Ruthenium Species Research Articles

Base-free transfer hydrogenation of carbonyl substrates catalysed by neutral ruthenium(salicylaldimine) complexes: Inhibitory effect of visible light

In this study, a series of neutral ruthenium salicylaldimine complexes were synthesized and evaluated as catalysts for the base-free transfer hydrogenation of carbonyl compounds, including acetophenone. Under base-free conditions, the complexes demonstrated high catalytic activity, achieving conversions of up to 79 % for acetophenone with a turnover number (TON) of 790 after 2 h at 82 °C. Comparatively, when a base (2 mol% KOH) was used, the conversion dropped to 17–25 %. Extending the reaction time to 3 h under base-free conditions increased the conversion to 90 %, with a TON of 900. The catalysts were also tested on a range of substrates: acetophenone derivatives with electron-donating substituents showed conversions up to 89 %, while electron-withdrawing groups resulted in lower conversions (67 %). Additionally, sterically hindered substrates like benzophenone yielded 72 % conversion. Visible light exposure significantly reduced catalytic activity, resulting in up to a 26 % decrease in conversion due to the formation of an inactive bis(salicylaldimine) ruthenium species. Mechanistic studies revealed that the reaction proceeds via an oxidative addition pathway, with the formation of a ruthenium-hydride intermediate confirmed by NMR and FT-IR spectroscopy.

Ruthenium‐Catalyzed Hydrosilylation of Aldehydes with Hydrooligosilanes

AbstractRuthenium‐catalyzed hydrosilylation of aldehydes with hydrooligosilanes is reported. Among the examined ruthenium catalysts, RuH2(CO)(PPh3)3 gave the best results. The reactions proceed with the Si−Si bonds preserved to afford the corresponding alkoxyoligosilanes in good yields. A series of aryl aldehydes with an electron‐withdrawing group is applicable, whereas those with an electron‐donating group are not suitable for the reaction. Mechanistic considerations suggest that the key points for the preservation of the Si−Si bonds are the formation of zero‐valent ruthenium species and the efficient coordination of the aldehyde to the ruthenium center prior to the oxidative addition of the Si−H bond.

Ordered Mesoporous Nitrogen Dope Carbon Synthesized from Aniline for Stabilization of Ruthenium Species in CO2 Hydrogenation to Formate

The hydrogenation of CO2 to produce formic acid has garnered increasing interest as a means to address climate change and promote the hydrogen economy. This research investigates the nanocasting technique for the synthesis of ordered mesoporous nitrogen-doped carbon (MNC-An). KIT-6 functioned as the silica template, while aniline served as the nitrogen–carbon precursor. The resultant MNC-An exhibits cubic Ia3D geometry, possesses significant mesoporosity, and has a high nitrogen content, which is essential for stabilizing ruthenium single atoms. The catalyst exhibited a specific activity of 252 mmolFAgcat−1 following a 2 h reaction at 120 °C. Moreover, the catalyst exhibited exceptional relative activity during five recycling experiments while preserving its catalytic efficacy. The atomically dispersed ruthenium and its Ru3+ oxidation state demonstrated perseverance both before and after the treatment. The results indicated that the synthesized catalyst possesses potential for the expedited commercialization of CO2 hydrogenation to produce formic acid. The elevated carbon yield, along with excellent thermal stability, renders it a viable substrate for attaching and stabilizing atomically dispersed ruthenium catalysts.

Selective reductive conversion of CO2 to CH2-bridged compounds by using a Fe-functionalized graphene oxide-based catalyst

Anthropogenic climate change drastically affects our planet, with CO2 being the most critical gaseous driver. Despite the existing carbon dioxide capture and transformation, there is much need for innovative carbon dioxide hydrogenation catalysts with excellent selectivity. Here, we present a fast, effective, and sustainable route for coupling diverse alcohols, amines and amides with CO2 via heterogenization of a natural metal-based homogeneous catalyst through decorating on functionalized graphene oxide (GO). Combined synthetic, experimental, and theoretical studies unravel mechanistic routes to convergent 4‑electron reduction of CO2 under mild conditions. We successfully replace the toxic and expensive ruthenium species with inexpensive, ubiquitously available and recyclable iron. This iron-based functionalized graphene oxide (denoted as Fe@GO-EDA, where EDA represents ethylenediamine) functions as an efficient catalyst for the selective conversion of CO2 into a formaldehyde oxidation level, thus opening the door for interesting molecular structures using CO2 as a C1 source. Overall, this work describes an intriguing heterogeneous platform for the selective synthesis of valuable methylene-bridged compounds via 4‑electron reduction of CO2.

