Ru Precursor Research Articles

Atomically dispersed ruthenium single-atom alloy catalysts enabling efficient iodide oxidation reaction electrolysis in acidic media

Single-atom catalysts exhibit immense potential across diverse reactions, yet their synthesis and stability in acidic environments pose significant challenges. Herein, we introduce a facile one-step hydrothermal approach to fabricate Ru single-atom alloy catalysts (Ru SAAC) through the reaction of Ru and Ti precursors, followed by annealing in an argon atmosphere. Analysis via extended X-ray absorption fine structure spectroscopy and aberration-corrected scanning transmission electron microscopy confirms the atomically dispersed Ru alloy catalyst anchored on a TiO2 support. Remarkably, Ru SAAC demonstrates exceptional electrocatalytic performance in the iodide oxidation reaction (IOR), achieving a benchmark current density of 10 mA/cm2 at a mere voltage of 0.64 V in acidic conditions within a three-electrode electrolyzer setup. Surpassing nanoscale Ru/TiO2 and RuO2/TiO2 counterparts, Ru SAAC exhibits the highest voltage efficiency (84.4%), lowest Tafel slope (36 mV/dec), and lowest overpotential (100 mV) under identical experimental conditions. This method enables facile control over Ru morphology. It enhances the kinetics and thermodynamic favorability of Ru SAAC in acidic media, opening avenues for synthesizing diverse transition metal-based single-alloy catalysts for varied applications.

Synthesis and reactivity of isomeric Ru complexes with hydroxypyridyl fragment: Active catalysts for β‑alkylation of secondary alcohols with primary alcohols

When the ligand LOH, containing a 2-hydroxy pyridine group, reacts with an equimolar amount of the precursor Ru(DMSO)4Cl2, two isomeric ruthenium complexes are formed. These isomers are termed cis-1 and trans-1, based on the relative positions of the N atom in N-(2-(6-hydroxy pyridin-2-yl)phenyl)acetamide and the pyridine groups of bis((1,4-pyridin-2-yl)methyl)amine. Treatment of these isomers with equimolar amounts of NaH results in deprotonation of the uncoordinated hydroxy pyridine groups, leading to the formation of complex 2 with newly coordinated pyridine groups. The catalytic activity of these three ruthenium complexes in the β-alkylation reaction of primary alcohols and secondary alcohols was evaluated, with complex 2 displaying the highest activity and selectivity. Complex 2 may be seen as an intermediate in the catalysis of the β-alkylation reaction by the isomers (cis-1 and trans-1). These findings are valuable for the development of more effective bifunctional catalysts.

Unveiling the Cation Dependence in Alkaline Hydrogen Evolution by Differently-Charged Ruthenium/Molybdenum Sulfide Hybrids.

The sluggish kinetics of hydrogen evolution reaction (HER) via water reduction limits the efficiency of alkaline water electrolysis. The HER kinetics is not only intimately related to the catalyst surface structure but also relevant to the cation identity of the electrolyte. The cation dependence also relies on the surface electronic structure and applied potential, but this interrelated effect and its underlying mechanism awaits elucidation. Herein, differently-charged molybdenum sulfide (MoSx) cluster supports ([Mo3S13]2- and [Mo3S7]4+) are utilized to hybridize with the identical metallic Ru centers. The specific electrostatic interaction between MoSx clusters and Ru precursors induces different Ru valences of the hybrids, with a higher valence state for Ru/Mo3S13 endowing a higher activity. The Ru/Mo3S13 and Ru/Mo3S7 exhibited drastically-different cation dependence, in which the charged support determines the local accumulation of cations and resulting water structures. The more negatively-charged Mo3S13 support induces the facile accumulation of cations, especially for less-hydrated K+ cations. The water activation capability by Ru valences and cation accumulation from the support effect in-together determine the cation-dependent alkaline HER activity. This work not only enriches the understanding about the cation-dependent HER mechanism but also shines a light on the rational optimization strategy of electrode/electrolyte interfaces.

Formation Mechanism and Hydrothermal Synthesis of Highly Active Ir1-xRuxO2 Nanoparticles for the Oxygen Evolution Reaction.

