparticles decorated curl-like porous carbons for high performance supercapacitors.

The synthesis of highly dispersed and stable ruthenium nanoparticles (RuNPs; ca. 2–3 nm) on porous activated carbons derived from Moringa Oleifera fruit shells (MOC) is reported and were exploited for supercapacitor applications. The Ru/MOC composites so fabricated using the biowaste carbon source and ruthenium acetylacetonate as the co-feeding metal precursors were activated at elevated temperatures (600–900 oC) in the presence of ZnCl2 as the pore generating and chemical activating agent. The as-prepared MOC carbonized at 900 oC was found to possess a high specific surface area (2522 m2 g−1) and co-existing micro- and mesoporosities. Upon incorporating RuNPs, the Ru/MOC nanocomposites loaded with modest amount of metallic Ru (1.0–1.5 wt%) exhibit remarkable electrochemical and capacitive properties, achiving a maximum capacitance of 291 F g−1 at a current density of 1 A g−1 in 1.0 M H2SO4 electrolyte. These highly stable and durable Ru/MOC electrodes, which can be facily fabricated by the eco-friendly and cost-effective route, should have great potentials for practical applications in energy storage, biosensing, and catalysis.