Deep Reconstruction of Ruthenate Perovskite Oxide Enables Efficient pH-Universal Hydrogen Evolution Reaction.

Designing highly efficient, stable, and pH-universal perovskites for hydrogen evolution reaction (HER) is urgently needed yet remains a grand challenge. Herein, a titanium-containing strontium ruthenate (SrTi0.5Ru0.5O3, STRO) is developed as an excellent HER electrocatalyst in a wide pH range. The introduction of Ti into SrRuO3 significantly reduces the size of STRO, endowing with a high reactivity that facilitates a deep surface-reconstruction during HER. Furthermore, Sr2+ leaching triggered reconstruction leads to STRO breaking into tiny nanoparticles accompanied by high-valence ruthenium (Ru) species reducing to metallic Ru. The generated active species, increased accessible sites, and improved electrical conductivity greatly boost HER. The reconstructed STRO displays remarkable HER activities with exceptional low overpotentials of 18, 24, and 55mV at 10mA cm-2 in 1m KOH, 0.5m H2SO4, and 1m PBS, respectively, surpassing most perovskites reported previously and comparable to or even outperforming that of commercial Pt/C. Moreover, the STRO exhibits excellent stabilities over 200h in alkaline and acidic media, superior to that of Pt/C. This work not only provides insights into structure reconstruction of perovskites during HER, but also opens new perspectives for developing high-efficiency and pH-universal electrocatalysts for future energy applications.

Oxidation of 5-Hydroxymethylfurfural into 2,5-Diformylfuran on Alkali Doped Ru/C Catalysts. Electron Properties of Ruthenium Species as Descriptor of Catalytic Activity.

Selective aerobic oxidation of 5-hydroxymethylfurfural into 2,5-diformylfuran has been achieved on alkali doped Ru/C catalyst. Optimization of Ru metal nanoparticles, as well as the nature and amount of the alkali dopant have been performed. The results showed that doping the Ru/C catalyst with controlled amount of potassium increases the catalytic activity, 2.5 fold with respect to the non-doped sample. Spectroscopic studies showed that these differences in activity can be attributed to a different oxidation reaction mechanism associated to the presence of electron rich Ru species in the promoted sample that facilitate the dissociation of O2, while prevents the oxidation of the metal. The Ru/C-K doped catalyst resulted very stable against leaching and metal sintering, being possible the reuse over several consecutive runs. Moreover, the catalyst could be successfully applied to the oxidation of different alcohols.

Dinitrogen-bridged ruthenium(II) complexes featuring dithiocarbamate ligands

In quest of low molecular weight metal-thiolate complexes as model complexes for nitrogenase, four binuclear ruthenium(II) dinitrogen-bridged complexes featuring dithiocarbamate ligands, [{(Me3tacn)Ru(κ2-S2CNR2)}2(µ-N2)][PF6]2 (Me3tacn = 1,4,7-trimethyl-1,4,7-triazacyclononane; 1, R = Me; 2, R = Et; 3, R = nPr; 4, R = iPr), were synthesized by reduction of [(Me3tacn)RuIII(κ2-S2CNR2)Cl]PF6 with zinc powder in a nitrogen atmosphere. A 16-electron mononuclear ruthenium(II) species [(Me3tacn)Ru(κ2-S2CNnPr2)]PF6 (3′) was isolated during preparation of 3, which may help elucidate the formation of complexes 1-4. Molecular structures of complexes 1, 2, 4 and 3′ were established by single crystal X-ray diffraction analysis. Moreover, complexes 1-4 were characterized by infrared, 1H NMR, UV–vis, fluorescence, Raman (solid state and solution state) spectroscopies and mass spectrometry, and their electrochemical properties were also investigated. Density functional theory (DFT) calculation was performed on complex 2 to study its Lewis structure and explain the UV–vis absorption spectra. Structural and DFT analyses demonstrate that N2 activation is accompanied by electron redistribution of the dithiocarbamate ligands.