Iridium dioxide (IrO2), ruthenium dioxide (RuO2), and their solid solutions (Ir1-xRuxO2) are very active electrocatalysts for the oxygen evolution reaction (OER). Efficient and facile synthesis of nanosized crystallites of these materials is of high significance for electrocatalytic applications for converting green energy to fuels (power-to-X). Here, we use in situ X-ray scattering to examine reaction conditions for different Ir and Ru precursors resulting in the development of a simple hydrothermal synthesis route using IrCl3 and KRuO4 to obtain homogeneous phase-pure Ir1-xRuxO2 nanocrystals. The solid solution nanocrystals can be obtained with a tunable composition of 0.2 < x < 1.0 and with ultra-small coherently scattering crystalline domains estimated from 1.3 to 2.6 nm in diameter based on PDF refinements. The in situ X-ray scattering data reveal a two-step formation mechanism, which involves the initial loss of chloride ligands followed by the formation of metal-oxygen octahedra clusters containing both Ir and Ru. These octahedra assemble with time resulting in long-range order resembling the rutile structure. The mixing of the metals on the atomic scale during the crystal formation presumably allows the formation of the solid solution rather than heterogeneous mixtures. The size of the final nanocrystals can be controlled by tuning the synthesis temperature. The facile hydrothermal synthesis route provides ultra-small nanoparticles with activity toward the OER in acidic electrolytes comparable to the best in the literature, and the optimal material composition very favorably combines low overpotential, high mass activity, and increased stability.

The surface chemistry of the atomic layer deposition of ruthenium on aluminum and tantalum oxide surfaces

The surface chemistry of Ru atomic layer deposition (ALD) processes based on the use of tris(2,2,6,6-tetramethyl-3,5-heptanedionato)ruthenium(III) (Ru(tmhd)3) and either molecular oxygen or atomic hydrogen on aluminum oxide films was characterized by a combination of surface-sensitive techniques. The thermal decomposition of the Ru metalorganic precursor was determined, by using a combination of reflection-absorption infrared spectroscopy (RAIRS), temperature programmed desorption (TPD), and X-ray photoelectron spectroscopy (XPS), to start below 400 K and to take place in a stepwise fashion over a wide range of temperatures. Gas-phase products from this chemistry include 2,2,6,6-tetramethyl-3,5-heptanedione (the protonated ligand, Htmhd; in a TPD peak at 520 K), isobutene (540 K; indicating the fragmentation of the organic ligands), and other products from isomerization and/or aldol condensation (650 and 730 K). This chemistry is accompanied by the reduction of the Ru3+ ions in two stages, involving the loss of some of their ligands and their direct bonding to the substrate first (between 500 and 600 K) and a full reduction to a metallic state later on (600–700 K). ALD cycles using either molecular oxygen or atomic hydrogen resulted in the slow build-up of Ru on the surface, but the co-deposition of carbon could not be avoided, at least in the initial cycles, while the alumina surface was still exposed. With O2, the Ru atoms alternate between partially-oxidized (after the O2 exposures) and zero-valent (after the Ru(tmhd)3 doses) states, and some Ru loss in the form of the volatile RuO4 oxide was seen after the second half of the ALD cycles; neither the Ru oxidation state alternation nor the elimination of some Ru from the surface were observed when using H·. The deposited Ru was determined, by combining results from angle-resolved XPS (ARXPS) and low-energy ion scattering (LEIS) experiments, to grow as 3D nanoparticles rather than as a layer-by-layer 2D film, presumably because the Ru precursor preferentially adsorbs (and decomposes more cleanly) on the metal surface. A discussion is provided of the implications of these results for the design of ALD processes.

Pt/C and PtRu/C Catalysts Prepared by Modified Sulfite Complex Routes for Fuel Cell Applications