Modulating the Coordination Chemistry of Cobalt Catalytic Sites by Ruthenium Species to Accelerate the Polysulfide Conversion Kinetics in Lithium-Sulfur Batteries.

The performance of lithium-sulfur batteries is compromised by the loss of sulfur as dissolved polysulfides in the electrolyte and consequently the polysulfide redox shutting effect. Accelerating the conversion kinetics of polysulfide intermediates into sulfur or lithium sulfide through electrocatalysis has emerged as a root-cause solution. Co-N-C composite electrocatalyst is commonly used for this purpose. It is illustrated here that how the effectiveness can be improved by modulating the coordination chemistry of Co-N-C catalytic sites through introducing Ru species (RuCo-NC). The well-dispersed Ru in the Co-NC carbon matrix altered the total charge distribution over the Co-N-C catalytic sites and led to the formation of electron-rich Co-N, which is highly active for the polysulfide conversion reactions. Using Ru to modulate the electronic structure in the Co-N-C configuration and the additional catalytic sites over the Ru-Nx species can manifest optimal adsorption behavior of polysulfides. Consequently, the sulfur cathode with RuCo-NC can reduce the capacity fade rate from 0.11 % per cycle without catalyst (initial capacity of 701 mAh g-1) to 0.054 % per cycle (initial capacity of 1074 mAh g-1) over 400 cycles at 0.2 C rate. The results of this study provide the evidence for a feasible catalyst modification strategy for the polysulfide electrocatalysis.

Enhanced electrocatalytic activity in hydrogen evolution reaction using 2D/2D nanohybrids of ruthenate nanoflakes and graphitic carbon nitride.

Photoelectrochemical and electrochemical water splitting was examined using ruthenate nanoflake (RuNF) and graphitic carbon nitride (g-C3N4) hybrids. A two-dimensional and visible-light-responsive photocatalyst g-C3N4 was hybridized with the RuNFs that we recently synthesized via a bottom-up process in aqueous solution, yielding 2D/2D nanocomposites. The influence of the 2D/2D nanocomposites on oxygen and hydrogen evolution during photoelectrochemical and electrochemical water splitting was investigated. First, electrolysis of a Na2SO4 aqueous solution was conducted with intermittent photo-irradiation. Both the g-C3N4 electrode and the RuNF/g-C3N4 hybrid electrode provided anodic and cathodic photocurrents at high and low potentials, respectively; however, the copresence of RuNFs decreased the photocurrents, probably because the RuNFs retarded the light absorption by g-C3N4. Moreover, the use of RuNF/g-C3N4 hybrids as electrodes facilitated both the oxygen and hydrogen evolution reactions without photo-irradiation. However, for the oxygen evolution reaction, the effect of the RuNFs was similar to that of RuO2 nanoparticles, indicating that the influence of the type and morphology of ruthenium species on the oxygen evolution reaction was small. Conversely, irrespective of the pH of the aqueous solutions in an electrolytic bath, the 2D/2D nanostructure of RuNFs and g-C3N4 decreased the overpotential of the hydrogen evolution reaction. However, the use of RuO2 particles instead of RuNFs did not cause such a phenomenon. Thus, it was revealed that the RuNFs synthesized via a bottom-up process were useful as a co-catalyst for the hydrogen evolution reaction.

Fundamental studies of ruthenium species supported on boron nitride nanotubes: metal loading and pretreatment effects on CO oxidation

RuOx/BNNT catalysts were prepared with varying metal loadings and under oxidation and reduction conditions. RuOx/BNNT showed superior catalytic activity than Ru/BNNT. The catalyst will be favorable to the ER mechanism over the LH mechanism.

Enhanced Photocatalytic Dehalogenation Performance of RuDoped In2O3 Nanoparticles Induced by Oxygen Vacancy

Due to its favorable excited-state physicochemical properties, indium oxide (In2O3) has widely captured attention as a potentially great photocatalyst. However, an inferior charge separation efficiency limits its application. Recently, an increasing amount of evidence has demonstrated that the construction of surface defects is an effective strategy to boost photocatalytic performances. In this work, a ruthenium (Ru) species was successfully introduced into the lattice of In2O3 nanoparticles through co-precipitation and thermal treatment. It was found that the content of surface oxygen vacancies was directly related to the amount of Ru3+ doping, which further determines the separation efficiency of photogenerated carriers. As a result, the 0.5% Ru-In2O3 samples enriched with oxygen vacancies exhibit dramatically enhanced photocatalytic dehalogenation performances of decabromodiphenyl ether and hexabromobenzene, about four times higher than that of the pure In2O3 nanoparticles. This study emphasized the significance of the surface defects of the photocatalyst and may provide a valuable strategy to prepare highly active photocatalysts for photocatalytic dehalogenation reactions.

Low-oxidation-state Ru sites stabilized in carbon-doped RuO2 with low-temperature CO2 activation to yield methane

The generation of methane fuel using surplus renewable energy with CO2 as the carbon source enables both the decarbonization and substitution of fossil fuel feedstocks. However, high temperatures are usually required for the efficient activation of CO2. Here we present a solid catalyst synthesized using a mild, green hydrothermal synthesis that involves interstitial carbon doped into ruthenium oxide, which enables the stabilization of Ru cations in a low oxidation state and a ruthenium oxycarbonate phase to form. The catalyst shows an activity and selectivity for the conversion of CO2 into methane at lower temperatures than those of conventional catalysts, with an excellent long-term stability. Furthermore, this catalyst is able to operate under intermittent power supply conditions, which couples very well with electricity production systems based on renewable energies. The structure of the catalyst and the nature of the ruthenium species were acutely characterized by combining advanced imaging and spectroscopic tools at the macro and atomic scales, which highlighted the low-oxidation-state Ru sites (Run+, 0 < n < 4) as responsible for the high catalytic activity. This catalyst suggests alternative perspectives for materials design using interstitial dopants.

Novel Reaction-Adsorption Method for Preparation of Ru–Zn–La/ZrO2 Catalysts with High Catalytic Performance for Selective Hydrogenation of Benzene

A novel wet-chemistry reaction-adsorption strategy via the facile acid–base interaction under mild conditions is demonstrated to fabricate the state-of-the-art Ru–Zn–La/ZrO2 catalysts for selective hydrogenation of benzene to cyclohexene. The catalyst preparation process is systematically investigated and verified with the combination of various characterization techniques. Preloading of lanthanide salts and alkali treatment after calcination not only favor the introduction of ruthenium and zinc species in the later stages but also help enhance the dispersion of the catalysts. The reaction rate constants (k1 and k2) decrease with the increment of the Zn/Ru molar ratio, and the selectivity at 40% conversion (S40) is positively correlated with the k1/k2 ratio, demonstrating the role of Zn species in retarding the hydrogenation activity of Ru and improvement of the selectivity to cyclohexene. In general, the catalytic behavior is dependent on the particle size of Ru, the La-to-Ru electron transfer effect, the content of Zn species, and the surface hydrophilicity of catalyst. These factors are generated by using different precursors and various predesigned La/Ru molar ratios in the preparation recipe. Moreover, a passivation treatment before the hydrogenation reaction can promote the cyclohexene selectivity of the catalyst Ru–Zn–La/ZrO2 (1.6 La/Ru) to 80.6% at a benzene conversion of 43.7%, which meets the industrial requirement. Notably, the specific activity of the catalyst is as high as 1224 gBZ·gRu–1·h–1, over 10 times higher than the industrial criterion. This work provides new insights into the design of Ru-based catalysts for benzene hydrogenation and other hydrogenation reactions as well.