In-house 30 wt.% Pt and 50 wt.% Pt1Ru1 catalysts supported on high-surface area carbon (Ketjenblack, abbreviated as KB) were synthesized by the sulfite complex route. Two different procedures involving either a direct mixing of Pt-sulfite and Ru-sulfite complexes or Pt-sulfite preparation and subsequent impregnation of Ru precursor were adopted for the bimetallic species. In both cases, an impregnation of the formed metal oxides onto KB was adopted to increase the electronic conductivity of the samples. Finally, a carbothermal treatment at 600°C in He atmosphere was carried out for the reduction of the metal oxides to metallic PtRu/C compounds. The Pt1Ru1 ratio was calculated and revealed by X-ray fluorescence (XRF) analysis whereas the carbon percentage was calculated by weight loss. 50 mg of sample was treated in air at 550°C for 2 h and, after cooling, the weight corresponded to 25 mg, confirming a carbonaceous matrix percentage of 50 wt.%. In a similar way, the 30 wt.% Pt/C was determined. X-ray diffraction (XRD) revealed that the samples showed face centered cubic (fcc) structure for Pt nanoparticles. It appears that two distinct crystallographic phases of Pt and Ru nanoparticles were encountered after the synthesis conducted by Ru impregnation. In contrast, only a single fcc phase is visible when the Pt and Ru sulfite precursors were mixed, confirming the formation of an alloy. Furthermore, Scanning Transmission Electron Microscopy-Energy dispersive X-ray spectroscopy (S/TEM-EDX) and X-ray Photoelectron Spectroscopy (XPS) were used to characterize the differences in morphology and surface characteristics of the catalysts.For the electrochemical measurements, rotating disc electrode (RDE) technique under acid and alkaline conditions was employed to investigate the half cell reactions. The catalysts were also deposited at the anode and cathode of fuel cells to evaluate the activity, performance, and short-term durability. Acknowledgement “This research was funded by the European Union – EIT Raw Materials in the framework of the following project: LYDIA- Recycling Critical Metals from Fuel Cells (G.A. 22019)”

Selective chlorine evolution reaction using Pt-RuO2 electrocatalysts in brackish water and seawater at circum-neutral pH and its application to seawater desalination

Precious metal-based mixed metal oxides have been widely used as catalysts for the chlorine evolution reaction (CER). However, a concurrent oxygen evolution reaction (OER) leads to insufficient selectivity for CER at circum-neutral pH. Herein, nanoparticulate Pt-RuO2 (PRO) is synthesized with various Pt/Ru ratios at sub-boiling temperatures, followed by post-annealing. The synthetic conditions significantly influence the physicochemical properties (crystalline structures, morphologies, surface areas, double-layer capacitance, and charge transfer resistance) and the electrocatalytic activities of CER in NaCl solutions (0.137 and 0.5 M) and seawater (with a salinity of 3.6 g L–1). Among PRO-x@y samples (where x is the mole fraction of Pt in the mixed Pt and Ru precursor solutions, and y is the annealing temperature [°C]), PRO-0.2@800 and PRO-0.8@500 show remarkable faradaic efficiencies (FEs) for CER (CER-FE). Despite their similar FEs (CER-FEs of approximately 95 % and 99 %, and OER-FEs of 4–6 % and <1 %, for PRO-0.2 and PRO-0.8, respectively), the Pt-rich PRO requires less potential for the same current density (J) and exhibits excellent stability at J = 800 mA cm–2 over 250 h in seawater at circum-neutral pH. The optimized PRO electrode is further used for seawater desalination and simultaneous production of HClO, achieving FEs of ∼100 %. Finally, various electrochemical analyses are conducted to elucidate the CER mechanism.

Investigation of an Ethanol Electroreforming Cell Based on a Pt1Ru1/C Catalyst at the Anode

The production of H2 from renewable sources represents a crucial challenge for the planet’s future to achieve net zero emissions and store renewable energy. A possible alternative to water electrolysis (WE), which requires high potential (E &gt; 1.48 V) to trigger the oxygen evolution reaction (OER), would be alcohol electrochemical reforming (ER), which implies the oxidation of short organic molecules such as methanol or ethanol. In ER, energy must be supplied to the system, but from a thermodynamic point of view, the energy request for the methanol or ethanol oxidation reaction is much lower than that of the OER. To study this process, an in-house 50 wt.% Pt1Ru1/C anodic catalyst was easily synthesized according to the Pt sulphite complex route and the impregnation of a carbon support (Ketjenblack, KB) and a Ru precursor. X-ray diffraction (XRD), X-ray fluorescence (XRF) spectroscopy, and Transmission Electron Microscopy (TEM) were used to characterize the structure, composition, and morphology of the catalyst. It appears that two distinct crystallographic phases of the Pt and Ru nanoparticles were encountered after the synthesis conducted by Ru impregnation. For the electrochemical measurements, ethanol electrooxidation (2 M CH3CH2OH) was studied first in a half cell with a rotating disc electrode (RDE) configuration under acid conditions and then in a direct ethanol electroreforming (or electrolysis) cell, equipped with a proton exchange membrane (PEM) as the electrolyte. The output current density was 0.93 A cm−2 at 1 V and 90 °C in 2 M ethanol. The remarkable current densities obtained in the alcohol electrolyzer at a low voltage are better than the actual state of the art for PEM ethanol ER.