Synthesis of Ruthenium-Promoted ZnO/SBA-15 Composites for Enhanced Photocatalytic Degradation of Methylene Blue Dye

Synthetic organic pigments like xanthene and azo dyes from the direct discharge of textile effluents are considered colossal global issues and attract the concern of scholars. Photocatalysis continues to be a very valuable pollution control method for industrial wastewater. Incorporations of metal oxide catalysts such as zinc oxide (ZnO) on mesoporous Santa Barbara Armophous-15 (SBA-15) support to improve catalyst thermo-mechanical stability have been comprehensively reported. However, charge separation efficiency and light absorption of ZnO/SBA-15 continue to be limiting its photocatalytic activity. Herein, we report a successful preparation of Ruthenium-induced ZnO/SBA-15 composite via conventional incipient wetness impregnation technique with the aim of boosting the photocatalytic activity of the incorporated ZnO. Physicochemical properties of the SBA-15 support, ZnO/SBA-15, and Ru-ZnO/SBA-15 composites were characterized by X-ray diffraction (XRD), N2 physisorption isotherms at 77 K, Fourier-transform infrared (FTIR), scanning electron microscopy (SEM), energy dispersive X-ray (EDS), and transmission electron microscopy (TEM). The characterization outcomes exhibited that ZnO and ruthenium species have been successfully embedded into SBA-15 support, andtheSBA-15 support maintains its structured hexagonal mesoscopic ordering in both ZnO/SBA-15 and Ru-ZnO/SBA-15 composites. The photocatalytic activity of the composite was assessed through photo-assisted mineralization of aqueous MB solution, and the process was optimized for initial dye concentration and catalyst dosage. 50 mg catalyst exhibited significant degradation efficiency of 97.96% after 120 min, surpassing the efficiencies of 77% and 81% displayed by 10 and 30 mg of the as-synthesized catalyst. The photodegradation rate was found to decrease with an increase in the initial dye concentration. The superior photocatalytic activity of Ru-ZnO/SBA-15 over the binary ZnO/SBA-15 may be attributed to the slower recombination rate of photogenerated charges on the ZnO surface with the addition of ruthenium.

Electronic interaction of ruthenium species on bimetallic phosphide for superior electrocatalytic hydrogen generation.

The exploitation of high-performance electrocatalysts to achieve the economic electrocatalytic hydrogen evolution reaction (HER) is significant in generating H2 fuel. Enhancing the activity of the carrier catalyst by modifying trace precious metals is one of the important strategies. Herein, a hybrid material is developed by incorporating trace Ru species into a bimetallic phosphide (NiCoP) matrix on nickel foam (NF), showing a superior catalytic activity for HER. The Ru-NiCoP/NF hybrid material has plenty of heterointerfaces, improved electronic interaction, and small interfacial charge transfer resistance, improving the reaction kinetics of the HER. Remarkable, the Ru-NiCoP/NF provides a low overpotential of 96 mV at the current density of 50 mA cm-2 and high stability in 1.0 M KOH solution presenting a promising potential for hydrogen production. In addition, the Ru-NiCoP/NF sample exhibits the highest TOF value of 0.54 s-1 at an overpotential of 100 mV, which outperforms the commercial Ru/C catalyst. This study offers a promising approach for the synthesis of other precious metal supported hybrid materials.

RuH‐Catalyzed Synthesis of 1,3‐Diaryl Ketones via Cross‐Coupling of Aromatic Enones with Aromatic Aldehydes and Mechanistic Insights

AbstractRuHCl(CO)(PPh3)3‐catalyzed cross‐coupling of alkenyl ketones with aldehydes has been extended to the synthesis of 1,3‐diaryl 1,3‐diketones. The reaction has been successfully applied to the synthesis of PPT (propyl pyrazole triol), a selective estrogen receptor modulator compound. A study of the stoichiometric reaction of phenyl vinyl ketone with RuHCl(CO)(PPh3)3 has revealed that the β‐ruthenium ketone PhCOCH2CH2RuCl(CO)(PPh3)2, a five‐membered ruthenacycle is formed with liberation of one molecule of PPh3. The observed catalytic activity of this ruthenacycle in the presence of PPh3 suggests that it serves as a resting state, in equilibrium with an oxa‐π‐allyl ruthenium species, which is the key coupling partner with aldehyde substrates.magnified image

Coupling of ruthenium with hybrid metal nitrides heterostructure as bifunctional electrocatalyst for water electrolysis