Hierarchical fluoride-containing zeolite Y supported Ru for catalytic conversion of xylose to xylitol

Hierarchical fluoride-containing zeolite HY (Hie-HY(F)) is an interesting material because it tunes both a high mesoporosity and a moderate acid property, which could benefit the transformation of xylose to xylitol. Herein, we synthesized a new Hie-HY(F) by etching NH4Y with ammonium fluoride (NH4F) under ultrasonication at 60 °C for 20, 40, and 60 min. After etching with NH4F solution, the Hie-HY(F)s contained fluoride in the zeolite frameworks with high mesoporosity and moderate acid properties. The sonication time longer than 20 min caused the structure to collapse rather than the creation of mesoporosity. The Hie-HY(F)s were further used as supports for the Ru catalyst. When loaded with Ru precursor and calcined in air, RuO2 phase was formed in all catalysts. The RuO2 supported on Hie-HY(F)s had a lower reduction temperature than that on HY. Ru supported on Hie-HY(F)-20 gave the reactivity of xylose conversion to xylitol, the highest yield of 80.1 %, providing the reusability up to four cycles.

Synergistically modulating d-band centers of bimetallic elements for activating cobalt atoms and promoting water dissociation toward accelerating alkaline hydrogen evolution

It is of great significance to synergistically modulate d-band centers (εd) of multiple transition metals (TMs) for designing and developing highly efficient hybridized-electrocatalysts. Herein, the downshift in Co εd is realized by synthesizing Co single atoms with low nitrogen-coordination number (CoN2) at high T during the pyrolysis step while upshifting Ru εd is achieved via decreasing Ru precursor mass to anchor Ru nanoclusters instead of nanoparticles on CoN2−containing carbon substrates (CoN2/Ru−NC). In our strategy, the downshift in Co εd leads to a favorable affinity between Co sites of CoN2/Ru−NC and H* for desorption of H2; additionally, upshifting Ru εd helps the adsorption of OH* intermediates on Ru nanoclusters for CoN2/Ru−NC to promote water dissociation toward accelerating alkaline producing H2. In consequence, CoN2/Ru−NC demonstrates an outstanding activity with an ultralow overpotential of ∼ 9.0 mV at 10.0 mA cm−2, which suppresses activities of Pt/C (24.0 mV) and most previously-reported Ru-based electrocatalysts.

Enhanced hydroconversion of polyethylene via dual-functional catalysis: Exploiting ZSM-22 pore-mouth catalysis and Ru electronic effect

The subject of extensive research, the low-temperature hydrocracking of polyethylene reveals the one-step synthesis of iso-alkanes via metal–acid bifunctional catalysis as an emerging strategy. Zeolites, with their superior compatibility with existing petrochemical infrastructure, serve as the acidic supports of choice. In this research, Ru nanoparticles were loaded onto ZSM-22, a zeolite known for its effective pore-mouth catalysis. Mechanical ball milling enhanced the pore-mouth area and the proximity of metal–acid sites, significantly boosting the hydrocracking reaction. The electronic properties of Ru were modified by selecting various Ru precursors and adjusting loading amounts. In-situ infrared studies showed the detachment of olefin intermediates from Ru sites as a critical factor in controlling hydrocracking and the terminal hydrogenolysis reactions. By combining catalyst characterization with reaction barrier calculations from density functional theory (DFT), it was found that oxidized Ru species aid in the release of olefin intermediates, facilitating Brønsted acid-driven β-scission and isomerization reactions. The study achieved a liquid-phase yield exceeding 82 wt% and an iso/n ratio surpassing 60% under low-energy consumption conditions using commercially available catalysts.

Precursor design and cascade mechanism of RuO2·xH2O atomic layer deposition

As the unique nanofabrication technique, atomic layer deposition (ALD) can be used to deposit high-quality, uniform, and conformal nanoparticle coatings. Ru and its oxides (RuOx) are important materials in the fields of microelectronics and catalysis. In this work, the reaction of Ru precursors with different ligands on the hydroxylated surfaces were explored. The elimination of the pyrrolyl (Py) ligand is easier than that of the cyclopentadienyl (Py) ligand on the hydroxylated surface. The reaction involved in RuO2·xH2O ALD using RuPy2 and H2O as precursors was further investigated. During the RuPy2 reaction, the pyrrolyl ligand is eliminated by the substitution reaction with a surface hydroxyl group. However, the desorption of the pyrrole molecule is difficult due to the strong adsorption between the pyrrole molecule and Ru surface. During the H2O reaction, the H2O molecules further help the elimination of pyrrolyl ligands from the surface and the dissociative desorption of pyrrole molecules This unique reaction mechanism involved in the ALD of RuO2 with the assistance of H2O can be termed new cascade mechanism. These findings provide theoretical guidance for precursor design and ALD growth of metal oxides.

Stabilization of NH- Group Adjacent to Naked Silicon(II) Atom in Base Stabilized Aminosilylenes.

Aminosilylene, comprising reactive NH- and Si(II) sites next to each other, is an intriguing class of compounds due to its ability to show diverse reactivity. However, stabilizing the reactive NH- group next to the free Si(II) atom is challenging and has not yet been achieved. Herein, we report the first examples of base stabilized free aminosilylenes Ar*NHSi(PhC(Nt Bu)2 ) (1 a) and Mes*NHSi(PhC(Nt Bu)2 ) (1 b) (Ar*=2,6-dibenzhydryl-4-methylphenyl and Mes*=2,4,6-tri-tert-butylphenyl), tolerating a NH- group next to the naked Si(II) atom. Remarkably, 1 a and 1 b exhibited interesting differences in their reactivity upon heating. With 1 a, an intramolecular C(sp3 )-H activation of one of the benzhydryl methine hydrogen atoms to the Si(II) atom produced the five-membered cyclic silazane 2. However, with 1 b, a rare 1,2-hydrogen shift to the Si(II) atom afforded a silanimine 3, with a hydride ligand attached to an unsaturated silicon atom. Further, the coordination capabilities of 1 a were also tested with Ru(II) and Fe(0) precursors. Treatments of 1 a with [Ru(η6 -p-cymene)Cl2 ]2 led to the isolation of a η6 -arene tethered complex [RuCl2 {Ar*NHSi(PhC(t BuN)2 )-κ1 -Si-η6 -arene}] (4), whereas with the Fe(CO)5 precursor a Fe(0) complex [Fe(CO)4 {Ar*NHSi(PhC(t BuN)2 )-κ1 -Si}] (5) was obtained. Density functional theory (DFT) calculations were conducted to shed light on the structural, bonding, and energetic aspects in 1-5.

Stabilization of NH− Group Adjacent to Naked Silicon(II) Atom in Base Stabilized Aminosilylenes

AbstractAminosilylene, comprising reactive NH− and Si(II) sites next to each other, is an intriguing class of compounds due to its ability to show diverse reactivity. However, stabilizing the reactive NH− group next to the free Si(II) atom is challenging and has not yet been achieved. Herein, we report the first examples of base stabilized free aminosilylenes Ar*NHSi(PhC(NtBu)2) (1 a) and Mes*NHSi(PhC(NtBu)2) (1 b) (Ar*=2,6‐dibenzhydryl‐4‐methylphenyl and Mes*=2,4,6‐tri‐tert‐butylphenyl), tolerating a NH− group next to the naked Si(II) atom. Remarkably, 1 a and 1 b exhibited interesting differences in their reactivity upon heating. With 1 a, an intramolecular C(sp3)−H activation of one of the benzhydryl methine hydrogen atoms to the Si(II) atom produced the five‐membered cyclic silazane 2. However, with 1 b, a rare 1,2‐hydrogen shift to the Si(II) atom afforded a silanimine 3, with a hydride ligand attached to an unsaturated silicon atom. Further, the coordination capabilities of 1 a were also tested with Ru(II) and Fe(0) precursors. Treatments of 1 a with [Ru(η6‐p‐cymene)Cl2]2 led to the isolation of a η6‐arene tethered complex [RuCl2{Ar*NHSi(PhC(tBuN)2)‐κ1‐Si‐η6‐arene}] (4), whereas with the Fe(CO)5 precursor a Fe(0) complex [Fe(CO)4{Ar*NHSi(PhC(tBuN)2)‐κ1‐Si}] (5) was obtained. Density functional theory (DFT) calculations were conducted to shed light on the structural, bonding, and energetic aspects in 1–5.