Noble metal-based materials are the benchmark catalysts for electrocatalysis, but their wide applications are hindered due to their scarcity and high cost. Developing a feasible strategy to achieve higher catalytic activity with low usage of noble metals is vital and urgent. Herein, a simple nitridation route is proposed to design a hybrid material with both ruthenium (Ru) species and mixed metal nitride matrixes (Ru-NiWNx). Benefitting from the intrinsic high conductivity of metal nitrides, abundant catalytic active sites, and strong electron interactions, the Ru-NiWNx catalyst shows excellent bifunctional activity in alkaline electrolytes. The overpotentials are 70 mV and 270 mV at the geometric current density of 100 mA cm−2 for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), respectively. After further assembly into an electrolyzer, the Ru-NiWNx also shows superior performance. The voltage of the electrolyzer only needs 1.49 V to reach 100 mA cm−2 at the test temperature of 80 °C, indicating the promising application for hydrogen production. Our work paves a new strategy to design high-active hybrid materials for overall water splitting.

Electronegativity Enhanced Strong Metal-Support Interaction in Ru@F-Ni3N for Enhanced Alkaline Hydrogen Evolution.

Precious metals (Pt, Ir, Ru, and so on) and related compounds usually demonstrate superb catalytic activity for electrochemical hydrogen production. However, scarcity and stability are still challenges for hydrogen evolution reaction, even for single-atomic-site electrocatalysts. Herein, a fluorine (F) doping strategy is proposed to enhance the strong metal-support interaction between the F-doped Ni3N support and the loaded ruthenium (Ru) species. Via synergistically modulating both the Ru loading amount and F doping concentration, outstanding HER activity was achieved in Ru@F-Ni3N with an overpotential (η) of 115 mV at 100 mA cm-2, superior to the benchmark Pt/C (η = 201 mV). Density functional theory simulation in combination with X-ray photoelectron spectra and X-ray absorption spectroscopy characterizations convincingly demonstrate that, with the strongest electronegativity, F doping could effectively stabilize Ru atoms doped in the F-Ni3N substrate and simultaneously reduce the H bonding strength, which accelerated the desorption of H2. These findings provide a facile strategy to modulate both catalytic activities and stabilities of heteroatom-loaded catalytic materials.

Impact of Cerium Oxide on the State and Hydrogenation Activity of Ruthenium Species Incorporated on Mesocellular Foam Silica.

Herein, the impact of cerium species loaded on mesoporous silica of MCF type on the state and catalytic activity of ruthenium species was studied. Up to 20 wt.% of cerium was incorporated on the silica surface, whereas the same 1 wt.% of Ru loading was applied. The samples prepared were examined by low temperature N2 adsorption/desorption, XRD, XRF, ICP-OES, XPS and H2 chemisorption. The catalytic activity of the materials obtained was investigated in the transformation of levulinic acid to γ-valerolactone. It was documented that the presence of Ce favored an increase in the dispersion of ruthenium species, which had a positive impact on the hydrogenation activity for up to 10 wt.% of Ce. Nevertheless, the highest cerium loading had a negative influence on the textural parameters of the support.

Enhancement of ammonia synthesis activity on La2O3-supported Ru catalyst by addition of ceria

The addition of Ce species in La2O3 can enhance the number of defect sites and generate the Ce1-xLaxO2-δ solid solution, thereby increasing the amount of the exposed ruthenium species and proportion of metallic ruthenium species. The presence of Ce species in Ru/La2O3 promotes the desorption of hydrogen, and hydrogen species prefers to desorb in the H2 molecule formation pathway. On the other hand, the difference in the Ce addition method strongly affects the exchange between the adsorbed hydrogen species on Ru catalyst with the gaseous hydrogen species. Owing to improvement of the proportion of oxygen vacancy, Ru0 and number of the exposure of ruthenium species, H2 species adsorbed on Ru/LaCe–C prepared by coprecipitation method preferentially desorbs in the formation of H2 pathway, and a large proportion of the adsorbed H species would exchange with the hydrogen species from the gaseous phase, which leads to improvement of ammonia synthesis rate by 75% in comparison with Ru/La2O3 catalyst.