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.

Facile Synthesis of Ru Nanoboxes with a Hexagonal Close-Packed Structure by Templating with Ag Nanocubes and Their Catalytic Properties.

Noble-metal nanoboxes offer an attractive form of nanomaterials for catalytic applications owing to their open structure and highly efficient use of atoms. Herein, we report the facile synthesis of Ag-Ru core-shell nanocubes and then Ru nanoboxes with a hexagonal close-packed (hcp) structure, as well as evaluation of their catalytic activity toward a model hydrogenation reaction. By adding a solution of Ru(acac)3 in ethylene glycol (EG) dropwise to a suspension of silver nanocubes in EG at 170 °C, Ru atoms are generated and deposited onto the entire surface of a nanocube. As the volume of the RuIII precursor is increased, Ru atoms are also produced through a galvanic replacement reaction, generating Ag-Ru nanocubes with a hollow interior. The released Ag+ ions are then reduced by EG and deposited back onto the nanocubes. By selectively etching away the remaining Ag with aqueous HNO3 , the as-obtained Ag-Ru nanocubes are transformed into Ru nanoboxes, whose walls are characterized by an hcp structure and an ultrathin thickness of a few nanometers. Finally, we evaluated the catalytic properties of the Ru nanoboxes with two different wall thicknesses by using a model hydrogenation reaction; both samples showed excellent performance.

Study of the catalytic wet air oxidation of p-hydroxybenzoic acid on a fresh ruthenium catalyst supported by different oxides

The catalytic wet air oxidation (CWAO) of p-hydroxybenzoic acid (p-HBA) was conducted in a batch reactor at 140 °C, and at a total air pressure of 50 bar over Ru-based catalysts. Four materials were selected as supports – TiO2, CeO2–TiO2, ZrO2–TiO2, and La2O3–TiO2 – all of which had mesopores in their texture and pollutant adsorption capacities. The supports were prepared by the sol-gel method, and then impregnated with 3 wt% of Ru precursor. Such characterization techniques as N2-sorption, XRD, XPS, H2–TPR, NH3-TPD, TEM, and HAADF-STEM were used to analyze the different solids. The correlation between catalytic activities and physicochemical properties was discussed. A significant specific surface area (SBET), a large amount of surface-active oxygen, and Lewis acidity sites were observed on cerium-containing catalysts (Ru/CeTi). Fresh Ru catalysts containing cerium showed higher activity than Ru/TiO2, Ru/ZrTi, and Ru/LaTi catalysts. It is assumed that the acidic sites and surface oxygen trap the p-HBA molecule, thus increasing the catalytic properties of the Ru particles which interact with the surface oxygen through the cerium redox process (Ce3+/Ce4+). As the presence of cerium increases surface-active oxygen, it inhibits the deposition of carbon on the surface of the Ru catalyst. The pseudo-second order (PSO) model adequately described the kinetic data of the p-HBA oxidation reaction using Ru catalysts.

Enhancement of the CO2 adsorption and hydrogenation to CH4 capacity of Ru–Na–Ca/γ–Al2O3 dual function material by controlling the Ru calcination atmosphere

Integrated CO2 capture and utilization (ICCU) technology requires dual functional materials (DFMs) to carry out the process in a single reaction system. The influence of the calcination atmosphere on efficiency of 4% Ru-8% Na2CO3-8% CaO/γ-Al2O3 DFM is studied. The adsorbent precursors are first co-impregnated onto alumina and calcined in air. Then, Ru precursor is impregnated and four aliquotes are subjected to different calcination protocols: static air in muffle or under different mixtures (10% H2/N2, 50% H2/N2 and N2) streams. Samples are characterized by XRD, N2 adsorption-desorption, H2 chemisorption, TEM, XPS, H2-TPD, H2-TPR, CO2-TPD and TPSR. The catalytic behavior is evaluated, in cycles of CO2 adsorption and hydrogenation to CH4, and temporal evolution of reactants and products concentrations is analyzed. The calcination atmosphere influences the physicochemical properties and, ultimately, activity of DFMs. Characterization data and catalytic performance discover the acccomodation of Ru nanoparticles disposition and basic sites is mostly influencing the catalytic activity. DFM calcined under N2 flow (RuNaCa-N2) shows the highest CH4 production (449 µmol/g at 370°C), because a well-controlled decomposition of precursors which favors the better accomodation of adsorbent and Ru phases, maximizing the specific surface area, the Ru-basic sites interface and the participation of different basic sites in the CO2 methanation reaction. Thus, the calcination in a N2 flow is revealed as the optimal calcination protocol to achieve highly efficient DFM for integrated CO2 adsorption and hydrogenation applications.

Synthesis of Novel Ru Precursors for Atomic Layer Depostion

Ruthenium (Ru), which has a low bulk resistivity and a high work function, is a well-known metal for electrode materials in various microelectronic applications, such as Dynamic Random Access Memories (DRAM), Ferroelectric Random Access Memories (FRAM), and metal-oxide-semiconductor field-effect transistors (MOSFET). Also, Ru thin films can be used as diffusion barrier layers to improve the electromigration resistance in interconnect systems due to the excellent adhesion characteristics between Ru and Cu. Therefore, research on Ru thin films, that can be deposited by methods such as MOCVD (Metal-Organic Chemical Vapor Deposition) and ALD (Atomic Layer Deposition), is attracting many researchers. To apply these deposition techniques, Ru precursors with volatility and thermal stability are required. In this study, for the synthesis of Ru precursors that can satisfy all conditions, new Ru precursors were designed and prepared by using Ru(η5-Tropone)(η5-CHT) (CHT = Cycloheptatriene) as a starting material, to yield five new ruthenium precursors: Ru(II)(C7H9)(C8H11O) (1), Ru(II)(C7H9)(C9H14O) (2), Ru(II)(C7H9)(C13H14O)(3), Ru(II)(C7H9)(C8H9O) (4), and Ru(II)(C7H9)(C9H11O) (5). These compounds were characterized by 1H-Nuclear Magnetic Resonance (NMR), Mass Spectrometry (MS), Fourier-transform Infrared Spectroscopy (FT-IR), Elemental Analysis (EA), Thermal Gravimetric Analysis (TGA), and single crystal X-ray diffraction.

Phase-Controlled Ruthenium Nanocrystals on Colloidal Polydopamine Supports and Their Catalytic Behaviors in Aerobic Oxidation Reactions.

The past decade has witnessed rapidly growing interest in noble metal nanostructures adopting unconventional metastable crystal phases. In the case of Ru, chemically synthesized nanocrystals typically form thermodynamically favored hexagonal close-packed (hcp) crystal lattices, whereas it remains significantly more challenging to synthesize Ru nanocrystals in the metastable face-centered cubic (fcc) phase. In this work, we have synthesized polydopamine (PDA)-supported hcp and fcc Ru nanocrystals in a phase-selective manner through one-pot thermal reduction of appropriate Ru(III) precursors in a polyol solvent. Benefiting from the unique surface-adhesion function of PDA, we have been able to grow phase-controlled sub-5 nm Ru nanocrystals directly on colloidal PDA supports without prefunctionalizing the particle surfaces with any molecular linkers or surface-capping ligands. Success in phase-controlled synthesis of capping ligand-free Ru nanocrystals dispersed on the same support material enables us to systematically compare the intrinsic mass-specific and surface-specific activities of fcc and hcp Ru nanocatalysts toward the aerobic oxidation of a chromogenic molecular substrate, 3,3',5,5'-tetramethylbenzidine (TMB), under a broad range of reaction conditions. We use UV-vis absorption spectroscopy to monitor the conversion of the reactant molecules into the one-electron and two-electron oxidation products in real time during Ru-catalyzed oxidation of TMB, which is found to be a mechanistically complex molecule-transforming process involving multiple elementary steps. The apparent reaction rates and detailed kinetic features are observed to be not only intimately related to the crystalline structures of the Ru nanocatalysts but also profoundly influenced by several other critical factors, such as the pH of the reaction medium, the initial concentration of TMB, Ru coverage on the PDA supports, and degree of nanoparticle aggregation.